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PREFACE TO THE FIFTH EDITION
The importance of a laboratory course attached to a theory course is undisputable in
science subjects. Chemistry is a practical science and an appropriate correlation between
teaching theory and practicals leads to a better understanding. My purpose of writing the
earlier editions of the book indeed was to present a laboratory course which correlated
with the lecture material. This fresh edition of the manual extends that concern. The
overall organization of the book has essentially been retained as that of the fourth edition.
An attempt has further been made to make necessary and useful inclusions in different
chapters to make it more user friendly.
The revised edition now consists of nine chapters instead of earlier eight. Chapter 7
has been divided into two separate chapters. All the chapters have been extensively revised
and improved for clarity, accuracy and ease of performance of an experiment. Redundant
material has been deleted. Throughout the book chemical reactions have been stressed
wherever possible. Chapter 2 which deals with the basic laboratory equipment and
techniques has been completely rewritten and expanded. The methods of distillations have
particularly been revised to make them more practical. This time care has been exercised
to include all the relevant tests and pertinent chemical reactions keeping in mind the
chemicals that will be available in a laboratory. Chapters 5–6 concern the tests of compounds
and preparation of the derivatives respectively. The derivatives selected are those that
can be easily synthesized by simple chemical means, easy to isolate and purify. A method
has been described to prepare the derivatives of unsaturated compounds normally the
alkenes and the alkynes. More compounds have been included in the tables to cover a
wide range of data of m.p. and b.p. This hopefully will assist the students in analysis and
eventually identifying an unknown compound. Guidelines for the separation of binary
mixtures of organic compounds are given.
Chapter 7 in the earlier edition has been split into two chapters, for convenience.
This is an obvious change in this edition. Chapter 7 now deals with estimations while
Chapter 8 consists of organic preparations. Several changes have been introduced in these
chapters. Chapter 7 has been reorganized and certain portions have been rewritten.
Isolation and estimation of Vit C is a new inclusion. Chapter 8 deals with the methods of
preparing organic compounds, some in a single step while many in multiple steps. A
knowledge of reaction mechanism is important in organic chemistry. Therefore, an
appropriate mechanism precedes the procedure for every preparation. Proper methods of
handling equipment and chemicals, work-up of product, calculation of yields and precautions
have been highlighted. Spectroscopy is one of the most valuable tools in the hands of an
organic chemist. These methods offer a rapid and most accurate information about the
compound under examination. Only two methods (I.R. and N.M.R.) are covered with
appropriate examples in the last chapter. Virtually no change has been affected in this
chapter.
1ho IognrIfhmIc fnlIos hnvo loon droµµod. 1ho dIngrnms hnvo loon rodrnwn. If Is n
vory usofuI nnd hnndy look for nII grndunfo nnd µosfgrndunfo IovoI sfudonfs.
I nm Indolfod fo nII fhoso rondors nnd usors of fhIs look who hnvo Inlourod fo sond
mo fhoIr commonfs nnd suggosfIons from fImo fo fImo. I wIII corfnInIy woIcomo fhoIr foodlnck
In fufuro ns woII.
I nIso wIsh fo µuf on rocord my grnfIfudo fo fho nufhors nnd µulIIshors of looks,
monogrnµhs nnd nrfIcIos whoso hnrd work hns ImmonsoIy guIdod mo In fho µroµnrnfIon of
fhIs odIfIon.
If gIvos mo n gronf µIonsuro fo ncknowIodgo fho Iovo nnd suµµorf of my wIfo durIng
fho µroµnrnfIon of fhIs µrojocf.
IInnIIy, I grnfofuIIy ncknowIodgo fho coIInlornfIon nnd dodIcnfIon of nII µrofossIonnIs
nf fho Þow Ago InfornnfIonnI (I) !fd., IulIIshors, Þow ÐoIhI for fho ndoµf hnndIIng of
fhIs odIfIon.
Dv. Ru] K. BunsuI
New DeIhI
viii PREFACE
CONTENTS
Prefoce ................................................................................................................ tii
1. SAI£TY IN TH£ CH£MICAI IABORATORY ...................................... 1÷?
l.l IrofocfIvo CIofhIng ................................................................................................. l
l.l.l IquIµmonf nnd Aµµnrnfus ........................................................................ 2
l.2 HnndIIng ChomIcnIs ................................................................................................ 2
l.3 IInmmnlIo MnforInIs .............................................................................................. 2
l.3.l CorrosIvo nnd 1oxIc !ongonfs ................................................................. 2
l.3.2 IrrIfnnf nnd !nchrymnfory ChomIcnIs .................................................... 2
l.4 Iyo IrofocfIon ......................................................................................................... 3
l.5 ÐIsµosnI of ChomIcnIs nnd SoIId Wnsfos ................................................................ 3
l.6 CuIdoIInos In Cnso of AccIdonf or Injury ............................................................... 3
l.? 1oxIcIfy nnd Hnznrds of ChomIcnIs ........................................................................ 4
2. IABORATORY £Q¡IPM£NTS AND T£CHNIQ¡£S ........................ B÷26
2.l CInsswnros ............................................................................................................... 8
2.2 AssomlIIos for !oncfIons ...................................................................................... l4
2.3 ÐIsfIIInfIon ............................................................................................................. l5
2.3.l SImµIo ÐIsfIIInfIon .................................................................................. l5
2.3.2 IrncfIonnI ÐIsfIIInfIon ............................................................................ l8
2.3.3 ÐIsfIIInfIon !ndor !oducod Irossuro.................................................... 20
2.3.4 Sfonm ÐIsfIIInfIon ................................................................................... 2l
2.4 CrysfnIIIznfIon........................................................................................................ 23
2.5 ÐryIng Agonfs ........................................................................................................ 25
2.6 CIonnIng Aµµnrnfus ............................................................................................... 26
3. D£T£CTION OI £I£M£NTS ............................................................... 2?÷36
3.l IhysIcnI Sfnfo ........................................................................................................ 2?
3.2 CoIor ................................................................................................................. 2?
3.3 Odor ................................................................................................................. 28
3.4 AcId or Inso Chnrncfor ......................................................................................... 28
3.5 IgnIfIon 1osf ......................................................................................................... 29
3.6 SoIulIIIfy ................................................................................................................ 29
3.? IIomonfnI AnnIysIs ................................................................................................ 3l
x CONTENTS
4. T£STS IOR I¡NCTIONAI GRO¡PS ................................................. 3?÷62
4.l AIcohoIIc Crouµ (!OH) ................................................................................................................. 3?
4.2 IhonoIIc Crouµ (A!OH) ............................................................................................................... 40
4.3 CnrlonyI Crouµ ...................................................................................... 43
4.4 CnrloxyI Crouµ .................................................................................. 49
4.5 Isfor Crouµ ........................................................................................ 49
4.6 Cnrlohydrnfos ........................................................................................................ 50
4.? ÞIfro Crouµ ........................................................................................... 52
4.8 AmIno Crouµ (ÞH
2
) ...................................................................................................................... 53
4.9 AmIdo Crouµ ................................................................................... 56
4.l0 AnIIIdo Crouµ ............................................................................... 5?
4.ll Hydrocnrlons ......................................................................................................... 58
4.l2 !nsnfurnfIon .................................................................................... 59
4.l3 CnrlonIc AcId ÐorIvnfIvos..................................................................................... 60
5. T£STS IOR COMMON ORGANIC COMPO¡NDS ......................... 63÷104
5.l AIcohoIs nnd IhonoIs ............................................................................................ 63
5.2 CnrloxyIIc AcIds..................................................................................................... ?3
5.3 AIdohydos nnd Kofonos ......................................................................................... 80
5.4 Isfors ................................................................................................................. 86
5.5 AmInos ................................................................................................................. 90
5.6 AmIdos nnd AnIIIdos .............................................................................................. 95
5.? AryI HnIIdos ........................................................................................................... 98
5.8 MIscoIInnoous Comµounds ................................................................................... l0l
6. PR£PARATION OI D£RIVATIV£S ................................................ 105÷142
6.l ÐorIvnfIvos of AIcohoIs ......................................................................................... l05
CONTENTS xi
6.2 ÐorIvnfIvos of IhonoIs ......................................................................................... l0?
6.3 ÐorIvnfIvos of AIdohydos nnd Kofonos ................................................................ l08
6.4 ÐorIvnfIvos of CnrloxyIIc AcIds ........................................................................... l09
6.5 ÐorIvnfIvos of Isfors ............................................................................................ lll
6.6 ÐorIvnfIvos of Cnrlohydrnfos .............................................................................. lll
6.? ÐorIvnfIvos of AmInos .......................................................................................... ll4
6.8 ÐorIvnfIvos of Hydrocnrlons ............................................................................... ll5
6.9 ÐorIvnfIvos of AIkonos nnd AIkynos ................................................................... ll6
6.l0 IhysIcnI Consfnnfs ...............................................................................................ll6
6.l0.l MoIfIng IoInf ......................................................................................... ll?
6.l0.2 IoIIIng IoInf .......................................................................................... ll9
6.ll SoµnrnfIon of IInnry MIxfuros ............................................................................ l2l
6.l2 IhysIcnI Consfnnfs of somo Common OrgnnIc Comµounds nnd
fhoIr ÐorIvnfIvos ................................................................................................... l23
?. £STIMATION OI I¡NCTIONAI GRO¡PS .................................. 143÷1?4
?.l IsfImnfIon of fho Þumlor of HydroxyI (OH) Crouµs In AIcohoIs ................... l43
?.2 ÐoformInnfIon of fho IurIfy of IhonoI ............................................................... l45
?.3 ÐoformInnfIon of IquIvnIonf WoIghf of n CnrloxyIIc AcId ............................... l4?
?.3.l SIIvor SnIf Mofhod (CrnvImofrIc Mofhod) ............................................ l4?
?.3.2 VoIumofrIc Mofhod ................................................................................l48
?.4 ÐoformInnfIon of SnµonIfIcnfIon IquIvnIonf of nn Isfor ................................... l49
?.5 IsfImnfIon of n Kofo Crouµ ................................................................ l50
?.6 IsfImnfIon of nn AIdohydo Crouµ ...................................................... l5l
?.? IsfImnfIon of SuIfur (Mossongor`s Mofhod) In 1hIouron ..................................l53
?.8 IsfImnfIon of ÞIfrogon (KjoIdnhI Mofhod) ......................................................... l54
?.9 IsfImnfIon of AmIno (ÞH
2
) Crouµ ...................................................................... l56
?.l0 IsfImnfIon of fho Þumlor of AmIdo Crouµs ....................................... l5?
?.ll IsfImnfIon of CIycIno (AmIno AcId) .................................................................... l58
?.l2 ÐoformInnfIon of Iorconfngo IurIfy of CIucoso (A !oducIng Sugnr) ............... l59
?.l3 IsfImnfIon of SnµonIfIcnfIon VnIuo of nn OII or Inf .......................................... l6l
?.l4 ÐoformInnfIon of IodIno Þumlor of nn !nsnfurnfod Comµound .....................l62
?.l5 IsfImnfIon of fho !oncfIon Consfnnf (H) ............................................................. l64
?.l6 ÐoformInnfIon of ChomIcnI Oxygon Ðomnnd (COÐ) ......................................... l65
?.l? IsfImnfIon of Kofo-InoI IquIIIlrIum of n Kofo Isfor ....................................... l66
?.l8 ÐoformInnfIon of fho Þumlor of Mofhoxy (OCH
3
) Crouµs .............................. l68
?.l9 ÐoformInnfIon of AscorlIc AcId ConconfrnfIon .................................................. l?l
?.20 ÐoformInnfIon of MoIocuInr WoIghf of n Sulsfnnco (!nsf`s Mofhod) ............... l?3
xii CONTENTS
B. ORGANIC PR£PARATIONS.............................................................. 1?5÷252
8.l IIocfroµhIIIc AromnfIc SulsfIfufIon !oncfIons .................................................. l?5
8.l.l IroµnrnfIon of ÞIfrolonzono (ÞIfrnfIon) .............................................l?6
8.l.2 IroµnrnfIon of o- nnd p-ÞIfroµhonoIs ................................................... l?8
8.l.3 IroµnrnfIon of 2, 4, 6-1rIlromonnIIIno (IromInnfIon) ........................ l?9
8.l.4 IroµnrnfIon of IIcrIc AcId (2, 4, 6-1rInIfroµhonoI) .............................. l?9
8.l.5 !oInfIvo !nfos of IIocfroµhIIIc AromnfIc SulsfIfufIon........................ l80
8.l.6 1ho IrIodoI-Crnffs !oncfIon.................................................................. l8l
8.l.6 (n) IroµnrnfIon of o-IonzoyIlonzoIc AcId (1ho IrIodoI-Crnffs
!oncfIon) ................................................................................................. l82
8.l.6 (l) IroµnrnfIon of ÐIµhonyImofhnno (1ho IrIodoI-Crnffs
!oncfIon) ................................................................................................. l83
8.l.6 (c) IroµnrnfIon of >-IonzoyIµroµIonIc AcId (1ho IrIodoI-Crnffs
!oncfIon) ................................................................................................. l84
8.l.6 (d) IroµnrnfIon of p-XyIono-2-SuIfonIc AcId ...............................................l85
8.2 1ho ÐIoIs-AIdor !oncfIon ..................................................................................... l85
8.2.l IroµnrnfIon of 9, l0-ÐIhydronnfhrncono-9 l0-=, >-SuccInIc
AnhydrIdo (1ho ÐIoIs-AIdor !oncfIon) .................................................. l85
8.3 1ho Iockmnnn !onrrnngomonf .......................................................................... l86
8.3.l IroµnrnfIon of IonznnIIIdo ...................................................................l86
8.4 1ho IorkIn !oncfIon ............................................................................................ l8?
8.4.l IroµnrnfIon of CInnnmIc AcId ............................................................... l8?
8.5 1ho CnnnIzznro !oncfIon ..................................................................................... l88
8.5.l Inso-CnfnIyzod OxIdnfIon-!oducfIon of IonznIdohydo........................ l88
8.6 1ho IrIos !onrrnngomonf ................................................................................... l89
8.6.l IroµnrnfIon of 2, 5-ÐIhydroxyncofoµhonono ....................................... l89
8.? 1ho Schöffon-Inumnnn !oncfIon........................................................................ l90
8.?.l IroµnrnfIon of IonznnIIIdo ...................................................................l90
8.8 IonzIIIc AcId !onrrnngomonf .............................................................................. l9l
8.8.l IroµnrnfIon of IonzIIIc AcId.................................................................. l9l
8.9 1ho !oImor-1Iomnnn !oncfIon ........................................................................... l93
8.9.l IroµnrnfIon of SnIIcyInIdohydo ............................................................. l93
8.l0 OxIdnfIon nnd !oducfIon ...................................................................................... l94
8.l0.l IroµnrnfIon of CycIohoxnnono (OxIdnfIon) .......................................... l94
8.l0.2 IroµnrnfIon of p-ÞIfrolonzoIc AcId (OxIdnfIon) ................................... l95
8.l0.3 IroµnrnfIon of AnfhrnquInono (OxIdnfIon) .......................................... l96
8.l0.4 IroµnrnfIon of AdIµIc AcId (OxIdnfIon) ................................................. l96
8.l0.5 IroµnrnfIon of IonzoIc AcId (OxIdnfIon) .............................................. l9?
8.l0.6 IroµnrnfIon of 1rImofhyIncofIc AcId (OxIdnfIon) ................................. l98
8.l0.? IroµnrnfIon of IfhyIlonzono (1ho WoIff-KIshnor !oducfIon) ............ l99
8.l0.8 IroµnrnfIon of IonzhydroI (!oducfIon) ................................................ 200
8.l0.9 IroµnrnfIon nnd SforoochomIsfry of Azolonzono (!oducfIon) ........... 200
CONTENTS xiii
8.l0.l0 IroµnrnfIon of n-ÞIfronnIIIno from n-ÐInIfrolonzono (!oducfIon) .202
8.l0.ll !oducfIon of p-ÞIfroncofoµhonono (SoIocfIvo !oducfIon) ................... 202
8.ll OrgnnomofnIIIc ChomIsfry ................................................................................... 203
8.ll.l IroµnrnfIon of IonzoIc AcId (1ho CrIgnnrd !oncfIon) ........................ 203
8.ll.2 IroµnrnfIon of 1rIµhonyImofhnnoI (1ho CrIgnnrd !oncfIon) ............. 204
8.ll.3 IroµnrnfIon of p-1oIuIc AcId from p-IromofoIuono ............................ 205
8.l2 ÐohydrnfIon ..........................................................................................................206
8.l2.l IroµnrnfIon of CycIohoxono .................................................................. 206
8.l2.2 IroµnrnfIon of SuccInIc AnhydrIdo ....................................................... 208
8.l2.3 ÐohydrnfIon of Cnmµhor OxImo (MoIocuInr !onrrnngomonf) ........... 208
8.l3 OµfIcnI AcfIvIfy ..................................................................................................... 209
8.l3.l !osoIufIon of !ncomIc =-IhonyIofhyInmIno ........................................ 2l0
8.l4 HoforocycIIc Comµounds ...................................................................................... 2ll
8.l4.l IroµnrnfIon of QuInoIIno (1ho Skrnuµ SynfhosIs) .............................. 2ll
8.l4.2 IroµnrnfIon of 2-IhonyIIndoIo (1ho IIschor-IndoIo SynfhosIs) ......... 2l2
8.l4.3 IroµnrnfIon of l-IhonyI-3-MofhyI-5-IyrnzoIono ................................. 2l3
8.l4.4 IroµnrnfIon of 5-Hydroxy-l, 3-IonzoxnzoI-2-Ono ................................2l4
8.l4.5 IroµnrnfIon of l, 2-ÐIµhonyI-5-ÞIfrolonzImIdnzoIo ............................ 2l5
8.l5 ÐInzofIsnfIon ......................................................................................................... 2l5
8.l5.l IroµnrnfIon of p-IodonIfrolonzono ....................................................... 2l6
8.l5.2 IroµnrnfIon of p-ChIorofoIuono (1ho Snndmoyor !oncfIon) ............... 2l6
8.l5.3 IroµnrnfIon of o-ChIorolonzoIc AcId (1ho Snndmoyor !oncfIon) ...... 2l?
8.l6 IroµnrnfIon of Ðyos .............................................................................................. 2l8
8.l6.l IroµnrnfIon of MofhyI Ornngo .............................................................. 2l8
8.l6.2 IroµnrnfIon of IhonoIµhfhnIoIn ........................................................... 2l9
8.l6.3 IroµnrnfIon of IIuoroscoIn ................................................................... 220
8.l6.4 IroµnrnfIon of IosIn .............................................................................. 22l
8.l6.5 IroµnrnfIon of MofhyI !od .................................................................... 22l
8.l? 1ho IInncoI-µInncoIono !onrrnngomonf ............................................................. 222
8.l8 ChromnfogrnµhIc Mofhods ................................................................................... 224
8.l8.l CoIumn Chromnfogrnµhy ...................................................................... 225
8.l8.2 1hIn !nyor Chromnfogrnµhy (1!C) ..................................................... 22?
8.l8.3 Inµor Chromnfogrnµhy ......................................................................... 229
8.l9 IoIymorIznfIon...................................................................................................... 230
8.l9.l IroµnrnfIon of IhonoI-IormnIdohydo !osIn ....................................... 23l
8.l9.2 IroµnrnfIon of 1hIokoI !ullor ............................................................. 23l
8.l9.3 IoIymorIznfIon of Sfyrono .................................................................... 232
8.l9.4 IroµnrnfIon of ÞyIon-66 ........................................................................ 233
8.20 CnfnIyfIc HydrogonnfIon ...................................................................................... 233
8.20.l ConvorsIon of CInnnmIc AcId fo HydrocInnnmIc AcId......................... 233
8.2l IhofochomIcnI !oncfIons ..................................................................................... 235
8.2l.l IroµnrnfIon of IonzoµInncoI ................................................................. 235
8.2l.2 IhofochomIcnI IsomorIznfIon of Azolonzono ...................................... 236
xiv CONTENTS
8.22 1ho HnIoform !oncfIon ........................................................................................ 23?
8.22.l IroµnrnfIon of Iodoform ........................................................................ 23?
8.23 IsoInfIon IxµorImonfs .......................................................................................... 23?
8.23.l IsoInfIon of CnffoIno from 1on .............................................................. 23?
8.23.2 IsoInfIon of !ycoµono from 1omnfoos .................................................. 238
8.23.3 IsoInfIon of CnsoIn from MIIk ............................................................... 239
8.23.4 IsoInfIon of IIµorIno from Ioµµor ........................................................239
8.23.5 IsoInfIon nnd IsfImnfIon of AsµIrIn ...................................................... 240
8.24 IroµnrnfIon of 1rIµfycono.................................................................................... 24l
8.25 AddIfIon of ÐIchIorocnrlono fo CycIohoxono...................................................... 242
8.26 MIscoIInnoous IroµnrnfIons................................................................................. 243
8.26.l IroµnrnfIon of MofhyI Ionzonfo ........................................................... 243
8.26.2 IroµnrnfIon of AcofnnIIIdo (AcofyInfIon) .............................................. 244
8.26.3 IroµnrnfIon of AsµIrIn (AcofyInfIon) ..................................................... 244
8.26.4 IroµnrnfIon of p-ÞIfronnIIIno ............................................................... 245
8.26.5 IroµnrnfIon of MnndoIIc AcId................................................................ 24?
8.26.6 IroµnrnfIon of AnfhrnnIIIc AcId ............................................................ 248
8.26.? IroµnrnfIon of IhonyIuron ...................................................................249
8.26.8 IroµnrnfIon of 2, 4-ÐInIfroµhonyIhydrnzIno ........................................ 249
8.26.9 IroµnrnfIon of ?-Hydroxy-4-MofhyIcoumnrIn ...................................... 250
8.26.l0 IroµnrnfIon of Sonµ from Inf ............................................................... 250
8.26.ll IroµnrnfIon of p-IromonnIIIno ............................................................. 25l
9. SP£CTROSCOPIC M£THODS ......................................................... 253÷26?
9.l Infrnrod Sµocfroscoµy (i.r.) ..................................................................................253
9.l.l InsfrumonfnfIon ......................................................................................... 254
9.l.2 IroµnrnfIon of SnmµIo ............................................................................... 254
9.l.3 InforµrofnfIon of Sµocfrn ........................................................................... 255
9.2 ÞucIonr MngnofIc !osonnnco Sµocfroscoµy (n.n.r.) .......................................... 258
9.2.l InsfrumonfnfIon nnd SnmµIo HnndIIng .................................................... 260
9.2.2 InforµrofnfIon of Sµocfrn ........................................................................... 262
SoIocfod !oforoncos ....................................................................................................... 269
AµµondIx l ...................................................................................................................................... 2?l
AµµondIx 2 ...................................................................................................................................... 2?3
AµµondIx 3 ...................................................................................................................................... 2?8
AµµondIx 4 ...................................................................................................................................... 2?9
AµµondIx 5 ...................................................................................................................................... 28l
AµµondIx 6 ...................................................................................................................................... 282
SoIocfod JournnIs .......................................................................................................................... 283
Indox ................................................................................................................................................ 285
ChupIer 1
SAFETY IN THE
CHEMICAL LABORATORY
A chomIsf works In a chomIcaI Iaborafory whIch consIsfs of oquIpmonfs, gIasswaros,
hazardous chomIcaIs, InfIammabIo IIquIds, ofc. WorkIng wIfh fhoso maforIaIs Is dangorous
and consoquonfIy fho occupafIon of a chomIsf Is hazardous. A workor musf fhus croafo a
safo onvIronmonf fo work In fho Iaborafory. If Is nof onIy hIs or hor IIfo buf of aII ofhors
fhaf Is af rIsk, fhoroforo, ono musf bo parfIcuIar abouf propor safofy whIIo workIng In fho
Iaborafory. Thoro aro corfaIn guIdoIInos whIch ovory ono musf foIIow fo avoId any accIdonf
fo hImsoIf or fo foIIow workors. AII fho porsons workIng In fho Iaborafory shouId Ioarn
sImpIo safofy ruIos fhrough brochuros, vIsuaI aIds or manuaIs. BosIdos If Is oxpocfod fhaf
oach chomIcaI Iaborafory Is provIdod af Ioasf wIfh a fIrsf aId box, fIro oxfInguIshors, fIro
aIarm, wasfo dIsposaI cans, showor, oyo washor and a foIophono. In fho foIIowIng pagos
sovoraI proIImInary guIdoIInos aro summarIzod whIch shouId bo obsorvod af aII fImos fo
mInImIzo accIdonfs and InjurIos whIIo workIng In fho Iaborafory.
1.1 PROTECTIVE CLOTHING
Ono shouId onfor fho Iaborafory In propor cIofhIng. ApproprIafo cIofhIng Is probabIy fho
fIrsf caufIon a workor nood fo fako. A Iaborafory coaf or apron shouId aIways bo worn whIIo
workIng. Ofhor profocfIvo cIofhIng such as gIovos and shoos shouId bo usod. ÐxponsIvo
cIofhIng shouId nof bo worn as fhoy may gof damagod by spIashIng of harmfuI IIquIds. A
Iaborafory coaf provIdos onough profocfIon In caso of spIashos and mInImIzos fho confacf of
chomIcaIs wIfh fho skIn. Shorfs and skIrfs shouId novor bo worn as fhoy oxposo Iargo aroas
of fho skIn. SpocIaI shoos aro nof nocossary, howovor, usIng sandaIs, opon-food shoos and
cIofh shoos aro nof safo.
2 LABORATORY MANUAL OF ORGANIC CHEMISTRY
1.1.1 Equipment and Apparatus
ÐquIpmonf shouId nof bo handIod unIoss ono Is suro If Is funcfIonIng proporIy. AII brokon
and crackod gIasswaros shouId bo rojocfod. Boforo assombIIng fho apparafus ono shouId bo
acquaInfod wIfh fho dIfforonf pIocos. Insfrucfor shouId aIways bo askod whon In doubf.
1.2 HANDLING CHEMICALS
AII chomIcaIs aro oIfhor dangorous, foxIc, hazardous, InfIammabIo or corrosIvo. If fhoy aro
nof handIod rIghfIy fhoy can causo varyIng dogroos of InjurIos. AcIds, aIkaIIos and bromIno
causo sovoro burns If broughf In confacf wIfh fho skIn. AcofIc anhydrIdo and acofyI chIorIdo
brIng foars fo fho oyos. AIcohoIs, bonzono, carbon dIsuIfIdo and ofhors aro hIghIy InfIammabIo.
ÐIazo compounds, poroxIdos and azIdos aro oxpIosIvo. SIIvor nIfrafo, morcurIc chIorIdo,
coppor suIfafo, ofc., aro consIdorabIy poIsonous If fakon InfornaIIy by ovorsIghf. An
oxcopfIonaI procaufIon shouId bo oxorcIsod In workIng wIfh such chomIcaIs. AIways road
fho InsfrucfIons on fho IaboI of fho boffIo boforo oponIng.
1.3 FLAMMABLE MATERIALS
AIways foIIow fho gonoraI guIdoIInos whon usIng fIammabIo maforIaIs or fIro hazard
chomIcaIs and roagonfs. SoIvonfs form a major parf of fho InfIammabIo maforIaI commonIy
usod In an organIc chomIsfry Iaborafory. Ono shouId nof hoaf a roacfIon fIask confaInIng a
soIvonf usIng a burnor. Such soIvonfs shouId bo dIsfIIIod or ovaporafod on a sfoam bafh,
hof pIafo or sand bafh. AIcohoIs, carbon dIsuIfIdo, bonzono, foIuono, ofhor, ofc., cafch fIro
oasIIy. ÐIofhyI ofhor has a vory Iow fIash poInf and has a consIdorabIo narcofIc offocf. Somo
gasos IIko hydrogon and corfaIn soIIds such as LIfhIum aIumInum hydrIdo IIborafo hydrogon
on roacfIon wIfh wafor whIch Is an oxfonsIvoIy InfIammabIo gas. SodIum and pofassIum
undorgo oxpIosIvo roacfIon wIfh wafor. Any oxcoss sodIum mofaI In sodIum fusIon shouId
bo dosfroyod In mofhanoI and nof In wafor.
1.3.1 Corrosive and Toxic Reagents
Such roagonfs roquIro spocIaI affonfIon durIng fhoIr uso. A corrosIvo roagonf causos vIsIbIo
dosfrucfIon of or IrrovorsIbIo chomIcaI acfIon af fho sIfo of confacf. WhIIo workIng wIfh
such roagonfs gIovos shouId bo worn. In caso of accIdonfaI spIII or confacf wIfh fho skIn, fho
affocfod aroa shouId bo washod ImmodIafoIy wIfh IIboraI quanfIfIos of wafor. PhonoI, bromIno
and varIous mInoraI acIds causo sovoro burns. MInoraI acIds aro aIso vory corrosIvo.
ToxIc chomIcaIs aro vory harmfuI on IngosfIon, InhaIafIon or absorpfIon by skIn. Thoso
chomIcaIs aro aIso vory hazardous fo hoaIfh. A IIsf of hazardous chomIcaIs Is gIvon In
socfIon 1.7.
1.3.2 Irritant and Lachrymatory Chemicals
ThIs cIass of compounds aro hIghIy Iachrymafory, such as acId chIorIdos, fhIonyI chIorIdos
and acId anhydrIdos.
SAFETY IN THE CHEMICAL LABORATORY 3
Thoso affocf fho oyos and fho rospIrafory sysfom. In gonoraI, many Iow boIIIng
compounds can aIso bo IIsfod undor fhIs cafogory. Thoso roagonfs shouId bo handIod In fho
fumo hood.
1.4 EYE PROTECTION
Tho human oyo Is fho mosf vaIuod sonso organ and af fho samo fImo fho mosf vuInorabIo
bocauso of Ifs fragIIIfy. ProfocfIon of fho oyo Is mosf Imporfanf. Whonovor possIbIo oyo
hazards shouId bo confroIIod af fho sourco, for oxampIo, spIashIng of IIquIds, fIyIng objocfs,
oncIosuros fo confIno dusf, vapors or fumos. BosIdos safofy gIassos musf aIways bo worn
whIIo porformIng an oxporImonf. OrdInary gIassos do nof provIdo adoquafo profocfIon sInco
fhoy do nof havo sIdo shIoIds, and aIso many may nof havo shaffor-proof Ionsos. Ðo nof Iook
dIrocfIy Info fho opon moufh of a fosf fubo In whIch a roacfIon Is boIng conducfod.
1.5 DISPOSAL OF CHEMICALS AND SOLID WASTES
In gonoraI, a wasfo Is consIdorod hazardous If If Is IgnIfabIo, corrosIvo, foxIc or roacfIvo. If
can bo consIdorod fhaf aII chomIcaI wasfos gonorafod In a chomIcaI Iaborafory aro hazardous.
If Is obsorvod fhaf wasfo chomIcaIs If wafor soIubIo aro sImpIy pourod down fho draIn
accompanIod wIfh a Iargo amounf of fap wafor. MaforIaI nof soIubIo In wafor Is sImpIy
fhrown ouf In fho frash. AII fhoso croafo sorIous onvIronmonfaI probIoms nowadays. If Is,
fhoroforo, fho dufy of ovoryono workIng In fho Iaborafory nof fo dIsposo off fho wasfo In a
haphazard mannor and fhus rIsk fho hoaIfh of ofhors.
OrganIc soIvonfs aro usod In pIonfy and many of fhom aro mIscIbIo wIfh wafor and aro
InfIammabIo. Thoso shouId nof bo fhrown In fho sInk. ÐIfforonf IaboIIod confaInors shouId
bo usod for sforIng fho soIvonfs. If possIbIo soIvonfs IIko acofono, ofhanoI and bonzono may
bo rodIsfIIIod for rouso for cIoanIng purposos. AcIds and aIkaIIos shouId bo noufraIIzod
boforo pourIng fhom down fho sInk. A Iargo amounf of soIId wasfo such as fIIfor papors,
dryIng agonfs, brokon gIasswaros, chromafographIc supporfs, coffon, aIumInum foII, ofc.,
Is gonorafod In fho Iaborafory. Thoso aro non-foxIc and shouId bo packagod In suIfabIo
confaInors and dIsposod off. ToxIc maforIaI, on fho ofhor hand roquIros spocIaI froafmonf
boforo dIsposaI. Tho Insfrucfor shouId bo consuIfod on fho procoduro.
1.6 GUIDELINES IN CASE OF ACCIDENT OR INJURY
Tho abovo guIdoIInos aro Infondod fo provonf accIdonfs In fho chomIcaI Iaborafory. Howovor,
In fho ovonf of an accIdonf or Injury ono shouId know whaf fo do. Tho fIrsf Imporfanf poInf
Is ono shouId nof panIc, fho Insfrucfor Is fo bo Informod ImmodIafoIy and modIcaI assIsfanco
caIIod If nocossary.
Mlnor Cuts from brokon gIasswaros aro common In fho Iaborafory. Tho cuf shouId
bo fhoroughIy fIushod undor fho fap and fhon covorod wIfh an approprIafo bandago. If fho
cuf Is sorIous modIcaI assIsfanco shouId bo soughf. SImIIarIy mInor burns from hof oquIpmonf
or chomIcaIs aro a consfanf hazard. Try nof fo fouch hof gIass. Wash fho affocfod aroa wIfh
wafor and ask for modIcaI assIsfanco.
4 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Burnlng Chemlculs und Clothlng from Iow boIIIng InfIammabIo organIc soIvonfs Is
fho mosf common fIro hazard In fho Iaborafory. If fho fIro Is IImIfod fo a smaII confaInor
IIko a boakor fhon covor If wIfh a wIro gauzo. SInco aII InfIammabIo soIvonfs aro Ioss donso
fhan wafor, wafor shouId novor bo usod fo oxfInguIsh fIro. Sand Is offon usofuI. !or Iargor
fIros, a fIro oxfInguIshor Is roquIrod whIch shouId bo avaIIabIo In fho Iaborafory. Loarn fho
IocafIon and oporafIon of a fIro oxfInguIshor. !or fIros boyond confroI, fho fIro aIarm shouId
bo soundod and fIro sorvIcos summonod.
In fho ovonf of ono`s cIofhos cafchIng fIro, fho vIcfIm shouId roII ovor on fho ground fo
oxfInguIsh fho fIro or shouId bo covorod wIfh a fIro bIankof. A fIro oxfInguIshor shouId nof
bo usod on a porson.
1.7 TOXICITY AND HAZARDS OF CHEMICALS
In our daIIy IIfo wo handIo chomIcaIs In ono form or fho ofhor whofhor If Is In fho Iaborafory
or fho houso or confamInafIon of fho afmosphoro. Mosf of fhoso chomIcaIs aro InhoronfIy
foxIc and hazardous. ToxIcIfy Is fho Inhoronf proporfy of a moIocuIo fo produco Injury on
roachIng a suscopfIbIo sIfo or In an organIsm. Thoy harm by InhaIafIon, IngosfIon or
absorpfIon by skIn. Thoy shouId, fhus bo handIod wIfh fho ufmosf caro fo avoId fhroaf fo
fho hoaIfh and IIfo. !or your own hoaIfh and safofy, oxorcIso caufIon whIIo handIIng chomIcaIs
and mInImIzo your oxposuro fo fhom. A brIof doscrIpfIon of fho hazardous proporfIos and
offocfs on fho human body of somo basIc chomIcaIs Is gIvon boIow:
AceIuIJehyJe· If Is a gas af room fomporafuro, b.p. 21
o
C, fIammabIo and pungonf
smoIIIng. Tho TLV` Is 200 ppm. InhaIafIon of Ifs vapors causos IrrIfafIon of oyos, skIn and
rospIrafory organs. AcofaIdohydo shouId bo sforod In a cooI pIaco.
AceIic unhyJriJe· If Is a IIquId b.p. 139.9
o
C, possoss a pungonf odor. If docomposos
sIowIy wIfh wafor fo form acofIc acId. Tho TLV Is 5 ppm. AcofIc anhydrIdo IrrIfafos oyos,
skIn and mucous mombrano and causos nausoa.
AceIoniIriIe· If Is a coIorIoss IIquId, b.p. 81.6
o
C, possoss aromafIc odor and Is foxIc. If
Is fIammabIo, TLV Is 40 ppm, If causos acufo hoadacho, dIzzInoss and nausoa whon InhaIod.
AceIyI chIoriJe· If Is a coIorIoss fumIng IIquId, b.p. 52
o
C. WIfh wafor, If docomposos
vIoIonfIy fo form acofIc acId and hydrochIorIc acId. If Is hIghIy IrrIfanf and causos
InfIammafIon of skIn. Sforo In woII vonfIIafod cooI room.
AcroIein· If Is a coIorIoss, fIammabIo and pungonf IIquId, b.p. 59.7
o
C. TLV Is 0.1 ppm.
Ifs vapors causo InfIammafIon of oyos, noso, skIn and fhroaf. AcroIoIn shouId bo handIod In
a fumo hood.
Ammoniu· AmmonIa Is coIorIoss gas, b.p. ÷33.5
o
C. If has a sharp IrrIfafIng odor and Is
soIubIo In mosf soIvonfs. TLV Is 50 ppm. Ifs InhaIafIon may causo suffocafIon and damago
fo Iungs. AmmonIa Is ImmonsoIy IrrIfanf fo skIn and aIso causos nausoa, cough, bronchIfIs
and puImonary ondoma.
`TLV tThroshoId IImIf vaIuo) Is fho conconfrafIon of an aIrbono consfIfuonf fo whIch a workor may bo
ropoafodIy oxposod wIfhouf advorso offocf for a normaI 8 hr work day.
SAFETY IN THE CHEMICAL LABORATORY 5
AniIine· If Is coIorIoss oIIy IIquId, b.p. 184
o
C. If darknoss on oxposuro fo aIr. TLV Is 5
ppm. If causos dIzzInoss, nausoa, abdomInaI paIn and maIaIso.
Benzene·  If Is a coIorIoss fo yoIIow IIquId, b.p. 80
o
C and hIghIy fIammabIo. TLV Is 10
ppm. BroafhIng bonzono causos ouphorIa, hoadacho, narcosIs, dIzzInoss and rapId hoarf
rafo. Long form oxposuro fo bonzono can affocf fho bono marrow and docroaso rod bIood
coIIs IoadIng fo anomIa.
Bromine· If Is a dark raddIsh brown IIquId, b.p. 58.8
o
C onIy sIIghfIy soIubIo In wafor.
BromIno rapIdIy vaporIzos af room fomporafuro, fho fumos aro vory IrrIfafIng and Is an
oxfromoIy unpIoasanf chomIcaI. TLV Is 0.1 ppm. If causos skIn burns, dIzzInoss, hoadacho,
bronchIfIs and nausoa. Sforo In a cooI dry pIaco and ouf of dIrocf sunIIghf.
n-BuIunoI· If Is a coIorIoss IIquId, b.p. 177
o
C. If has a modorafo fIro rIsk. TLV Is 100
ppm. On InhaIafIon If causos rospIrafory InfIammafIon, paraIysIs and dIzzInoss.
n-BuIyI uceIuIe· If Is a voIafIIo IIquId wIfh fruIfy odor, b.p. 126.5
o
C. TLV Is 150 ppm.
If causos conjuncfIvIfIs, cough, hoadacho and anoroxIa tIoss of appofIfo).
n-BuIyIIiIhium· CommorcIaIIy a sfabIo soIufIon of n-bufyIIIfhIum Is obfaInod In ponfano
or hopfano. If Is sfrongIy IrrIfanf and foxIc and IgnIfIos on confacf wIfh moIsf aIr. Tho
soIufIon shouId bo prosorvod boIow 15
o
C.
Curbon JisuIjiJe· If Is a coIorIoss or faInfIy yoIIow IIquId, b.p. 46
o
C and vory
fIammabIo. Carbon dIsuIfIdo Is a pofonfIaIIy fIro hazard and foxIc. TLV Is 20 ppm. If causos
hoadacho, vomIfIng and abdomInaI paIn.
Curbon IeIruchIoriJe· If Is coIorIoss non-fIammabIo hoavy IIquId, b.p. 77
o
C. TLV Is
10 ppm. If has swoof odor and Is foxIc. Carbon fofrachIorIdo causos IrrIfafIon of oyos,
hoadacho, abdomInaI cramps and norvousnoss.
ChIorine· If Is a groonIsh-yoIIow gas havIng a suffocafIng odor. ChIorIno Is foxIc and
IrrIfafIng. TLV Is 1 ppm. Ifs InhaIafIon causos IrrIfafIon of oyos, dIffIcuIf broafhIng, cough,
paIn, nausoa and cyanosIs.
ChIorouceIyI chIoriJe· If Is a coIorIoss or sIIghfIy yoIIow IIquId, b.p. 106
o
C.
Ðocomposos wIfh wafor, and Is non-combusfIbIo. If causos IrrIfafIon of oyos, noso and fhroaf.
ChIorojorm· If Is a coIorIoss, hoavy IIquId, b.p. 61
o
C and possossos a swoof fasfo. If Is
voIafIIo. TLV Is 50 ppm. ChIoroform causos unconscIousnoss, shorfnoss of broafh and
vomIfIng.
DiuzomeIhune· If Is a yoIIow gas af room fomporafuro and soIubIo In ofhor. If
docomposos oxpIosIvoIy by wafor or aIcohoI. If possossos a sovoro oxpIosIon hazard. TLV Is
0.2 ppm. ÐIazomofhano Is sovoroIy foxIc and IrrIfanf.
DieIhyI eIher· If Is a coIorIoss, vory voIafIIo and fIammabIo IIquId, b.p. 34.5
o
C. If has
a vory Iow fIash poInf. If fravoIs consIdorabIo dIsfanco fo fho sourco of IgnIfIon. TLV Is
400 ppm. Ðfhor has a ponofrafIng smoII. On InhaIafIon If causos hoadacho, vomIfIng, paraIysIs
and IrrIfafIon of rospIrafory fracf. Sforo In a cooI aroa.
6 LABORATORY MANUAL OF ORGANIC CHEMISTRY
1, 2- DichIoroeIhune· If Is coIorIoss oIIy IIquId wIfh chIoroform IIko odor, b.p. 83
o
C. If
Is sIIghfIy soIubIo In wafor buf fIammabIo. TLV Is 50 ppm. If causos IrrIfafIon of rospIrafory
fracf, hoadacho, woaknoss, anxIofy and convuIsIons.
FormuIJehyJe· If Is a coIorIoss gas wIfh pungonf odor, oasIIy soIubIo In wafor. If Is
hIghIy roacfIvo and roadIIy poIymorIzos wIfh many organIc subsfancos. TLV Is 3 ppm.
!ormaIdohydo causos conjuncfIvIfIs, cornoaI burns and dormafIfIs.
HyJruzine· If Is a coIorIoss, fumIng IIquId, b.p. 113.5
o
C. If has ponofrafIng ammonIacaI
odor. If Is hIghIy dangorous. If has fIro and oxpIosIon rIsk. TLV Is 1 ppm. HydrazIno causos
conjuncfIvIfIs, IrrIfafIon of frachoaI fracf and skIn as woII as nausoa.
HyJrogen cyuniJe· If Is a coIorIoss gas possossIng faInf aromafIc odor. If Is mIscIbIo
wIfh wafor and aIcohoI. If Is fIammabIo and a fIro hazard. TLV Is 10 ppm. Hydrogon cyanIdo
causos nausoa, hoadacho, paIpIfafIon, unconscIousnoss and doafh.
HyJroxyIumine · If consfIfufos of Iargo whIfo fIakos or noodIos, m.p. 33
o
C. If Is hIghIy
hygroscopIc and unsfabIo. If causos hoadacho, dIzzInoss, dIspnoa tdIffIcuIf broafhIng),
vomIfIng and jaundIco.
¡oJine· If forms hoavy, groyIsh bIack pIafos or granuIos, has a characforIsfIc odor,
m.p. 113.5
o
C. IodIno Is soIubIo In aIcohoI, carbon dIsuIfIdo, ofhor and chIoroform. If causos
hoadacho, dIzzInoss, cough, puImonary ondoma and dIffIcuIf broafhIng.
Mercury· If Is sIIvory and hoavy IIquId and has a Iow vapor prossuro t0.002 mm/20
o
C).
TLV Is 0.1 mg/m
3
. SwaIIowIng causos burnIng In fho moufh and fhroaf, fhIrsf, nausoa and
bIoody dIarrhoa. InhaIafIon of morcury vapors causo InfIammafIon of moufh, abdomInaI
cramps, cough and fovor.
PhenoI· If Is a whIfo crysfaIIIno mass buf furns pInk on oxposuro fo aIr, b.p. 182
o
C. If
absorbs moIsfuro from fho afmosphoro and IIquIfIos. TLV Is 5 ppm. PhonoI causos burns on
confacf wIfh skIn, pharynx, vomIfIng, cough and puImonary ondoma.
Phosgene· If Is a coIorIoss gas soIubIo In wafor formIng paIo yoIIow IIquId and non-
combusfIbIo. Phosgono Is oxfromoIy foxIc. TLV Is 0. ppm. If causos hoadacho, rapId
rospIrafIon, cough, cyanosIs, vomIfIng and paIn In fho uppor abdomon.
Phosphorus penIuchIoriJe· If Is a yoIIow powdor and subIImos af 160÷165
o
C wIfhouf
moIfIng. If Is fIammabIo, TLV Is 1 mg/m
3
. If causos IrrIfafIon of oyos, bronchIfIs and nophrIfIs
tInfIammafIon of kIdnoy).
PoIussium cyuniJe· If Is whIfo amorphous powdor. If has a faInf aImond-IIko odor.
TLV Is 5 mg/m
3
. If Is ImmonsoIy foxIc.
PyriJine· If Is a sIIghfIy yoIIow or coIorIoss IIquId, fIammabIo wIfh nausoafIng odor,
b.p. 115
o
C. TLV Is 5 ppm. PyrIdIno causos conjuncfIvIfIs, pruIfus tIfchIng), oczoma, hoadacho,
vomIfIng and abdomInaI paIn.
SIyrene· If Is a coIorIoss fo yoIIowIsh oIIy IIquId wIfh ponofrafIng odor and sparIngIy
soIubIo In wafor. Sfyrono roadIIy undorgoos poIymorIzafIon. TLV Is 100 ppm. If causos
conjuncfIvIfIs, Iack of appofIfo, nausoa, woaknoss and drowsInoss.
SAFETY IN THE CHEMICAL LABORATORY 7
ThionyI chIoriJe· If Is a paIo yoIIow, pungonf IIquId, b.p 79
o
C. If Is docomposod roadIIy
by wafor. TLV Is 5 ppm. If causos conjuncfIvIfIs, dormafIfIs tskIn InfIammafIon) and
pnoumonIa.
ToIuene· If Is a coIorIoss and fIammabIo IIquId wIfh bonzono IIko odor, b.p. 110.6
o
C. If
Is mIscIbIo wIfh aIcohoI, chIoroform, ofhor and acofono. TLV Is 200 ppm. ToIuono causos
dormafIfIs, nausoa, woaknoss and IncoordInafIon. ToIuono Is aIso known fo causo cancor
and norvous sysfom dIsordors.
References
1. Ha:arJs in thc Chcnica/ Laboratory, 4fh odn., tÐd. by L. BrofhorIck), RoyaI SocIofy
of ChomIsfry, London t1986).
2. FruJcnt Fracticcs jor HanJ/ing Ha:arJous Chcnica/s in Laboratorics, NafIonaI
Rosoarch CouncII, NafIonaI Acadomy Pross, WashIngfon, Ð.C. t1981).
3. M.J. PIff and Ð. PIff, HanJbooh oj Laboratory Wastc Disposa/, WIIoy, Now York
t1985).
4. 8igna-A/Jrich Library oj Chcnica/ 8ajcty Data, 2nd odn., tÐd. by R.Ð. Longa)
t1988).
5. Ð.A. PIpIfono, 8ajc 8toragc oj Laboratory Chcnica/s, WIIoy, Now York t1991).
6. M.J. Lofovro, First AiJ Manua/ jor Chcnica/ AcciJcnts, Ðowdon ct a/., Sfroudsborg,
Pa t1980).
?. 8ajc usc oj 8o/ocnts, tÐd. by A.J. CoIIIns and S.G. Luxon), AcadomIc Pross, Now
York t1982).
ChupIer 2
LABORATORY EQUIPMENTS AND
TECHNIQUES
In an organIc chomIsfry Iaborafory a varIofy of gIasswaros and fochnIquos aro usod for fho
synfhosIs, soparafIon and purIfIcafIon of organIc compounds as woII as for roufIno work.
Tho apparafus, howovor, bocomos moro sophIsfIcafod In a rosoarch Iaborafory. If Is hIghIy
dosIrabIo fhaf fho sfudonf bo famIIIar wIfh fho uso and handIIng of fho apparafus. Tho
Iaborafory fochnIquos doscrIbod horo aro basIc fo aImosf aII oxporImonfafIon In organIc
chomIsfry.
2.1 GLASSWARES
A brIof dIscussIon of fho common fypos of gIasswaros and apparafus usod In fho chomIcaI
Iaborafory Is gIvon horo.
(a) Flasks
Thoso aro fho common fypos of fIasks usod for a varIofy of purposos. !Iasks ta) fo to) aro
ompIoyod for rofIuxIng and dIsfIIIafIon. !Iasks wIfh sfandard-fapor ground gIass joInfs and
fhoso wIfhouf aro In common uso In a chomIcaI Iaborafory. !Iasks ta) and tb) aro fho onos
wIfh fho ground gIass joInfs. Thoy roquIro groasIng and propor cIoanIng affor uso.
LABORATORY EQUIPMENTS AND TECHNIQUES 9
Tho ÐrIonmoyor fIask tf) Is usod for mIxIng and fIfrafIon. !Igs. tg) fo tI) roprosonf
dIfforonf dIsfIIIafIon fIasks wIfh condonsors affachod. Tho fIrsf fwo aro fho roguIar dIsfIIIafIon
fIasks buf tI) Is caIIod fho CIaIson fIask wIfh a fracfIonafIng coIumn.
(b) Measuring devices
Tho Pasfour pIpoffo Is usod for fransforrIng a smaII quanfIfy of a soIufIon or a IIquId, whIIo
ofhor pIpoffos doIIvor a fIxod voIumo of fho soIufIon. Tho moasurIng cyIIndor tb) Is usod for
moasurIng approxImafo voIumos.
10 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(c) Condensers
Tho condonsors ta) and tb) aro usod for rofIuxIng and roufIno dIsfIIIafIon. Tho aIr condonsor
tc) Is ompIoyod If fho IIquId dIsfIIIIng has a vory hIgh boIIIng poInf.
(d) Funnels
!Iguro ta) shows an Iong sfom funnoI usod for fransforrIng or fIIforIng of IIquIds and roagonf
soIufIons, whIIo tb) Is fho HIrsch funnoI for fIIforIng vory smaII soIId sampIos. Whoroas tc)
and td) aro fho soparafory funnoIs usod for fho oxfracfIon of a producf from a roacfIon
mIxfuro; to) Is a droppIng funnoI ompIoyod for fho addIfIon of a roacfanf fo a roacfIon fIask.
LABORATORY EQUIPMENTS AND TECHNIQUES 11
ÐurIng fho oxfracfIon of a producf whIIo workIng wIfh aIkaIIno soIufIons If Is obsorvod
fhaf an omuIsIon Is usuaIIy formod whIch provonfs fho soparafIon of fwo ImmIscIbIo Iayors.
Tho omuIsIon so formod can bo brokon up by ono of fho foIIowIng fwo mofhods.
tE) GonfIy swIrIIng fho soparafory funnoI whIIo hoIdIng If In an uprIghf posIfIon.
tEE) SafurafIng fho aquoous Iayor of fho roacfIon mIxfuro wIfh a saIf such as sodIum
chIorIdo.
Tho socond fochnIquo docroasos fho soIubIIIfy of fho Inorf organIc soIufos as woII as
fho oxfracfIon soIvonfs such as ofhor In fho wafor Iayor. ThIs procoss Is roforrod fo as fho
sultlng-out eIIect. Tho Buchnor funnoI and fho Buchnor fIask aro usod oxfonsIvoIy In
synfhosIs for fIIfrafIon of a soIId producf.
Tho arrangomonf for fIIfrafIon tc) usIng a wafor pump or aspIrafor Is shown In
!Iguro t2.1):
Fig. 2.1: Apparatus for collection of crystals by suction filtration.
12 LABORATORY MANUAL OF ORGANIC CHEMISTRY
A wafor frap Is IncIudod bofwoon fho sysfom and fho wafor aspIrafor. ThIs fonds fo
provonf wafor suckIng back Info fho apparafus whon a suddon drop In prossuro occurs. Tho
vacuum gonorafod doponds on fho spood of wafor rushIng fhough fho aspIrafor.
(e) Stirrers
Thoso fIguros roprosonf varIous fypos of sfIrrors usod for sfIrrIng purposos. Thoso aro
usuaIIy mado of gIass buf fhoso mado of sfaInIoss sfooI or fofIon aro aIso In common uso. A
sfIrror Is affachod dIrocfIy fo a smaII oIocfrIc mofor wIfh fho aId of a smaII prossuro fubIng
and mochanIcaI agIfafIon Is achIovod.
A magnofIc sfIrror on fho ofhor hand, Is a usofuI dovIco for smaII quanfIfIos and non-
vIscous roacfIon mIxfuros. Tho sfIrrIng Is achIovod by a magnofIc spInnor bar whIch Is
addod fo fho roacfIon mIxfuro.
Largo scaIo and vIscous roacfIon mIxfuros roquIro a mochanIcaI sfIrror and nood groafor
powor of an oxfornaI mofor unIf for furnIng a sfIrror bIado. A fypIcaI modoI Is shown In
fIg. 2.2.
LABORATORY EQUIPMENTS AND TECHNIQUES 13
Fig. 2.2: A mechanical stirrer.
(f) Drying apparatus
Tubo ta) Is usuaIIy packod wIfh anhydrous caIcIum chIorIdo and Is usod fo oxcIudo moIsfuro
from a roacfIon vossoI. Tho dryIng fubo Is offon usod If fho roacfIon noods fo bo porformod
undor dry condIfIons. Tho vacuum dosIccafor fInds appIIcafIon for dryIng a compound af Iow
prossuro.
14 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho boffom of fho dosIccafor may bo fIIIod oIfhor wIfh anhydrous caIcIum chIorIdo or
conc. suIfurIc acId. SomofImos, If Is dIffIcuIf fo romovo fho moIsfuro compIofoIy from a wof
soIId In a vacuum dosIccafor. In fhaf caso compIofo romovaI of moIsfuro can bo achIovod
usIng fho Abderhulden drylng plstol. Tho apparafus Is shown In fIguro tc). In fhIs caso,
fho soIId producf Is oncIosod In a smaII boaf tA) In a gIass-sfopporod dryIng fubo tB). ThIs
fubo Is hoafod confInuousIy by rofIuxIng a suIfabIy soIocfod IIquId tsuch as foIuono) In fho
fIask tC). Tho dryIng fubo Is connocfod fo a chambor tÐ) confaInIng an offIcIonf dosIccanf.
Bofh fho dryIng fubo and fho dosIccanf chambor aro ovacuafod by appIyIng vacuum fhrough
fho sfopcock tÐ). On hoafIng fho soIvonf, fho dryIng fubo Is surroundod by fho hof vapors.
Tho wafor vapors from fho sampIo aro capfurod by a chomIcaI dryIng agonf such as
phosphorus ponfoxIdo pIacod In tÐ).
(g) Adapters
Adapfors ta) and td) aro normaIIy usod fo facIIIfafo fho doIIvory of a dIsfIIIafo from fho
condonsor fo a rocoIvor. A vacuum can aIso bo appIIod fo adapfor td) If noodod. !Ig. tb)
roprosonfs a sImpIo dIsfIIIafIon hoad whIIo tc) Is fho wIdoIy usod CIaIson dIsfIIIafIon hoad.
2.2 ASSEMBLIES FOR REACTIONS
In fIguro 2.3 a round-boffomod fIask Is fIffod wIfh a wafor condonsor. Tho joInfs couId
oIfhor bo sfandard or Insfoad a cork can bo usod fo fIx fho condonsor fo fho fIask. ThIs fypo
of sofup Is ompIoyod for rofIuxIng a roacfIon mIxfuro. BoIIIng sfonos aro aIways usod fo
onsuro smoofh rofIuxIng. A fhroo-nockod fIask tb) oquIppod wIfh a wafor condonsor, droppIng
funnoI and a mochanIcaI sfIrror wIfh a morcury soaI Is fho mosf common fypo of assombIy
usod In synfhosIs. Morcury soaI provonfs fho oscapo of gasos durIng sfIrrIng. A dryIng fubo
can bo fIxod on fho wafor condonsor fo oxcIudo afmosphorIc moIsfuro.
LABORATORY EQUIPMENTS AND TECHNIQUES 15
Fig. 2.3: Apparatus for carrying out reactions.
2.3 DISTILLATION
ÐIsfIIIafIon Is a cIassIcaI fochnIquo In fho Iaborafory for fho purIfIcafIon of IIquIds from
voIafIIo and non-voIafIIo ImpurIfIos. If may aIso bo usod for fho soparafIon of fwo mIscIbIo
IIquIds. Tho procoss of dlstlllutlon may bo doscrIbod as fho parfIaI vaporIzafIon of a IIquId
and carryIng ovor and condonsafIon of fhoso vapors back fo IIquId In a dIfforonf parf of fho
dIsfIIIafIon apparafus. Tho dIsfIIIod IIquId Is caIIod fho dlstlllute, dopondIng on fho nafuro
and boIIIng poInf of fho subsfanco fo bo dIsfIIIod, dIfforonf mofhods of dIsfIIIafIon aro ompIoyod
In a chomIcaI Iaborafory.
2.3.1 Simple Distillation
SImpIo dIsfIIIafIon Is a Iaborafory mofhod for fho purIfIcafIon of organIc soIvonfs. AII IIquIds
possoss vapor prossuro whIch Is aIways consfanf af a consfanf fomporafuro. Tho vapor
prossuro Is duo fo fho fondoncy of fho IIquId moIocuIos fo oscapo from fho surfaco of fho
IIquId. ThIs oscapIng fondoncy Is dIfforonf for dIfforonf IIquIds. ThIs causos a dIfforonco In
fho vapor prossuro and honco fho boIIIng poInf. !or Insfanco, ofhor ovaporafos rapIdIy
16 LABORATORY MANUAL OF ORGANIC CHEMISTRY
whIIo gIycorIno doos so sIowIy bocauso fho vapor prossuro of ofhor Is Iow. Tho vapor prossuro
Incroasos wIfh fho Incroaso In fomporafuro. If fho fomporafuro Is raIsod, fho IIquId sfarfs
boIIIng. Tho bolllng polnt of a IIquId Is dofInod as fho fomporafuro af whIch Ifs vapor
prossuro Is oquaI fo fho oxfornaI prossuro. If fho oxfornaI prossuro Is 760 mm tI.o., fho
afmosphorIc prossuro) a IIquId sfarfs fo boII fIII Ifs vapor prossuro roachos fhIs vaIuo. Tho
prosonco of ImpurIfIos Iowors fho vapor prossuro and fhus Incroasos fho boIIIng poInf. As
sfafod abovo, vapor prossuro Incroasos as fho fomporafuro Is raIsod. ThIs Is IIIusfrafod
nIcoIy In !Ig. 2.4. As If Is obvIous whon a puro subsfanco Is hoafod and If fho fomporafuro
Fig. 2.4: The vapor pressure of a liquid versus temperature plot.
Is raIsod, fho vapor prossuro of fho subsfanco bocomos oquaI fo fho afmosphorIc prossuro
and fho subsfanco boIIs. !or Insfanco, wafor boIIs af 100
o
C whon fho oxfornaI prossuro Is
760 mm t1 afm). Thoroforo, wafor has a vapor prossuro 760 mm Hg af 100°C. Two IIquIds
can bo soparafod from ono anofhor provIdod fhoIr boIIIng poInfs aro nof foo cIoso fogofhor.
!suaIIy fho dIfforonco In boIIIng poInfs shouId nof bo Ioss fhan 70
o
C or moro. Tho apparafus
for carryIng ouf a sImpIo dIsfIIIafIon Is pIcfurod In !Ig 2.5.
Tho assombIy consIsfs of a round-boffomod dIsfIIIafIon fIask oquIppod wIfh a fhormomofor,
a sfIIIhoad and a wafor condonsor. CoId wafor Is cIrcuIafod Info fho condonsor from fho Iowor fo
uppor ond. Tho ofhor ond of fho condonsor Is affachod fo a rocoIvIng fIask fhrough a rocoIvIng
adapfor. NormaI groaso Is usod for groasIng fho joInfs.
Tho IIquId tor fho mIxfuro of IIquIds) fo bo dIsfIIIod Is fransformod fo fho dIsfIIIafIon fIask
wIfh fho hoIp of a funnoI. Tho fIask shouId nof bo fIIIod wIfh fho IIquId moro fhan haIf. If Is now
hoafod wIfh a propor hoaf sourco. A wafor or sfoam-bafh Is rocommodod for Iow boIIIng soIvonfs.
An oIocfrIcaIIy hoafod oII-bafh Is noodod for hIgh boIIIng IIquIds. A Bunson burnor shouId novor
bo usod. AIso avoId usIng a hoafIng manfIo, as fho fomporafuro Is nof confroIIabIo. Tho hoafIng
shouId bo carrIod ouf sIowIy fo provonf supor hoafIng of vapors, I.o., rIso of fomporafuro abovo
fho boIIIng poInf, and causIng bumpIng. Bumplng Is fho sfago af whIch a porIodIcaIIy suddon
ojocfIon of oxcossIvo vapors fakos pIaco. Af fImos If can bocomo vory dangorous.
600
400
200
0 20 40 60 80
V
a
p
o
r

p
r
e
s
s
u
r
e

(
a
t
m
)
LABORATORY EQUIPMENTS AND TECHNIQUES 17
Fig. 2.5: Apparatus for simple distillation.
Boforo hoafIng fho IIquId 2-3 smaII boIIIng chIps shouId bo addod fo fho dIsfIIIafIon fIask. A
bolllng chlp Is a smaII pIoco of porcoIaIn fIIo. Tho oscapIng gas bubbIos from fho boIIIng chIp
wIII broak fho surfaco of fho IIquId and wIII promofo smoofh boIIIng and provonf bumpIng.
Tho rIsIng vapors of fho IIquId wIII pass fhrough fho nock of fho fIask, gof condonsod by
fho coId nock and drop back Info fho fIask. ThIs procoss wIII confInuo fIII an oquIIIbrIum Is
roachod bofwoon fho rIsIng vapors and fho condonsIng IIquId. Tho vapors wIII fhon roach fho
fhormomofor and fhrough fho sIdo fubo Info fho condonsor. SInco coId wafor Is boIng cIrcuIafod
fhrough fho condonsor, fho vapors wIII condonso and coIIocf by moans of a curvod adapfor Info
fho rocoIvIng fIask. Tho fomporafuro wIII romaIn consfanf fIII aII fho IIquId has dIsfIIIod. Tho
ImpurIfIos romaIn In fho fIask. Tho fhormomofor shouId nof bo Immorsod Info fho IIquId bocauso
In fhaf caso, a fomporafuro abovo fho boIIIng poInf of IIquId Is rocordod. To obsorvo fho corrocf
boIIIng poInf, fho fhormomofor bo pIacod IdoaIIy In fho vapors. Tho dIsfIIIafIon of a IIquId may
bo accompIIshod oIfhor af afmosphorIc prossuro or undor roducod prossuro. In gonoraI, If fho
boIIIng poInf of fho sampIo Is abovo 180°C, fhon a roducod prossuro dIsfIIIafIon Is rocommondod.
In dIsfIIIafIon, wo offon dIsfIII a mIxfuro of fwo mIscIbIo IIquIds fhaf form 'IdoaI` soIufIon.
An ldeul solutlon Is somofImos dofInod as ono whIch oboy`s RaouIf`s Iaw. Howovor, fhoro aro
a numbor of IIquId mIxfuros fhaf faII fo oboy fhIs Iaw. Such IIquIds may form an azoofropo. An
uzeotope or an uzeotroplc mlxture Is a mIxfuro of dofInIfo composIfIon fhaf dIsfIIIs af a
consfanf fomporafuro as If If woro a puro IIquId. Tho boIIIng poInf of an azoofropo dIffors
sIIghfIy In somo casos from fho boIIIng poInf of onIy ono compononf. A famIIIar oxampIo Is ofhyI
aIcohoI and wafor confaInIng 95.5 porconf ofhyI aIcohoI and 4.5 porconf wafor and boIIs af 78.15
°C whoroas puro aIcohoI boIIs af 78.3°C. An azoofropIc mIxfuro cannof bo soparafod by sImpIo
dIsfIIIafIon.
18 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Questions
2.1 Whaf Is fho funcfIon of addIng boIIIng chIps fo fho IIquId boforo hoafIng7
2.2 ÐoscrIbo supor hoafIng.
2.3 If a IIquId boIIs af a consfanf fomporafuro ovor fho whoIo rango, couId you concIudo
fhaf If Is puro7
2.4 Why Is coId wafor cIrcuIafod fhrough a condonsor from fho Iowor fo fho uppor ond7
2.5 CouId you rocord fho corrocf boIIIng poInf If fho fhormomofor fIp Is Immorsod Info fho
IIquId7
2.3.2 Fractional Distillation
SImpIo dIsfIIIafIon Is ompIoyod for fho soparafIon of a bInary homogonoous mIxfuro of IIquIds
whoso boIIIng poInf dIfforonco Is nof Ioss fhan 70°C. Howovor, for a mIxfuro of IIquIds wIfh
Iossor dIfforonco In boIIIng poInfs, soparafIon can bo offocfod by ropoafIng fho sImpIo
dIsfIIIafIon sovoraI fImos. ThIs procoss apparonfIy Is vory cumborsomo and fImo consumIng.
AIfornafIvoIy, soparafIon of such a mIxfuro may bo achIovod by InfroducIng a fracfIonafIng
coIumn. !racfIonaI dIsfIIIafIon Is sImpIy a mofhod of accompIIshIng a whoIo sorIos of ropoafod
dIsfIIIafIons Info a sIngIo confInuous oporafIon. A fracfIonafIng coIumn, In prIncIpIo, Is fho
oIongafIon of fho nock of fho dIsfIIIIng fIask whIch provIdos an oxfonsIvo surfaco aroa for
hoaf oxchango af oquIIIbrIum condIfIons.
Thoro aro sovoraI fypos of fracfIonafIng coIumns avaIIabIo. In a sImpIo fypo gIass boads
or gIass hoIIcs may bo usod as packIng maforIaI In a pyrox gIass fubo. Tho packIng may bo
supporfod by usIng a mofaI gauzo. In ofhor fypos IndonfafIons wIfh downward sIanf In fho
sIdo of fho gIass fubo caIIod Vlgreuux column or fho gIass spIraI of fho Wldmer column
may bo usod. If Is gonoraIIy Ioss offocfIvo fhan fho packod coIumn buf Is good for roufIno
dIsfIIIafIon.
LABORATORY EQUIPMENTS AND TECHNIQUES 19
A packod coIumn provIdos a Iargo surfaco aroa for offIcIonf dIsfIIIafIon. Tho offIcIoncy
of a coIumn Is oxprossod In forms of fhoorofIcaI pIafos. A theoretlcul plute Is fho coIumn
wIfhIn fho coIumn fhaf Is oquaI fo a sImpIo dIsfIIIafIon. Thoroforo, a coIumn wIfh fhoorofIcaI
pIafos Is oquaI fo numbor of dIsfIIIafIons. A fracfIonafIng coIumn porforms fho funcfIon of
sovoraI hundrod dIsfIIIafIons. Tho apparafus for fracfIonaI dIsfIIIafIon Is shown In !Ig. 2.6.
Fig. 2.6: Apparatus for fractional distillation.
ThIs assombIy dIffors from fhaf of sImpIo dIsfIIIafIon In fhaf a fracfIonafIng coIumn
has boon Incorporafod bofwoon fho dIsfIIIIng fIask and fho sfIIIhoad. A boIIIng chIp Is addod
and fho IIquId Is hoafod as usuaI In fho dIsfIIIIng fIask. Tho moro voIafIIo IIquId vaporIzos
fasfor fhan fho hIgh boIIIng IIquId, fhoso vapors gof condonsod on fho coIumn packIng. ThIs
confInuos and ovonfuaIIy fho vapors gof onrIchod In fho Iowor boIIIng compononf.
ÐquIIIbrafIons occur In aII parfs of fho coIumn and vapors fhaf pass Info fho rocoIvor aro
20 LABORATORY MANUAL OF ORGANIC CHEMISTRY
fhoso of fho puro Iow boIIIng IIquId. Tho rosIduo In fho fIask Is fho hIgh boIIIng IIquId. Tho
fomporafuro romaIns consfanf fIII aII fho moro voIafIIo IIquId has boon dIsfIIIod. Tho
fomporafuro fhan drops a IIffIo IndIcafIng ono compononf of fho mIxfuro has boon romovod.
Moro hoaf shouId bo appIIod af fhIs sfago, and fho socond IIquId commoncos fo dIsfIII.
Questions
2.6 ÐofIno a fhoorofIcaI pIafo.
2.7 ÐxpIaIn why a packod fracfIonafIng coIumn Is moro offIcIonf af soparafIng a mIxfuro
of cIosoIy boIIIng IIquIds fhan an unpackod ono.
2.8 If fho rafo of dIsfIIIafIon fhrough a packod coIumn In foo rapId, whaf wIII bo Ifs offocf
on fho offIcIoncy of soparafIon7
2.3.3 Distillation Under Reduced Pressure
A IIquId boIIs whon Ifs vapor prossuro oquaIs fho oxfornaI prossuro. Many organIc compounds
cannof bo purIfIod by dIsfIIIafIon af ordInary prossuro bocauso fhoy docomposo whon hoafod
ovon boIow fhoIr known boIIIng poInfs. BoIIIng poInf Is dopondonf on oxfornaI prossuro,
fhoroforo, If can bo roducod by roducIng fho prossuro. Thus fo mako fho purIfIcafIon of such
subsfancos possIbIo fhoy aro dIsfIIIod undor roducod prossuro. Whon fho prossuro Is roducod,
fho subsfanco boIIs af a Iowor fomporafuro. ThIs Is known as dIsfIIIafIon undor roducod
prossuro or vacuum dIsfIIIafIon. A vacuum of fho ordor of 0.1 ÷ 1.0 mm Hg can bo obfaInod
by usIng an oII ImmorsIon rofary vacuum pump. If Is rocommondod fhaf vacuum dIsfIIIafIon
bo usod If fho normaI boIIIng poInf Is groafor fhan abouf 150°C.
An ouffIf for vacuum dIsfIIIafIon Is dopIcfod In !Ig. 2.7.
SuIfabIo sfandard joInf fIasks aro usod. Mako suro fho joInfs aro groasod proporIy
usIng a good quaIIfy vacuum groaso. A sfandard joInf round boffom fIask Is fIffod wIfh a
CIaIson hoad whIch Is affachod fo a wafor condonsor. Tho condonsor Ioads fo a rocoIvor
consIsfIng of four smaII round boffom fIask usuaIIy caIIod a 'plg' fhrough a rocoIvor adapfor
whIch Is connocfod fo a vacuum pump. ÐIfforonf fracfIons aro coIIocfod by sImpIy rofafIng
fho adapfor. A prossuro moasurIng dovIco Is Insorfod bofwoon fho vacuum pump and fho
adapfor. Tho sampIo Is Infroducod Info fho dIsfIIIIng fIask and hoafod sIowIy fo mako suro
fhaf fho boIIIng procoods smoofhIy wIfhouf bumpIng. A vory fIno capIIIary Is Insorfod Info
fho dIsfIIIIng fIask fo aIIow a fhIn sfroam of aIr bubbIo or nIfrogon fo fho boIIIng IIquId. Tho
boIIIng chIps do nof work undor vacuum. Affor fho dIsfIIIafIon Is ovor, romovo fho hoaf
sourco fIrsf and Ioavo fho apparafus fo cooI fo room fomporafuro boforo roIoasIng fho
vacuum.
LABORATORY EQUIPMENTS AND TECHNIQUES 21
Fig. 2.7: (a) Apparatus for distillation under reduced pressure (b) Pressure measuring device.
Question
2.9 Whon 1-phonyIofhanoI Is purIfIod by dIsfIIIafIon, roducod prossuro Is aIways ompIoyod7
ÐxpIaIn.
2.3.4 Steam Distillation
Sfoam dIsfIIIafIon Is a mofhod usod for fho soparafIon of sIIghfIy voIafIIo and wafor tsfoam)
InsoIubIo compounds from non-voIafIIo compounds. If Is parfIcuIarIy usofuI whon fho voIafIIo
compononf possossos a hIgh boIIIng poInf and Is IIkoIy fo docomposo If a dIrocf dIsfIIIafIon Is
affompfod. ThIs fochnIquo aIso makos possIbIo soparafIon and convonIonf purIfIcafIon of
many IIghf boIIIng compounds by Iow fomporafuro dIsfIIIafIon. A famIIIar oxampIo Is fho
soparafIon by sfoam dIsfIIIafIon of a mIxfuro of - and F- nIfrophonoIs obfaInod by nIfrafIon
of phonoI. A fypIcaI apparafus pIcfurod In !Ig. 2.8 Is usod for sfoam dIsfIIIafIon.
22 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Fig. 2.8: Apparatus for steam distillation.
Sfoam from fho gonorafor tor a sfoam IIno) Is passod fhrough a fIask confaInIng fho
mIxfuro fo bo soparafod. Tho sfoam InIof fubo oxfonds fo fho boffom of fho fIask. ThIs fIask
Is aIso hoafod dIrocfIy by a Bunson burnor. Tho fIask Is aIso fIffod wIfh a CIaIson hoad and
a sfIIIhoad. Tho sfIIIhoad confaIns fho fhormomofor whIIo Ifs ofhor ond Is affachod fo a
condonsor. SInco fho compounds dIsfII aIong wIfh wafor, If Is ossonfIaI fo Incorporafo an
adapfor bofwoon fho gonorafor and fho dIsfIIIIng fIask. Sfoam aIso confaIns wafor, fhoroforo,
If shouId bo romovod boforo admIffIng fho sfoam Info fho fIask In ordor fo provonf fho
voIumo of IIquId In fho fIask whIch wIII bocomo oxcoodIngIy Iargo. Affor fho dIsfIIIafIon Is
ovor, fho organIc compound can bo soparafod from fho wafor-compound mIxfuro In a
soparafory funnoI. If fho quanfIfy of fho compound Is smaII, fhon If can bo oxfracfod wIfh
ofhor. Tho ofhor soIufIon Is drIod wIfh a dryIng agonf and ofhor ovaporafod.
Questions
2.10 ÐoscrIbo fho prIncIpIo of sfoam dIsfIIIafIon.
2.11 Can a mIxfuro of saIIcycIIc acId and FdIchIorobonzono bo soparafod safIsfacforIIy by
sfoam dIsfIIIafIon7 GIvo roasons.
2.12 WouId you oxpocf bromobonzono fo bo purIfIod by sfoam dIsfIIIafIon7
LABORATORY EQUIPMENTS AND TECHNIQUES 23
2.4 CRYSTALLIZATION
CrysfaIIIzafIon Is fho mosf offocfIvo fochnIquo of purIfyIng soIId organIc compounds. If Is
fhough nof appIIcabIo fo subsfancos fhaf roacf chomIcaIIy wIfh wafor. Producfs of organIc
roacfIons aro soIdom puro as fhoy may bo confamInafod oIfhor wIfh fho sfarfIng maforIaI or
somo sIdo-producf. ThIs wIII rosuIf In IoworIng of fho moIfIng poInf. Thoroforo, fo obfaIn
roasonabIy safIsfacfory physIcaI consfanfs, fho subsfanco noods fo bo purIfIod. To accompIIsh
fhIs, dIfforonf mofhods havo boon ompIoyod dopondIng on fho physIcaI sfafo of fho organIc
compound. ÐIsfIIIafIon mofhods as doscrIbod oarIIor aro usod for fho purIfIcafIon of IIquIds.
!or soIIds, on fho ofhor hand, fho fochnIquo of crysfaIIIzafIon Is ompIoyod. A soIId subsfanco
Is dIssoIvod In a suIfabIo soIvonf af Ifs boIIIng poInf and fhon procIpIfafod In a crysfaIIIzod
form on cooIIng. Tho subsfanco Is saId fo bo crysfaIIIzod and fhIs procoss Is roforrod fo as
crystulllzutlon. CrysfaIIIzafIon doponds on fho dIfforonfIaI soIubIIIfy of a subsfanco In a
hof and a coId soIvonf. If Is dosIrabIo fhaf fho soIubIIIfy of fho subsfanco bo hIgh In fho hof
and Iow In fho coId soIvonf. Tho gIasswaros shown boIow aro froquonfIy usod In crysfaIIIzafIon.
PurIfIcafIon by crysfaIIIzafIon roquIros much skIII and pafIonco. A soIvonf Is gonoraIIy
choson In whIch fho ImpurIfIos aro moro soIubIo fhan fho soIId boIng purIfIod. SoIocfIon of
a soIvonf Is nof an oasy maffor fhough Ifs soIocfIon Is vory Imporfanf. Tho maffor Is
sImpIIfIod, If fho subsfanco Is known, fhan fho soIvonf for Ifs crysfaIIIzafIon has boon roporfod.
In fhIs caso ono can Iook up fho soIvonf In fho IIforafuro. On fho ofhor hand, If fho subsfanco
Is now, a suIfabIo soIvonf musf bo soIocfod. Tho bosf way fo fInd a soIvonf for a gIvon
compound Is oxporImonfaI frIaI. ÐIfforonf pofonfIaI soIvonfs may bo frIod by usIng a
25÷30 mg sampIo of fho compound fakon In a fosf fubo. In many ofhor casos, fho soIocfIon
of fho ruIo llke dlssolves may bo foIIowod. AccordIng fo fho ruIo, a subsfanco wIII dIssoIvo
In a soIvonf confaInIng sImIIar groups, or poIar soIvonfs wIII dIssoIvo poIar moIocuIos and
non-poIar soIvonfs wIII dIssoIvo non-poIar moIocuIos. !or Insfanco, for hydrocarbons tnon-
poIar moIocuIos) uso hoxano or pof ofhor. Thoso moIocuIos confaInIng poIar groups such as
ofc. aro moro convonIonfIy crysfaIIIzod from hydroxyIIc
poIar soIvonfs such as aIcohoI. Somo gonoraI suggosfIons for soIocfIng a soIvonf aro IIsfod
In TabIo 2.1.
24 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Table 2.1: Common Organic Solvents used for Recrystallization
Solvent B.P. (
°
C) Denslty Types oI compounds thut cun be
recrystulllzed
Wafor 100 1.00 SaIfs of organIc compounds
95% ofhanoI 78 0.8 AIcohoIs, osfors and acIds
Acofono 56.2 0.792 CarbonyI compounds
ÐfhyI acofafo 77.1 0.900 CarbonyI compounds
ÐIofhyI ofhor 34.5 0.714 Ðfhors
Pof ofhor 30-60 0.601 Hydrocarbons and haIo compounds
LIgroIn 65-75 0.710 Hydrocarbons and haIo compounds
CycIohoxano 80.7 0.799 Hydrocarbons
MofhanoI 65.0 0.791 AIcohoIs, osfors and carboxyIIc acIds
If a sIngIo soIvonf Is nof found safIsfacfory fhan a mIxfuro of fwo soIvonfs may hoIp.
Tho bInary mIxfuro of soIvonfs Is so choson fhaf fho subsfanco Is soIubIo Is ono whIIo
InsoIubIo In fho ofhor. In such a caso, fho compound Is dIssoIvod In ono soIvonf on hoafIng
and fo fho hof soIufIon, fho ofhor soIvonf Is addod dropwIso wIfh swIrIIng fho fIask fIII a
furbIdIfy appoars. Af fhIs sfago a fow drops of fho fIrsf soIvonf aro addod fIII fho soIufIon
bocomos cIoar. Koop fho soIufIon undIsfurbod for crysfaIIIzafIon.
SampIos fo bo crysfaIIIzod offon confaIn soIubIo oxfranoous coIorIng maffor. Thoroforo,
a smaII amounf of acfIvafod charcoaI, I.o., 'Norlt' shouId bo addod fo fho soIufIon and boIIod
for a fow mInufos. Tho amounf of charcoaI shouId bo kopf fo a mInImum as somo of fho
dosIrod producf Is InvarIabIy absorbod on charcoaI. Tho soIufIon Is fIIforod whIIo sfIII hof fo
mInImIzo ovaporafIon of fho hof soIufIon durIng fIIfrafIon. If fhIs Is nof dono, fho soIvonf Is
IIkoIy fo crysfaIIIzo on fho fIIfor papor. Tho fIIfrafo Is cooIod sIowIy af fIrsf and fhon In an
Ico-bafh If nocossary. SIow cooIIng of fho soIufIon Is nocossary bocauso If wIII rosuIf In Iargo
crysfaIs. RapId cooIIng and sfIrrIng wIII Ioad fo smaIIor crysfaIs. Tho sIzo of fho crysfaIs
doponds on fho rafo of cooIIng.
If may bo poInfod ouf fhaf rapId formafIon of soIId maforIaI amounfs fo procIpIfafIon
and Is nof oxacfIy fho samo as crysfaIIIzafIon.
If affor cooIIng fho soIufIon, no crysfaIs appoar, fhon If Is wIso fo Induco crysfaIIIzafIon
by addIng a fow sood crysfaIs of fho puro subsfanco aIroady avaIIabIo fo fho soIufIon. ThIs
wIII provIdo a nucIous for fho crysfaIs fo grow, fhIs procoss Is caIIod seedlng. If fhIs faIIs,
aIfornafIvoIy fho sIdos of fho confaInor may bo scrafchod wIfh a gIass rod. ThIs procoss
provos offocfIvo In InducIng crysfaIIIzafIon. Buf If fhIs aIso faIIs fhon probabIy fhoro Is foo
much soIvonf whIch shouId bo romovod by boIIIng and fho romaInIng soIufIon cooIod agaIn.
!InaIIy, fho soIufIon may bo cooIod In dry Ico-acofono bafh If aII fhoso affompfs faIIs. If fho
compound Is IncapabIo of crysfaIIIzafIon, somo ofhor fochnIquo such as chromafography
may provo hoIpfuI.
LABORATORY EQUIPMENTS AND TECHNIQUES 25
Affor fho crysfaIIIzafIon Is compIofo, fho crysfaIs aro fIIforod In a smaII Buchnor funnoI.
Tho fIIfrafo or fho soIufIon romaInIng affor fho romovaI of crysfaIs Is caIIod fho mother
llquor. ThIs aIso confaIns a sIgnIfIcanf quanfIfy of crysfaIs. Somo soIvonf may bo ovaporafod
from fhIs soIufIon and fho romaInIng soIufIon Ioff for crysfaIIIzafIons fo obfaIn a socond
crop of fho subsfanco. CrysfaIs from mofhor IIquor aro aImosf aIways somowhaf Ioss puro
fhan fho crysfaIs whIch soparafo fIrsf. Tho crysfaIs aro fhon frood of adhorIng soIvonf. !or
fhIs fho crysfaIs aro prossod bofwoon fho foIds of fIIfor papor and squoozod. Thoy aro fhon
fransforrod fo a cIoan wafch gIass. CrysfaIs may bo drIod In aIr af room fomporafuro or In
a vacuum dosIccafor. SmaII sampIos can bo drIod In an AborhaIdon pIsfoI. Tho moIfIng
poInf of fho subsfanco Is fInaIIy doformInod. Two or moro crysfaIIIzafIons may bo nocossary
In somo casos If a safIsfacfory moIfIng poInf Is nof obfaInod of fho crysfaIIIzod sampIo.
Questions
2.13 How Is coIorod producf docoIorIzod from a proparafIon7
2.14 ÐurIng crysfaIIIzafIon, fho soIufIon shouId nof bo rapIdIy cooIod In Ico. Why7
2.15 Whaf objocfIon mIghf bo offorod fo fho uso of a parfIcuIarIy dryIng agonf In fho caso
IIsfod boIow:
ta) CaIcIum chIorIdo for anIIIno.
tb) Phosphorus ponfoxIdo for IsopropyI aIcohoI.
tc) PofassIum hydroxIdo for mofhyI bufyrafo.
2.16 WouId you rocommond sucfIon fIIfrafIon for a soIufIon In whIch pofroIoum ofhor Is fho
soIvonf7
2.17 How doos fho sIzo of crysfaIs dopond on fho rafo of cooIIng of fho soIufIon7
2.18 Whaf Is fho affocf of ImpurIfIos on fho moIfIng poInf of a compound7
2.19 ÐurIng rocrysfaIIIzafIon fho soIufIon shouId nof bo suddonIy cooIod In Ico. Why7
2.5 DRYING AGENTS
If Is nocossary fo dry organIc roacfIon producfs boforo furfhor anaIysIs Is undorfakon.
Prosonco of moIsfuro nof onIy affocfs fho moIfIng poInf and boIIIng poInf buf aIso fho succoss
of fho subsoquonf roacfIons. SoIIds aro normaIIy drIod oIfhor In aIr or In a vacuum dosIccafor.
!or dryIng soIufIons of organIc compounds dIfforonf fypos of dryIng agonfs aro ompIoyod.
Thoso agonfs oIfhor roacf wIfh wafor or form a hydrafo wIfh If. An IdoaI dryIng agonf
shouId nof roacf wIfh fho organIc IIquId and bo oasIIy soparafod by fIIfrafIon from fho drIod
IIquId. Tho agonfs mosf offon usod aro unhydrous sults whIch form hydrafos wIfh wafor
and somo of fhoso aro doscrIbod boIow:
CuIcium suIjuIe tCaSO
4
): If Is aIso known as drlerlte. If Is oxfromoIy fasf and vory
offIcIonf dryIng agonf. Howovor, caIcIum suIfafo has a Iow capacIfy as fwo moIocuIos of
caIcIum suIfafo combIno wIfh onIy ono moIocuIo of wafor t2CaSO
4
. H
2
O) fo form fho hydrafo.
26 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Mugnesium suIjuIe tMgSO
4
): If Is a good dryIng agonf and forms hopfahydrafo
tMgSO
4
. 7H
2
O). ThIs Is probabIy fho mosf safIsfacfory roagonf for gonoraI dryIng purposos.
BosIdos, If Is aIso choap.
SoJium suIjuIe tNa
2
SO
4
): If Is a hIgh capacIfy roagonf buf possossos Iow acfIon and
offIcIoncy. If combInos wIfh sovon and fon moIocuIos of wafor, and Is rocommondod for
romovaI of wafor, ospocIaIIy from ofhor soIufIon of organIc compounds. If Is Ioss offIcIonf
fhan MgSO
4
.
CuIcium chIoriJe tCaCI
2
): If Is good In forms of bofh InfonsIfy and capacIfy, fhough,
If cannof bo usod fo dry amInos, aIcohoIs, phonoIs, acIds and osfors. If Is good for haIIdos
and hydrocarbons.
PoIussium curbonuIe tK
2
CO
3
): If Is a basIc dryIng agonf and Is faIrIy good. If roacfs
wIfh fwo moIocuIos of wafor. If Is good for oxygon and nIfrogon confaInIng compounds.
PoIussium hyJroxiJe tKOH): If Is a basIc dryIng agonf.
Phosphorus penIoxiJe tP
2
O
5
): If Is an acIdIc dryIng roagonf. Tho drIod soIufIon can
bo dIsfIIIod from fho dryIng agonf.
2.6 CLEANING APPARATUS
If Is vory ossonfIaI fhaf cIoan gIasswaros bo usod for carryIng ouf a roacfIon. Prosonco of
ImpurIfIos may havo an advorso offocf on fho dosIrod roacfIons as woII as fho purIfy of fho
fInaI producfs. Ðvory pIoco shouId bo proporIy washod and drIod. NormaIIy any kInd of a
popuIar brand of washIng powdor may bo usod. Buf If fho apparafus Is boIIod wIfh a farry
maforIaI, fhon If can bo dIsIodgod wIfh a smaII quanfIfy of commorcIaI acofono or spocIaI
washIng soIufIons such as chromIc acId soIufIon. Affor fhIs fho apparafus shouId bo rInsod
wIfh wafor and washod wIfh soap soIufIon and fInaIIy agaIn wIfh wafor. !or dryIng an
oIocfrIc ovon may bo usod.
ChupIer 3
DETECTION OF ELEMENTS
In quaIIfafIvo organIc anaIysIs fho prIncIpaI concorn Is wIfh fho dofocfIon and IdonfIfIcafIon
of unknown organIc compounds. Tho unknown may bo a soIId or IIquId. Tho procoss of
IdonfIfIcafIon InvoIvos a sorIos of sfops fhaf hoIp fo osfabIIsh fho IdonfIfy of fho unknown
compound. Tho anaIysIs commoncos wIfh corfaIn proIImInary fosfs whIch offor fho workor
corfaIn cIuos abouf fho fypo and cIass of compound undor oxamInafIon. Any concIusIon
drawn, howovor, doponds on ono`s chomIcaI InfuIfIon and oxporIonco. A sysfomafIc anaIysIs
of dofocfIng fho oIomonfs Is InIfIaIIy carrIod ouf whIch onabIos a rafIonaI choIco of subsoquonf
fosfs fo bo porformod. If Is fhus advIsabIo fo sfarf wIfh fho doformInafIon of physIcaI
proporfIos and fho fypos of oIomonfs prosonf In fho unknown compound.
3.1 PHYSICAL STATE
Tho physIcaI sfafo of fho unknown compound whofhor If Is a soIId or IIquId shouId bo
IndIcafod as a proIImInary oxamInafIon. Tho formor Is somowhaf oasIor fo handIo fhan fho
Iaffor. A soIId somofImos bocomos ¯wof¨ on koopIng bocauso of Ifs hygroscopIc nafuro. ThIs
can aIso happon whon fwo soIIds aro powdorod fogofhor. Affor a carofuI oxamInafIon of fho
shapo and coIor of fho crysfaIs If may bo possIbIo somofImos fo doformIno whofhor fho
unknown Is sIngIo or a mIxfuro of fwo compononfs. HandIo fho chomIcaIs wIfh caro and
novor fasfo anyfhIng.
3.2 COLOR
Nofo fho coIor of fho unknown compound. Nof many organIc compounds aro coIorod. A
coIorod sampIo, fhoroforo, may bo characforIsfIc of corfaIn groups of subsfancos or funcfIonaI
group prosonf In fho unknown. Tho coIor of a compound Is affrIbufod fo fho prosonco of
28 LABORATORY MANUAL OF ORGANIC CHEMISTRY
chromophorIc groups such as ÷NO
2
, ÷NH
2
, C O, ÷N N÷, ofc. Whon such groups
aro Infroducod Info a moIocuIo, absorpfIon maxIma aro shIffod fowards fho vIsIbIo rogIon
and fho subsfanco appoars coIorod. Many sImpIo phonoIs, howovor, affaIn coIor on koopIng
bocauso of afmosphorIc oxIdafIon. Somo oxampIos of fypIcaIIy coIorod compounds aro gIvon
boIow:
Table 3.1: Typical Colors of Some Organic Compounds
Compound Color
F-NIfrofoIuono Lomon
-NIfrophonoI, Iodoform YoIIow
NIfroanIIIno Orango
NIfroanIIIno GoIdon yoIIow
FNIfroanIIIno PaIo yoIIow
NIfrobonzoIc acId CoIorIoss
RosorcInoI LIghf pInk
FCrosoI Ðark pInk
-CrosoI Ðark pInk
>-NaphfhoI ChacoIafo
SuIfanIIIc acId Groy
AnIIIno hydrochIorIdo CoIorIoss buf bocomos
bIack on koopIng
PIcrIc acId YoIIow
Azobonzono Orango
FBonzoquInono YoIIow
3.3 ODOR
SInco a Iargo numbor of organIc compounds possoss characforIsfIc odors, If Is anfIcIpafod
fhaf oIfacfIon may dIscIoso fho prosonco of corfaIn groups of subsfancos. Ðxcopf aromafIc
carboxyIIc acIds ofhor compounds such as aIcohoIs, osfors, aIdohydos, amInos and kofonos
possoss odor. Caro musf bo oxorcIsod In smoIIIng organIc compounds as fho vapors of a
Iargo numbor of compounds aro dangorous. ÐopondIng on fho oxporIonco of fho workor If
may bo possIbIo fo roIafo fho unknown fo a corfaIn cIass of compounds, for Insfanco, osfors
havo famIIIar fruIfy odor whIIo aromafIc hydrocarbons possoss characforIsfIc aroma.
3.4 ACID OR BASE CHARACTER
AcIdIc or basIc nafuro of fho sampIo can bo oasIIy osfabIIshod by usIng a IIfmus or pH papor.
A fow mIIIIgrams of fho compound aro dIssoIvod In a suIfabIo soIvonf IIko wafor, ofhanoI or
DETECTION OF ELEMENTS 29
dIoxano and fosfod wIfh IIfmus papor. A chango In coIor from bIuo fo rod IndIcafos fhaf fho
subsfanco Is acIdIc and rod fo bIuo IndIcafos a basIc subsfanco. On fho ofhor hand, If fhoro
Is no chango fhon fho compound Is noufraI such as aIdohydos, kofonos, osfors or
hydrocarbons. AmInos aro basIc.
3.5 IGNITION TEST
A smaII amounf of fho sampIo Is pIacod on a pIafInum spafuIa and burnf on a nakod fIamo.
ThIs fosf hoIps fo draw somo gonoraI Inforoncos. !or Insfanco, If fho subsfanco burns wIfh
a smoky fIamo fhon If Is consIdorod aromafIc buf aIIphafIc If fho fIamo Is yoIIowIsh. SuIfanIIIc
acId sooms fo bo an oxcopfIon as If doos nof burn wIfh a smoky fIamo. CorfaIn compounds
IIko sugars char and Ioavo a bIack rosIduo on fho spafuIa and omIf a characforIsfIc odor.
OrganIc compounds fhaf do nof burn In fho IgnIfIon fosf may havo a hIgh moIocuIar woIghf
or a hIgh rafIo of haIogon fo hydrogon.
3.6 SOLUBILITY
In gonoraI, Iow moIocuIar woIghf organIc compounds confaInIng poIar funcfIonaI groups
aro soIubIo In wafor. Ofhors aro soIubIo In common organIc soIvonfs such as ofhanoI, acofono,
bonzono, chIoroform, ofc. Tho soIubIIIfy characforIsfIcs of a compound may bo usofuI In fho
cIassIfIcafIon of fho unknown. Tho quanfIfy of fho compound and fho soIvonf ompIoyod In
fho soIubIIIfy fosf aro crIfIcaI If roIIabIo InformafIon Is fo bo dorIvod. NormaIIy a compound
Is consIdorod soIubIo If fho soIubIIIfy of fhaf compound Is groafor fhan 3 parfs of compound
por 100 parfs of fho soIvonf af room fomporafuro. In ofhor words, fho compound Is soIubIo
If If dIssoIvos fo fho oxfonf of abouf 30 mg of soIId or ono drop of fho IIquId In 1 mI of fho
soIvonf. Tho soIvonfs rocommondod for uso In fhIs fosf aro wafor, 5% sodIum hydroxIdo,
5% hydrochIorIc acId and 5% sodIum bIcarbonafo. By chockIng fho soIubIIIfy of a compound
In fhoso roagonfs, If may bo possIbIo fo doformIno whofhor fho unknown has a Iow moIocuIar
woIghf, noufraI compound, an acId, a baso or a saIf. Tho foIIowIng schomo may bo usofuI for
cIassIfIcafIon by moans of soIubIIIfy tp. 30).
ThIs charf offors onIy a guIdoIIno of cIassIfyIng fho compounds by moans of soIubIIIfy.
If Is nof ossonfIaI fo fosf fho compounds In aII of fho soIvonfs, buf soIvonfs shouId bo usod
In fho ordor IIsfod. In caso fho subsfanco Is soIubIo In wafor, If shouId bo fosfod In ofhor In
ordor fo doformIno If If Is a saIf. Howovor, If fho compound Is InsoIubIo In wafor fhoro Is no
nood fo fry ofhor as soIvonf, rafhor froafod wIfh sodIum hydroxIdo, hydrochIorIc acId, sodIum
bIcarbonafo. If fhoro Is a doubf whofhor or nof an approcIabIo quanfIfy of fho subsfanco has
dIssoIvod In acId or baso, fho cIoar soIufIon shouId bo soparafod from fho rosf of fho
compound and noufraIIzod fo soo If fho orIgInaI compound soparafos.
Questions
3.1 Whaf aro fho Inforoncos drawn from fho soIubIIIfy fosf7
3.2 ÐfhyI IodIdo Is poIar buf unIIko such poIar compounds as aIcohoI and acofIc acId If Is
InsoIubIo In wafor. ÐxpIaIn.
3
0
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
DETECTION OF ELEMENTS 31
3.7 ELEMENTAL ANALYSIS
Affor makIng fho procodIng proIImInary oxamInafIons, fho noxf Imporfanf cIass of fosfs Is
fho dofocfIon of oIomonfs In fho unknown. Tho oIomonfs usuaIIy dofocfod aro N, S and fho
haIogons t!, CI, Br, I) whoroas C and H aro aIways assumod fo bo prosonf. Tho prosonco of
oxygon as a parf of fho funcfIonaI group wIII bocomo apparonf Iafor. !or fho dofocfIon of
oIomonfs fho organIc subsfanco Is fIrsf docomposod by fusIon wIfh sodIum mofaI fo proparo
an oxfracf, caIIod fho sodIum fusIon oxfracf.
Procedure: !roshIy cuf a pIoco of sodIum mofaI abouf a quarfor sIzo of a poa and dry In fho
foIds of a fIIfor papor tsodIum Is dangorous, fhoroforo, handIo If carofuIIy). !so a sharp
knIfo fo cuf sodIum. Novor fhrow scraps of sodIum In wafor. PIaco fho sodIum pIoco In an
IgnIfIon fubo hoId wIfh a paIr of fongs. Hoaf fho Iowor parf of fho fubo on a fIamo unfII
sodIum moIfs. Romovo fho fubo from fho fIamo and rapIdIy add a smaII amounf t0.2 g of fho
soIId or 4 drops of fho IIquId) of fho sampIo dIrocfIy ovor fho moIfod sodIum. AgaIn hoaf fho
fubo fo rodnoss, a brIsk roacfIon Is obsorvod. Romovo fho fubo from fho fIamo, add anofhor
smaII porfIon of fho unknown sampIo and hoaf fho fubo agaIn fIII If Is rod hof. Thon
ImmodIafoIy Immorso fho fubo In 15 mI of dIsfIIIod wafor fakon In a chIna dIsh, and crush
Info smaII pIocos wIfh a gIass rod. ThIs wIII hydroIyzo sodIum and dIssoIvo fho Ions In
wafor. BoII fho mIxfuro for 5 mInufos and fIIfor hof fo romovo fho gIass spIInfors. Tho
aIkaIIno fIIfrafo so obfaInod Is usuaIIy caIIod fho sodlum Iuslon extruct. ThIs soIufIon Is
usod In subsoquonf fosfs for oIomonfaI anaIysIs.
ChemicuI reucIions·
C, N Na
+
CN
÷
S Na
2
+
S

X Na
+
X
÷
X = CI, Br, I
ÐurIng fhIs procoss sodIum mofaI combInos wIfh fho oIomonfs prosonf In fho sampIo
and convorfs fhom Info wafor soIubIo saIfs as shown In fho abovo oquafIons.
(a) Tests for nitrogen
Tako 1 mI of sodIum fusIon oxfracf In a fosf fubo and add 2 drops of froshIy proparod
safurafod forrous suIfafo soIufIon. A groon procIpIfafo shouId bo obfaInod. In caso no such
procIpIfafo Is obfaInod, add a fow drops of sodIum hydroxIdo soIufIon. Af fhIs sfago a groon
procIpIfafo shouId appoar. Tho groon procIpIfafo Is duo fo fho formafIon of !otOH)
2
and nof
duo fo fho prosonco of nIfrogon. !orrous hydroxIdo roacfs wIfh sodIum cyanIdo fo form
sodIum forrocyanIdo. BoII fho mIxfuro for 10 soc. and acIdIfy wIfh dII. suIfurIc acId, whIIo
tI) Na
tII) H
2
O
32 LABORATORY MANUAL OF ORGANIC CHEMISTRY
shakIng fIII a cIoar soIufIon Is obfaInod. A PrussIan bIuo coIor IndIcafos fho prosonco of
nIfrogon. ThIs Is caIIod fho Lussulgn's test.
ChemicuI reucIions·
+
4
!oSO 2NaOH
4 2 2
SO Na ) OH t !o +
+
2
!otOH) 6NaCN
 
+
 
1 6 1
Þu Io(CÞ) 2ÞuSO
   
+
   
4 6 2 4
3
3Na !otCN) 2 !o tSO)
 
+
 
4 6 2 4
3
!o !otCN) 6Na SO
On boIIIng fho aIkaIIno soIufIon somo forrIc Ions aro producod by fho oxIdafIon of
forrous Ions by aIr. Bofh forrous and forrIc hydroxIdos dIssoIvo on addIng dII. suIfurIc acId.
Tho forrocyanIdo roacfs wIfh forrIc Ions fo produco fho PrussIan bIuo coIor of forrI-
forrocyanIdo.
Tho aIkaIIno soIufIon shouId nof bo acIdIfIod by hydrochIorIc acId bocauso fho yoIIow
coIor duo fo fho forrIc chIorIdo formod causos PrussIan bIuo fo appoar groonIsh. !orrIc
chIorIdo, as Is usuaIIy rocommondod, shouId nof bo addod for fho samo roason.
Questions
3.3 Why shouId forrous suIfafo soIufIon bo frosh and safurafod In fho fosf for fho dofocfIon
of nIfrogon7
3.4 WouId hydrazIno hydrochIorIdo gIvo LassaIgno`s fosf for nIfrogon7
(b) Tests for sulfur
Tho prosonco of suIfIdo Ion and honco of suIfur In fho sodIum oxfracf Is oasIIy dofocfod
sInco many mofaI Ions tPb, Ag, ofc.) form InsoIubIo suIfIdos.
In a fosf fubo acIdIfy 1 mI of sodIum oxfracf wIfh dII. acofIc acId. In acId any suIfIdo Ion
prosonf Is convorfod fo hydrogon suIfIdo gas. Add 1÷2 drops of Ioad acofafo soIufIon
tproforabIy safurafod soIufIon). Tho appoaranco of a bIack procIpIfafo duo fo fho formafIon
of Ioad suIfIdo IndIcafos suIfur.
ChemicuI reucIions·
+ −
+
2
2 3
Na S 2CH COOH
− +
+
3 2
2CH COO Na H S
tCH
3
COO)
2
Pb + H
2
S PbS + 2 CH
3
COOH
!orrI-forrocyanIdo
SodIum forrocyanIdo
DETECTION OF ELEMENTS 33
SomofImos a brownIsh procIpIfafo Is formod whIch IndIcafos suIfur confaInIng ImpurIfIos
In fho sampIo.
Add 1÷2 drops of froshIy proparod soIufIon of sodIum nIfroprussIdo fo 0.5 mI of fho
sodIum fusIon oxfracf In a fosf fubo. A doop rod or vIoIof coIor confIrms suIfur.
ChemicuI reucIion·
[ ] NO ) CN t !o Na S Na
5 2
2
2
+
− +
[ ] NOS ) CN t !o Na
5 4
(c) Tests for sulfur and nitrogen present together
Whon bofh of fhoso oIomonfs aro prosonf In fho unknown, fhIs ImpIIos fhaf fusIon Is
IncompIofo and no sodIum cyanIdo or sodIum suIfIdo Is formod buf formafIon of sodIum
fhIocyanafo confaInIng bofh N and S oIomonfs fakos pIaco. Tho sodIum oxfracf doos nof
rospond fo IndIvIduaI fosfs for nIfrogon and suIfur. In such a caso procood as foIIows:
AcIdIfy 1 mI of sodIum oxfracf wIfh dII. hydrochIorIc acId and add 1÷2 drops of forrIc
chIorIdo soIufIon, a bIood rod coIor IndIcafos fho prosonco of bofh suIfur and nIfrogon duo fo
fho formafIon of sodIum suIfocyanIdo.
ChemicuI reucIions·
C + N + S NaCNS
3 NaCNS + !oCI
3
!o tCNS)
3
+ 3 NaCI
(d) Tests for halogens
(l) Bellsteln test:
Mako a smaII Ioop t2÷3 mm dIamofor) af ono ond of a coppor wIro t10 cm or
Iongor). Insorf fho ofhor hand of fho wIro In a cork. Hoaf fho Ioop fo rodnoss In a
fIamo and fhon cooI If. ÐIp fho Ioop Info fho unknown and hoaf If In fho non-
IumInous tbIuo) fIamo of fho burnor appoaranco of groon or bIuo fIamo IndIcafos a
haIogon compound.
Try fhIs fosf, fIrsf fakIng a sImpIo haIogon compound such as chIorobonzono.
(ll) Sllver nltrute test:
AcIdIfy 2 mI of fho sodIum fusIon oxfracf wIfh dII. nIfrIc acId and boII. Add sovoraI
drops of sIIvor nIfrafo soIufIon. If haIogons aro prosonf a fIoccuIonf whIfo or yoIIow
procIpIfafo whIch darkons on oxposuro fo IIghf and Is soIubIo In ammonIum
hydroxIdo IndIcafos fho prosonco of haIogons. Tho acIdIfIcafIon of fho sodIum
fusIon oxfracf Is nocossary boforo addIng sIIvor nIfrafo soIufIon fo provonf fho
procIpIfafIon of sIIvor hydroxIdo or sIIvor oxIdo.
SodIum nIfroprussIdo
SodIum fhIocyanafo
!orrIc suIfocyanIdo
tÐoop rod or vIoIof)
Na
34 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuI reucIion·
Na
+
X
÷
+ AgNO
3
AgX + NaNO
3
Tho abovo fosf shows fho prosonco of haIogons In fho sampIo. SInco aII fho haIogons
procIpIfafo In fhIs fosf as AgX, fhIs doformInafIon Is IncompIofo, fhoroforo, fho prosonco of
IndIvIduaI haIogon has fo bo mado. !IuorIno Is nof dofocfod In fhIs fosf sInco sIIvor fIuorIdo
Is soIubIo In wafor. In ordor fo dofocf fho IndIvIduaI haIogons procood as foIIows.
AcIdIfy 2 mI of fho sodIum oxfracf wIfh dII. nIfrIc acId and boII. Add 4÷5 drops of carbon
fofrachIorIdo and 1 mI of frosh chIorIno wafor. Shako fho confonfs vIgorousIy. If fho rosuIfanf
carbon fofrachIorIdo Iayor Is coIorIoss and aIso a fIoccuIonf whIfo procIpIfafo Is obfaInod on
fho addIfIon of sIIvor nIfrafo whIch Is soIubIo In ammonIum hydroxIdo, fhon If IndIcafos
chIorIno. A brown coIor of fho carbon fofrachIorIdo Iayor IndIcafos bromIno whIIo a vIoIof
coIor IndIcafos IodIno. Tho advanfago In fhIs fosf Is fhaf bromIno and IodIno havo
characforIsfIc coIors.
ChemicuI reucIions·
AgCI + 2 NH
3
( )
− +
CI NH Ag
2 3
2 NaBr + CI
2
2 NaCI + Br
2
tRod-orango)
2 NaI + CI
2
2 NaCI + I
2
tVIoIof)
(e) Detection of more than one halogens
If fho sampIo confaIns moro fhan ono haIogons fhon fho foIIowIng procoduro may bo
adopfod. ThIs Is a sonsIfIvo fosf and fhus shouId bo porformod carofuIIy.
AcIdIfy 2 mI of sodIum fusIon oxfracf wIfh acofIc acId. If fho unknown has boon shown
fo confaIn nIfrogon or suIfur fhon fho mIxfuro Is boIIod fo oxpoI hydrogon cyanIdo or hydrogon
suIfIdo gas and fho fIIfrafo Is fakon. To fho fIIfrafo add 3÷4 drops of carbon fofrachIorIdo
and sovoraI drops of sodIum nIfrIfo soIufIon t20%). Appoaranco of vIoIof coIor In carbon
fofrachIorIdo Iayor IndIcafos fho prosonco of IodIno.
ChemicuI reucIion·
2 NaI + 2 NaNO
2
+ 4 CH
3
COOH I
2
+ 2 NO + 4CH
3
COO
÷
Na
+
+ 2H
2
O
IodIno Is romovod from fhIs soIufIon by a ropofIfIon of fho abovo procoss fIII fho carbon
fofrachIorIdo Iayor bocomos coIorIoss. BoII fho aquoous Iayor fo romovo nIfrous oxIdo.
dII. HNO
3
SIIvor dIamIno compIox
DETECTION OF ELEMENTS 35
CooI and add a pInch of Ioad oxIdo and boII fho mIxfuro. If bromIno Is prosonf a sfrIp of
fIuoroscoIn papor pIacod across fho moufh of fho fubo furns pInk.
ChemicuI reucIion·
Romovo bromIno and acIdIfy fho aquoous Iayor wIfh nIfrIc acId and add sIIvor nIfrafo
soIufIon, a hoavy whIfo procIpIfafo soIubIo In ammonIum hydroxIdo IndIcafos chIorIno.
ChemicuI reucIion·
AgCI + 2 NH
4
OH ( ) O H CI NH Ag
2 2 3
+
− +
AIfornafIvoIy fho foIIowIng procoduro may bo usod If chIorIno or ono of fho ofhor
haIogons Is prosonf.
AcIdIfy 2 mI of fho sodIum oxfracf wIfh dII. nIfrIc acId and add sIIvor nIfrafo soIufIon.
!IIfor fho procIpIfafo and wash fwIco wIfh dIsfIIIod wafor. Transfor fho procIpIfafo fo a
smaII fosf fubo and shako wIfh 3 mI of ammonIum carbonafo soIufIon and 2 mI of ammonIum
hydroxIdo soIufIon. !IIfor agaIn and acIdIfy fho cIoar fIIfrafo wIfh dII. nIfrIc acId. Appoaranco
of a fIoccuIonf procIpIfafo IndIcafos fho prosonco of chIorIno. WIfh anofhor fosf porfIon of
fho sodIum oxfracf procood as In Soc. 2.7td) fo fosf for bromIno or IodIno.
(f) Detection of halogens in the presence of nitrogen or sulfur
If fho sampIo confaIns nIfrogon or suIfur or bofh of fhoso oIomonfs fhoy shouId bo romovod
In fho form of gasoous compounds. SodIum cyanIdo If prosonf In sodIum fusIon oxfracf wIII
form a whIfo procIpIfafo of sIIvor cyanIdo wIfh sIIvor nIfrafo whIch Is aIso soIubIo In
ammonIum hydroxIdo.
To 2 mI of fho sodIum oxfracf add a fow drops of dII. nIfrIc acId and boII unfII fho
voIumo Is roducod fo haIf. CyanIdo or suIfIdo Ions aro romovod as hydrogon cyanIdo or
hydrogon suIfIdo gas rospocfIvoIy. CooI fho soIufIon and add dIsfIIIod wafor foIIowod by
sIIvor nIfrafo soIufIon. A hoavy procIpIfafo IndIcafos fho prosonco of haIogons.
ChemicuI reucIions·
NaCN + HNO
3
HCN + NaNO
3
Na
2
S + 2 HNO
3
H
2
S + 2 NaNO
3
A sIIghf furbIdIfy Is nof a posIfIvo fosf. To dofocf fho IndIvIduaI haIogons procood as In
Soc. 3.7 td).
!IuorIno as sfafod oarIIor Is nof dofocfod bocauso sIIvor fIuorIdo Is soIubIo In wafor. If
If Is dosIrod fo dofocf fIuorIno, fho foIIowIng fosf couId bo porformod.
36 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tako 2 mI of sodIum fusIon oxfracf and acIdIfy If wIfh gIacIaI acofIc acId. BoII fho
mIxfuro and roduco fho voIumo fo ono haIf. WIfh a gIass rod, spof fhIs soIufIon on a zIrconIum
- aIIzarIn rod S papor. Tho appoaranco of a yoIIow spof Is a posIfIvo fosf for fho prosonco of
fIuorIno.
Questions
3.5 Why Is fho sodIum fusIon oxfracf acIdIfIod boforo fosfIng for haIogons7
3.6 Why shouId hydrogon cyanIdo and hydrogon suIfIdo bo oxpoIIod boforo a fosf Is mado
for haIIdo Ion7
3.7 How wIII you dIsfInguIsh bofwoon a haIogon prosonf In fho sIdo chaIn and fhaf In fho
aromafIc nucIous7
3.8 How wIII you dofocf chIorIno In fho prosonco of IodIno7
3.9 WrIfo aII fho porfInonf chomIcaI roacfIons InvoIvod for fho dofocfIon of chIorIno In fho
prosonco of nIfrogon.
3.10 Why Is fIuorIno nof dofocfod In fho sodIum fusIon oxfracf wIfh sIIvor nIfrafo7 Suggosf
a mofhod for Ifs dofocfIon.
ChupIer 4
TESTS FOR FUNCTIONAL GROUPS
ÐofocfIon of a funcfIonaI group Is fho noxf sfop In fho IdonfIfIcafIon of an unknown organIc
compound. A carofuI dofocfIon of oIomonfs Is of groaf hoIp In fho osfabIIshmonf of fho
nafuro of fho funcfIonaI group. A numbor of assorfod fosfs for IndIvIduaI groups nood fo bo
porformod for fhoIr IdonfIfIcafIon. In fhIs chapfor fosfs for somo soIocfod funcfIonaI groups
wIII bo doscrIbod.
4.1 ALCOHOLIC GROUP (R–OH)
AIcohoIs may bo consIdorod as noufraI compounds. Thoy aro soIubIo In wafor or dIoxano.
Mosf aIcohoIs oncounforod for anaIysIs wIII bo IIquId. Tho foIIowIng fosfs can bo porformod
for doformInIng fho prosonco of an ÷OH group In a compound.
(a) Ceric ammonium nitrate test
ÐIssoIvo 0.5 mI of fho unknown compound In 1 mI of wafor tor dIoxano for wafor InsoIubIo
compounds) and add 1 mI of corIc ammonIum nIfrafo soIufIon. Shako fho mIxfuro. A rod
coIor Is obfaInod If aIcohoIs aro prosonf whoroas phonoIs gIvo a groon-brown coIor.
ChemicuI reucIion·
(b) Xanthate test
Add a poIIof of pofassIum hydroxIdo fo 0.5 mI of fho unknown IIquId sampIo and warm If fIII
fho poIIof dIssoIvos. CooI and add a fow drops of carbon dIsuIfIdo and shako. Appoaranco of
a yoIIow procIpIfafo IndIcafos an aIcohoI. ThIs fosf Is posIfIvo for prImary, socondary and
forfIary aIcohoIs.
38 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuI reucIions·
(c) Test with acetyl chloride
In a dry fosf fubo, fako fho unknown sampIo t0.5 mI of IIquId or 500 mg soIId). Add 0.3 mI
acofyI chIorIdo dropwIso usIng a pIpoffo. An ImmodIafo roacfIon, IndIcafod by fho mIxfuro
bocomIng hof and an osfor-IIko odor Is posIfIvo IndIcafIon for an aIcohoI ta prImary or
socondary). AmInos and phonoIs aIso roacf, buf amInos do nof gIvo pIoasanf odors.
(d) Vanadium oxine test
In a fosf fubo, pIaco a drop of aquoous ammonIum vanadafo soIufIon and 1 drop of
8-hydroxyquInoIIno soIufIon toxIno) In dII. acofIc acId. A groon compIox of vanadIum oxIno
Is formod. Now add 2 mI of aIcohoI tor a soIufIon In dIoxano for wafor InsoIubIo aIcohoIs)
and shako. A rod coIor Is obfaInod for prImary aIcohoIs tofhanoI, n-bufanoI), whIIo socondary
aIcohoIs tIsopropanoI, scc. bufanoI) yIoId orango coIor on koopIng, and a IIghf orango coIor
on Iong sfandIng Is obfaInod In fho caso of forfIary aIcohoIs tforf. bufanoI) fosf.
(e) Distinction between primary, secondary and tertiary alcohols
Onco If has boon osfabIIshod fhaf an aIcohoIIc group Is prosonf, fho noxf IogIcaI sfop Is fo
dIsfInguIsh bofwoon prImary, socondary and forfIary aIcohoIs. To achIovo fhIs, fho unknown
Is froafod wIfh a roagonf and fho dIsfIncfIon Is fhon mado oIfhor on fho fImIng of fho
roacfIon bofwoon fho roagonf and fho compound or on fho soparafIon of dIfforonf producfs.
Tho Lucus test ufIIIzos fho formor concopf. ThIs fosf may bo usod onIy wIfh wafor soIubIo
aIcohoIs. Add 3÷4 drops of aIcohoIs fo 2 mI of Lucus reugent tanhyd. zInc chIorIdo + conc.
hydrochIorIc acId) In a fosf fubo, shako fho mIxfuro and fhon aIIow fo sfand af room
fomporafuro. ImmodIafo soparafIon of fwo phasos duo fo fho formafIon of an InsoIubIo
chIorIdo IndIcafos a forfIary aIcohoI. A cIoudy soIufIon Is producod In 5÷10 mIn In fho caso
of socondary aIcohoI whIIo fho soIufIon romaIns cIoar for a prImary aIcohoI.
TESTS FOR FUNCTIONAL GROUPS 39
ChemicuI reucIions·
A posIfIvo fosf doponds on fho facf fhaf aIcohoI Is soIubIo In fho roagonf whIIo fho
aIkyI chIorIdo Is nof.
ThIs fosf faIIs If zInc chIorIdo Is nof anhydrous or If fho roagonf had boon sIffIng on fho
shoIf for a Iong fImo. In caso of doubf whofhor fho aIcohoI Is forfIary or socondary, conc.
hydrochIorIc acId may bo ompIoyod.
To 1 mI of aIcohoI In a fosf fubo add 5 mI of conc. hydrochIorIc acId and shako. A Iayor
of aIkyI chIorIdo soparafos ImmodIafoIy In fho caso of forfIary aIcohoI buf socondary aIcohoIs
roacf sIowIy and fho soIufIon romaIns cIoar tor If may bocomo furbId affor somofImo).
ChemicuI reucIion·
(f) Chromic acid test
A rafhor rapId fosf for dIsfInguIshIng a forfIary from socondary and prImary aIcohoIs InvoIvos
fho oxIdafIon wIfh chromIc anhydrIdo.
ÐIssoIvo 1 g of chromIc anhydrIdo In 10 mI of conc. suIfurIc acId or chromIc acId and
pour fho soIufIon sIowIy wIfh consfanf sfIrrIng Info 30 mI of dIsfIIIod wafor. CooI fho rosuIfanf
doop orango soIufIon. ThIs Is fho oxIdIzIng roagonf.
40 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ÐIssoIvo 1 drop t10 mg) of fho unknown aIcohoI In 1 mI of puro acofono. Add 1 drop of
fho abovo roagonf whIIo shakIng, fho orango coIor dIsappoars. PrImary and socondary aIcohoIs
roacf fo gIvo a procIpIfafo fhaf causo fho soIufIon fo bocomo opaquo wIfh a groonIsh or
groonIsh bIuo fInf. TorfIary aIcohoIs do nof roacf and fho fosf soIufIon romaIns orango. Any
of fhoso changos fakIng pIaco affor fwo mIn may bo dIsrogardod. !or fho succoss of fhIs fosf
fho sampIo shouId nof confaIn an aIdohydo funcfIon.
ChemicuI reucIions·
Questions
4.1 Whaf Is fho basIs of fho Lucas fosf7
4.2 Why Is If ossonfIaI fo uso anhydrous zInc chIorIdo In fho Lucas fosf7
4.2 PHENOLIC GROUP (AR–OH)
PhonoIs aro coIorIoss compounds buf affaIn coIor duo fo oxIdafIon. Moroovor, fhoy aro
acIdIc and dIssoIvo In 5% sodIum hydroxIdo soIufIon buf nof In sodIum bIcarbonafo soIufIon.
Tho fosfs usod fo dofocf phonoIs aro aIso basod on fho roacfIons of fho phonoIIc group.
PhonoIs aro gonoraIIy hIghIy roacfIvo In oIocfrophIIIc afomafIc subsfIfufIons. On
bromInafIon tbromIno wafor) of phonoI, 2,4,6- frIbromophonoI a whIfo soIId compound Is
obfaInod.
(a) Ferric chloride test
To 1 mI of a dIIufo soIufIon t50 mg In 1 mI of wafor or aquoous mofhanoI or ofhanoI) of
phonoI, add 1-2 drops tonIy) of 5% noufraI forrIc chIorIdo soIufIon. A coIorod soIufIon of a
compIox Is producod.
TESTS FOR FUNCTIONAL GROUPS 41
Table 4.1: Observation of Colors in FeCl
3
Addition to Phenols
Color observed Compound gluss
BIuo or bIuIsh vIoIof RosorcInoI, crosoIs, phIorogIucInoI,
saIIcyIIc acId
Groon tdarkons rapIdIy) CafochoI
VIoIof tpurpIo) PhonoI, p-bromophonoI, p-chIorophonoI
RoddIsh brown PyrogaIIoI
Rod vIoIof n- or p-nIfrophonoIs
Offon a whIfo procIpIfafo =-NaphfhoI
Groon >-NaphfhoI
Tho coIor producod may nof bo pormanonf, fhoroforo, obsorvafIon shouId bo mado af
fho fImo of addIfIon. AIways uso a dIIufo soIufIon of phonoI. ThIs fosf Is nogafIvo wIfh
n-and p-hydroxybonzoIc acIds.
ChemicuI reucIion·
Tho roacfIon fakos pIaco In poIar soIvonfs, fhoroforo, a fow drops of pyrIdIno aro noodod
If If Is carrIod ouf In a non-poIar soIvonf, tofhor, bonzono, ofc.). CorfaIn phonoIs IIko
o-nIfrophonoI and quInoI do nof gIvo any coIor In fhIs fosf.
!orrIc compIoxos aro formod In fhoso roacfIons and poIar soIvonfs IIko mofhanoI Is
fho mosf suIfabIo modIum. NIfrophonoIs can bo oxprossod as mosomorIc sfrucfuros wIfh a
posIfIvo chargo on fho nIfrogon afom and compofIng wIfh forrIc Ions In fhoIr InfIuonco on
oIocfron paIr fhus woakonIng fho Iron-oxygon bond. AddIfIon of acIds dosfroys fho coIor In
fhIs fosf, p-hydroxybonzoIc acId doos nof gIvo coIor for fhIs roason. SaIIcyIIc acId, on fho
ofhor hand gIvos a bIuo coIor bocauso If forms a sfrong compIox wIfh forrIc chIorIdo.
Question
4.3 Why doos o-nIfrophonoI gIvo no coIor wIfh !oCI
3
soIufIon7
42 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(b) Liebermann test
PIaco 0.2 g of fho unknown In a dry fosf fubo and dIssoIvo In 1 mI of conc. suIfurIc acId. Add
a fow crysfaIs of sodIum nIfrIfo. ImmodIafoIy a bIuo groon or bIuo vIoIof coIor Is formod.
ÐIIufo fho confonfs wIfh wafor, fho coIor changos fo rod whIch furns bIuo on dIIufIon wIfh
sodIum hydroxIdo soIufIon. CoIor formafIon Is obsorvod duo fo fho producfIon of a saIf of
IndophonoI.
ChemicuI reucIion·
OnIy fhoso phonoIs possossIng a froo para posIfIon rospond fo fhIs fosf. RosorcInoI
rosponds fo fhIs fosf.
(c) Phthalein test
Hoaf 0.2 g oach of fho unknown and phfhaIIc anhydrIdo wIfh onIy 2 drops of conc. suIfurIc
acId In a fosf fubo for 1 mIn. CooI and carofuIIy add fho confonfs fo 10% sodIum hydroxIdo
soIufIon fakon In a boakor. CharacforIsfIc coIors aro obfaInod.
Table 4.2: Colors observed in Phthalein Test
Color observed Llkely ulcohol
PInk PhonoI
BIuo CafochoI
Rod soIufIon wIfh groon RosorcInoI
fIourosconco
Ðoop purpIo HydroquInono
!aInf groon =-and >-NaphfhoIs
No coIor p-CrosoI
TESTS FOR FUNCTIONAL GROUPS 43
ChemicuI reucIion·
Questions
4.4 In fho bromInafIon tBr
2
+ H
2
O) of phonoI fhough hydrogon bromIdo Is ovoIvod buf Ifs
ovoIufIon Is nof obsorvod why7
4.5 Is bromInafIon of phonoI fasfor In wafor or carbon fofrachIorIdo7
4.3 CARBONYL GROUP
Tosfs for fho dofocfIon of aIdohydos and kofonos groups wIII bo dIscussod undor
fhIs socfIon. Thoso aro noufraI compounds and confaIn roacfIvo carbonyI group. In mosf
chomIcaI roacfIons aIdohydos aro moro roacfIvo fhan kofonos. In many casos fhoy undorgo
sImIIar roacfIons, for oxampIo, addIfIon and roducfIon. Thus If Is nocossary af fIrsf fo
44 LABORATORY MANUAL OF ORGANIC CHEMISTRY
dIsfInguIsh fhom from aIcohoIs. Ono usofuI mofhod fo do fhIs Is fo froaf fhom wIfh 2,4-
dInIfrophonyIhydrazIno, whoroby a brIghf orango crysfaIIIno soIId soparafos ouf In fho caso
of carbonyI compounds onIy, buf nof aIcohoIs.
Tho hIgh roacfIvIfy of fho compounds wIfh fhIs roagonf Is duo fo fho characfor of fho
carbonyI group.
In a fosf fubo fako 0.1 g t3 drops If IIquId) of fho unknown and dIssoIvo In 2 mI of 95%
ofhanoI. Add 2÷3 drops of fho 2, 4-dInIfrophonyIhydrazIno soIufIon Info fho fubo and shako.
AIIow fho fubo fo sfand for 15 mInufos or fIII a procIpIfafo Is formod. Scrafch fho sIdos of
fho fubo If nocossary ÷ formafIon of a crysfaIIIno yoIIow or orango-rod procIpIfafo IndIcafos
an aIdohydo or kofono.
AIdohydos aro gonoraIIy moro roacfIvo fhan kofonos, fho formor aro IdonfIfIod by
oxIdIzIng roagonfs such as ToIIons, BonodIcf and chromIc acId.
(a) Tollens’ test
In a fosf fubo pIaco 1 mI of froshIy proparod 10% sIIvor nIfrafo soIufIon. To fhIs add 1 mI of
10% ammonIum hydroxIdo soIufIon shakIng If fIII fho procIpIfafo formod jusf dIssoIvos.
ThIs soIufIon confaIns fho sIIvor dIamIno compIox AgtNH
3
)
2
+
whIch Is a woak oxIdIzIng
agonf. If Is roadIIy roducod fo mofaIIIc sIIvor. Add a fow drops t0.2 g) of fho unknown aIong
fho sIdos of fho fubo. A sIIvor mIrror Is doposIfod duo fo fho roducfIon of sIIvor Ions fo
mofaIIIc sIIvor In fho coId or on warmIng In a boakor of hof wafor.
ChemicuI reucIion·
Kofonos, ofhors and ovon aIcohoIs do nof rospond fo fhIs fosf bocauso IIko aIdohydos
fhoy cannof bo oxIdIzod fo carboxyIIc acIds. AromafIc aIdohydos rospond poorIy.
=-Hydroxykofonos aro oxIdIzod, fhough, fo dIkofons.
TESTS FOR FUNCTIONAL GROUPS 45
(b) Schiff’s test
SchIff `s roagonf consIsfs of an aquoous soIufIon of fuchsIno tp-rosanIIIno hydrochIorIdo)
docoIorIzod by passIng suIfur dIoxIdo gas. If Is a spocIfIc fosf for aIdohydos and rosforafIon
of fho pInk coIor of SchIff`s roagonf fakos pIaco.
To 1.5 mI of fho roagonf tI) add a fow drops of fho unknown subsfanco. A pInk coIor tII)
appoars In fho prosonco of an aIdohydo In fho coId. Ðo nof warm fho soIufIon.
ChemicuI reucIions·
Tho appoaranco of coIor Is nof causod by sImpIo oxIdafIon fo fuchsIno rafhor roprosonfs
a spocIfIc roacfIon of fho aIdohydo group. !uchsIno IoukosuIfonIc acId tI) roacfs wIfh aIdohydo
and suIfurous acId whIch on oIImInafIon of a moIocuIo of suIfurous acId yIoIds fho coIorod
mosomorIc cafIon tII). Tho roacfIon mIxfuro shouId nof bo hoafod ofhorwIso a pInk coIor Is
obfaInod ovon In fho absonco of an aIdohydo. In a sfrongIy acIdIc soIufIon, formaIdohydo
yIoIds a bIuo-vIoIof coIor. AII aIIphafIc and aromafIc aIdohydos and p-hydroxybonzaIdohydo
rospond fo fhIs fosf, buf saIIcyIaIdohydo doos nof.
46 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(c) Benedict’s solution test
ThIs Is a modIfIcafIon of !ohIIng`s soIufIon fosf and consIsfs of aIkaIIno cuprIc Ions compIoxod
wIfh cIrrafo Ions.
PIaco 4 mI of BonodIcf`s roagonf In a fosf fubo and add a fow drops of fho unknown tor
a soIufIon of fho soIId In ofhanoI or wafor). Hoaf fho mIxfuro fo boIIIng. A posIfIvo fosf Is
IndIcafod by fho formafIon of a yoIIow fo rod procIpIfafo of cuprous oxIdo. ThIs fosf Is gIvon
onIy by aIphafIc aIdohydos buf fho roagonf Is nof capabIo of oxIdIzIng fho aromafIc aIdohydos
such as bonzaIdohydo. Thus If sorvos fo dIsfInguIsh bofwoon ullphutlc and uromutlc
uldehydes.
ChemicuI reucIion·
(d) Chromic acid test
ThIs Is anofhor mofhod fo dIsfInguIsh bofwoon aIdohydos and kofonos. ThIs roagonf oxIdIzos
prImary and socondary aIcohoIs and aII aIdohydos wIfh a characforIsfIc coIor chango.
ÐIssoIvo 0.1 g of fho subsfanco In 1 mI of good grado acofono In a fosf fubo. To fhIs add
ono drop of fho acIdIc chromIc anhydrIdo roagonf and shako fho fubo. ÐIsappoaranco of fho
orango coIor of fho roagonf and formafIon of groon or bIuo groon procIpIfafo IndIcafos a
posIfIvo fosf for aIdohydos.
Thoro Is no vIsIbIo coIor chango wIfh forfIary aIcohoIs and kofonos.
ChemicuI reucIions·
Kofonos rospond nogafIvoIy fo fho abovo fosfs and fhus can bo dIsfInguIshod from
aIdohydos. Tho foIIowIng fosf can bo ompIoyod for fho dofocfIon of kofonos.
(a) Iodoform test (ketones containing grouping)
ÐIssoIvo 0.1 g of fho unknown kofono In 2 mI wafor tmofhanoI or dIoxano for wafor InsoIubIo
TESTS FOR FUNCTIONAL GROUPS 47
subsfanco). To fhIs add 1 mI of 10% sodIum hydroxIdo soIufIon and IodIno-pofassIum IodIdo
roagonf dropwIso fIII a dofInIfo dark coIor of IodIno porsIsfs. AIIow If fo sfand for sovoraI
mInufos af room fomporafuro. If fho coIor dIsappoars add moro roagonf fIII fho coIor porsIsfs.
AIIow fo sfand for 15 mIn. A posIfIvo fosf Is IndIcafod by fho formafIon of a yoIIow procIpIfafo
of Iodoform tm.p. 120
o
C) of characforIsfIc odor. If fho subsfanco was InsoIubIo In wafor fhon
af fho ond of fho roacfIon dIIufo wIfh 10 mI wafor.
ChemicuI reucIions·
ThIs roacfIon fakos pIaco fhrough fho formafIon of a carbanIon, fhoroforo, fho hydroxyI
Ions shouId aIways bo prosonf In oxcoss.
48 LABORATORY MANUAL OF ORGANIC CHEMISTRY
AIIphafIc kofonos tacofono, mofhyI ofhyI kofono, 2-hopfanono, mofhyI propyI kofono,
ofc.), mIxod kofonos tacofophonono and Ifs p-subsfIfufod dorIvafIvos) and aIcohoIs tofhanoI,
iso-propanoI, scc-bufanoI, 2-ocfanoI, ofc.) aIso rospond fo fhIs fosf.
SInco corfaIn aIcohoIs whIch can bo oxIdIzod fo mofhyI kofonos gIvo a posIfIvo fosf In
fho Iodoform roacfIon fhIs fosf fhus onIy bo carrIod ouf If prosonco of a carbonyI group Is
confIrmod.
(b) m-Dinitrobenzene test
ThIs fosf Is aIso ompIoyod proforabIy for mofhyI kofonos.
To a dIIufo soIufIon of fho unknown kofono In ofhanoI add 1% ofhanoIIc n-
dInIfrobonzono soIufIon and 2 drops of dII. sodIum hydroxIdo soIufIon. ÐovoIopmonf of a rod
coIor Is obsorvod. Acofono, mofhyI ofhyI kofono, acofophonono gIvo rod coIor ImmodIafoIy.
Bonzophonono and bonzaIdohydo gIvo a IIghf rod coIor In fho bogInnIng whIch doopons on
sfandIng. SaIIcyIaIdohydo gIvos a yoIIow coIor In fho bogInnIng whIch furns pInk on sfandIng.
SInco n-dInIfrobonzono IfsoIf gIvos a pInk coIor wIfh sodIum hydroxIdo soIufIon a
sampIo may bo proparod for coIor comparIson.
Questions
4.6 Why aro aIdohydos moro roacfIvo fhan kofonos7
4.7 Why do wo nof uso ofhanoI as soIvonf In Iodoform fosf7
4.8 AIdohydos roacf wIfh noufraI pofassIum pormanganafo fo dIschargo fho purpIo coIor
and gIvo brown procIpIfafo. Why Is fhIs nof usod as a fosf for aIdohydos7
4.9 A compound gIvos a posIfIvo fosf wIfh 2, 4-dInIfrophonyIhydrazIno buf If doos nof
roduco ToIIons` roagonf. Whaf Is fho nafuro of fho compound7
4.10 GIvon aro fhroo sampIos of 3-ponfanono, ponfanaI and 2-ponfanono. How wouId you
doformIno by sImpIo fosfs whIch Is whIch7 WrIfo chomIcaI roacfIons.
4.11 WrIfo fho producf of fho roacfIon:
4.12 How wouId you dIsfInguIsh bofwoon aIIphafIc and aromafIc aIdohydos7
TESTS FOR FUNCTIONAL GROUPS 49
4.4 CARBOXYL GROUP
CarboxyIIc acIds do nof gIvo characforIsfIc coIor roacfIons fhoroforo, for fhIs cIass of
compounds fho dofocfIon doponds on fhoIr acIdIfy. ThIs Is doformInod by moans of IIfmus
papor for wafor soIubIo acIds tIowor moIocuIar woIghf acIds) and wIfh sodIum bIcarbonafo
for wafor InsoIubIo acIds.
(a) Litmus paper test
ÐIssoIvo 0.1 g of fho unknown In a mInImum voIumo of wafor. WIfh a gIass rod appIy a drop
on a bIuo IIfmus papor. A chango fo rod coIor IndIcafos fho subsfanco fo bo acIdIc.
(b) Sodium bicarbonate test
PIaco 0.2 g of fho unknown In a fosf fubo and add 1 mI of 5% aquoous sodIum bIcarbonafo
soIufIon. Appoaranco of offorvosconco IndIcafos fho prosonco of an acId.
ChemicuI reucIion·
ThIs fosf aIso dIfforonfIafos bofwoon acIds and phonoIs as fho Iaffor aro InsoIubIo In
sodIum bIcarbonafo soIufIon. Howovor, fhoso phonoIs whIch confaIn oIocfron-wIfhdrawIng
groups such as 2, 4-dInIfrophonoI aro soIubIo In sodIum bIcarbonafo. A safIsfacfory
IdonfIfIcafIon of an acId roquIros fho proparafIon of Ifs approprIafo dorIvafIvo.
Questions
4.13 How wouId you dIsfInguIsh bofwoon bonzoIc acId and phonoI7
4.14 WouId you oxpocf a carboxyI group fo form an oxImo7
4.5 ESTER GROUP
Ðsfors aro noufraI and many of fhom possoss characforIsfIc fruIfy smoII.
(a) Phenolphthalein test
ÐIssoIvo fwo drops of fho unknown In 1÷2 mI of ofhanoI and add fwo drops of phonoIphfhaIoIn
50 LABORATORY MANUAL OF ORGANIC CHEMISTRY
IndIcafor and fwo drops of 0.1 sodIum hydroxIdo soIufIon. If on hoafIng fho pInk coIor
dIsappoars fhon an osfor Is IndIcafod.
(b) Hydroxamic acid test
PIaco 0.1 g of fho unknown In a fosf fubo and add 1 mI of hydroxyIamIno hydrochIorIdo
soIufIon In ofhanoI. Mako fho soIufIon aIkaIIno wIfh 10% sodIum hydroxIdo soIufIon. Hoaf
fho mIxfuro jusf fo boIIIng. CooI and jusf acIdIfy fho soIufIon wIfh dII. hydrochIorIc acId.
Add 1-2 drops of forrIc chIorIdo soIufIon. ÐovoIopmonf of a rod-vIoIof coIor IndIcafos fho
prosonco of an osfor. In fhIs fosf fho osfor Is convorfod fo a hydroxamIc acId whIch fhon
compIoxos wIfh forrIc Ions fo yIoId a coIorod spocIos forrIc hydroxymafo.
ChemicuI reucIions·

AcId chIorIdos, amIdos and anhydrIdos aIso rospond fo fhIs fosf.
4.6 CARBOHYDRATES
Mono- and - dIsaccharIdos aro coIorIoss soIIds soIubIo In wafor buf InsoIubIo In mosf organIc
soIvonfs. Thoy do nof possoss sharp moIfIng poInfs rafhor docomposo on hoafIng. Thoy
confaIn roacfIvo groups whIch gIvo corfaIn coIor roacfIons. A cIassIfIcafIon Info roducIng
and non-roducIng sugars can bo affocfod by fho BonodIcf`s roagonf.
AII monosaccharIdos and many dIsaccharIdos aro roducIng sugars. ThIs Is ascrIbod fo
fho prosonco of an aIdohydo or =-hydroxy kofo group In fho sugar fhaf can parfako In an
oxIdafIon-roducfIon roacfIon. ÐIsaccharIdos In whIch ono of fho rIngs Is a homIacofaI aro
roducIng sugars, buf fhoso In whIch bofh rIngs aro In acofaI or kofaI form aro non-roducIng
sugars. ThIs Is basod on fho facf fhaf fhoy cannof bo In oquIIIbrIum wIfh fho aIdohydIc or
fho kofonIc form.
TESTS FOR FUNCTIONAL GROUPS 51
(a) Molisch test
ThIs Is a gonoraI fosf for carbohydrafos.
ÐIssoIvo 0.1 g of fho unknown In 1 mI wafor In a fosf fubo. Add 3÷4 drops of a 10%
soIufIon of =-naphfhoI In ofhanoI and add 1.5 mI of conc. suIfurIc acId aIong fho sIdos of fho
fubo. A vIoIof or rod coIor Is formod af fho Inforfaco of fho fwo IIquIds. On shakIng, fho
soIufIon affaIns a dark vIoIof coIor.
GIucoso and frucfoso tmonosaccharIdos), sucroso, Iacfoso and maIfoso tdIsaccharIdos)
rospond fo fhIs fosf
(b) Charring of carbohydrates
If fho abovo fosf Is posIfIvo fhon porform fho foIIowIng fosf.
In a smaII fosf fubo hoaf 0.25 g of fho carbohydrafo wIfh 1 mI of conc. suIfurIc acId.
ImmodIafo charrIng fakos pIaco, whIch IndIcafos a carbohydrafo.
(c) Benedict’s test
To 2 mI of BonodIcf`s roagonf, add 0.2 mI of a 2% soIufIon In wafor of fho unknown. BoII fho
mIxfuro and fhon aIIow If fo cooI. A rod procIpIfafo forms wIfh a roducIng sugar, whIIo fho
soIufIon romaIns cIoar wIfh a non-roducIng sugar.
ChemicuI reucIion·
IdonfIfIcafIon of IndIvIduaI sugars Is osfabIIshod by proparIng fho osazono tsoo chapfor 6).
CorfaIn IndIvIduaI fosfs may aIso bo ompIoyod for oach sugar.
Glucose
Tako 2 mI of fho aquoous soIufIon of sugar In a fosf fubo add 50 mg of Ioad acofafo and
hoaf fo boIIIng. Add 5 mI of dII. ammonIum hydroxIdo and boII fho mIxfuro agaIn for 1
mIn÷roso pInk coIor appoars.
Fructose
To 2 mI of fho aquoous soIufIon of sugar In a fosf fubo add an oquaI voIumo of conc.
hydrochIorIc acId and 10 mg of rosorcInoI warm fho fubo In a boakor of boIIIng wafor for 2
mIn÷a doop rod coIor appoars foIIowod by a procIpIfafo.
52 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Guluctose
PIaco 0.5 g of fho subsfanco In a dry fosf fubo and add 1.5 mI of 50% nIfrIc acId. AIIow
fho fubo fo sfand In a boakor of boIIIng wafor unfII rod fumos ovoIvo. Thon koop fho fubo
for 15 mIn In anofhor boakor confaInIng wafor af 70
o
C÷a whIfo procIpIfafo rosuIfs.
Sucrose
Sucroso doos nof roduco !ohIIng`s soIufIon. On froafmonf wIfh conc. suIfurIc acId, If
gofs charrod ovon In coId. Sucroso aIso rosponds fo coIor fosfs.
ÐIssoIvo 0.5 g of fho subsfanco In 2 mI of dIsfIIIod wafor. To fhIs add 0.1 g of rosorcInoI
and 1.5 mI conc. hydrochIorIc acId. BoII fho mIxfuro for 2 mIn÷a doop wIno rod coIor
appoars.
Questions
4.15 Whaf Is fho coIor duo fo In fho MoIIsch fosf for carbohydrafos7
4.16 How wIII you dIsfInguIsh bofwoon roducIng and non-roducIng sugars7
4.17 How wIII you dIsfInguIsh bofwoon sfarch and gIucoso7
4.7 NITRO GROUP
Prosonco of a nIfro group Is usuaIIy IndIcafod by Iongfhy roducfIon or oxIdafIon roacfIons.
(a) Reduction to hydroxylamine compound
ÐIssoIvo 0.1 g of fho unknown In 2 mI ofhanoI and add 5 drops of caIcIum chIorIdo soIufIon.
Add a pInch of zInc dusf and boII fho confonfs for 5 mIn. !IIfor fho soIufIon Is a fosf fubo
confaInIng 1 mI of ToIIons` roagonf. A groy or bIack procIpIfafo tAg) IndIcafos fho prosonco
of a nIfro group. Insfoad zInc and acofIc acId may bo usod for fho roducfIon of fho nIfro
group. In fhIs fosf fho nIfro group Is parfIaIIy roducod fo hydroxyIamIno whIch Is IfsoIf a
roducIng agonf and gIvos a posIfIvo ToIIons` fosf.
ChemicuI reucIions·
ThIs fosf Is appIIcabIo If fho orIgInaI unknown gIvos a nogafIvo ToIIons` fosf.
TESTS FOR FUNCTIONAL GROUPS 53
(b) Ferrous hydroxide test
PIaco abouf 20 mg of fho unknown In a smaII fosf fubo and mIx wIfh 1.5 mI of froshIy
proparod 5% soIufIon of forrous ammonIum suIfafo. Add 1 drop of 6 N suIfurIc acId foIIowod
by 1 mI of 2N pofassIum hydroxIdo soIufIon In mofhanoI. Sfoppor fho fubo quIckIy and
shako vIgorousIy÷rod-brown procIpIfafo Is obfaInod.
ChemicuI reucIion·
Question
4.18 Is fho ovaIuafIvo fosf for fho nIfro group appIIcabIo fo p-nIfrobonzaIdohydo7 ÐxpIaIn.
4.8 AMINO GROUP (–NH
2
)
AmInos aro basIc subsfancos InsoIubIo In wafor buf soIubIo In mInoraI acIds.
(a) Diazotisation and coupling
ÐIssoIvo 50 mg of fho unknown amIno In 2 mI of 2N hydrochIorIc acId In a fosf fubo. CooI
fho soIufIon fo 5
o
C In an Ico-bafh. In a socond fosf fubo cooI 50 mg of >-naphfhoI In 2 mI of
10% sodIum hydroxIdo soIufIon. Whon fho soIufIons aro cooIod add sodIum nIfrIfo soIufIon
fo fho amIno wIfh shakIng, foIIowod by fho addIfIon of >-naphfhoI soIufIon. !ormafIon of an
orango fo rod dyo Is IndIcafIvo of a prImary aromafIc amIno.
ChemicuI reucIion·
(b) Carbylamine test
PIaco a smaII amounf of fho amIno In a fosf fubo and dIssoIvo In aIcohoIIc sodIum hydroxIdo
soIufIon. Add a fow drops of chIoroform and warm fho mIxfuro gonfIy. A fouI odor of IsonIfrIIo
tcarbyIamIno) Is producod.
54 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuI reucIion·
ThIs roacfIon shouId bo porformod In fho fumo chambor. Bofh aIIphafIc and aromafIc
prImary amInos rospond fo fhIs fosf. ThIs fosf Is nogafIvo bofh for socondary and forfIary
amInos. Boforo pourIng Info fho sInk, fho mIxfuro shouId bo acIdIfIod wIfh dII. hydrochIorIc
acId. ThIs wouId convorf fho IsonIfrIIo Info fho corrospondIng hydrochIorIdo of fho amIno.
A dIsfIncfIon bofwoon a prImary aIIphafIc and aromafIc prImary amInos can bo mado by fho
coupIIng fosf tparf a).
An addIfIonaI fosf for prImary aIIphafIc amInos may bo porformod.
Add 1÷2 drops of fho subsfanco t0.1 g for soIId) In a fosf fubo. Add 3 mI wafor foIIowod
by 1 mI acofono. Shako fo mIx. Add 2 drops of 1% aquoous soIufIon of sodIum nIfroprusIdo.
A rod-vIoIof coIor appoars.
As In fho caso of aIcohoIs If Is aIso ossonfIaI fo dIsfInguIsh bofwoon prImary, socondary
and forfIary amInos. ThIs can bo achIovod by fho HInsborg fosf.
(c) The Hinsberg test
In a fosf fubo add fhroo drops tor 0.1 g) of fho unknown amIno, 0.2 g of p-foIuonsuIfonyI
chIorIdo and 5 mI of 10% sodIum hydroxIdo soIufIon. Shako fho fubo for 5 mIn. If no roacfIon
appoars fo occur, hoaf fho roacfIon mIxfuro on a sfoam-bafh for 1 mIn and cooI In Ico. On
cooIIng, If no soIId soparafos ouf fhon fho subsfanco Is probabIy a farfIary amIno. If a
procIpIfafo appoars In fho aIkaIIno modIum add 5 mI of wafor and shako. If fho procIpIfafo
doos nof dIssoIvo If IndIcafos a socondary amIno. If fho soIufIon Is cIoar, acIdIfy wIfh dII.
hydrochIorIc acId. Appoaranco of a procIpIfafo IndIcafos a prImary amIno.
ChemicuI reucIion·
Prlmury umlne
Tho monosubsfIfufod suIfonamIdo Is soIubIo In sodIum hydroxIdo soIufIon. A procIpIfafo
appoars on addIng hydrochIorIc acId.
TESTS FOR FUNCTIONAL GROUPS 55
Secondury umlne
Tho dIsubsfIfufod suIfonamIdo Is InsoIubIo In sodIum hydroxIdo soIufIon.
Tertlury umlne
Tho prosonco of a socondary amIno as IndIcafod by fho HInsborg fosf can bo confIrmod
as foIIows:
ÐIssoIvo 0.1 g of NICI
2
. 6H
2
O In 20 mI of wafor and add suffIcIonf carbon dIsuIfIdo
unfII a smaII gIobuIo romaIns undIssoIvod affor fho mIxfuro has boon shakon vIgorousIy.
To 1 mI of fhIs roagonf add 1 mI of conc. ammonIum hydroxIdo foIIowod by a soIufIon of
0.1 g of fho unknown In 5 mI of wafor, fo whIch 2 drops of conc. hydrochIorIc acId havo boon
addod, If nocossary fo compIofo dIssoIufIon of fho amIno. Shako ÷ a procIpIfafo Is formod.
ChemicuI reucIion·
Questions
4.19 How wIII you dIsfInguIsh bofwoon a prImary and socondary amIno7
4.20 2, 4-ÐInIfroanIIIno doos nof form a saIf wIfh 20% hydrochIorIc acId. Suggosf a roason.
4.21 Why aro bonzamIdos of prImary amInos InsoIubIo In aquoous aIkaII whIIo fho
corrospondIng suIfonamIdos aro soIubIo7
4.22 Why do forfIary amInos nof roacf In fho HInsborg fosf7
4.23 WrIfo fho coupIIng roacfIons of bonzono dIazonIum chIorIdo wIfh:
ta) >-naphfhoI tb) PhonoI
4.24 Ðo aromafIc prImary amInos undorgo coupIIng roacfIons7
4.25 Ðo aIIphafIc amInos gIvo dIazofIsafIon and coupIIng fosf7
4.26 ÐurIng dIazofIsafIon why fho mInoraI acId shouId bo usod In oxcoss7
56 LABORATORY MANUAL OF ORGANIC CHEMISTRY
4.9 AMIDE GROUP
(a) Ammonia evolution test
A prImary amIdo can bo hydroIyzod fo carboxyIIc acId saIf In aquoous sodIum hydroxIdo. In
a boIIIng fubo fako 0.2 g of fho unknown and add 1-2 mI of 10% aquoous sodIum hydroxIdo
soIufIon. BoII fho confonfs. ÐvoIufIon of ammonIa gas and a bIuo coIor of fho rod IIfmus
papor IndIcafos fho prosonco of an amIdo group.
ChemicuI reucIions·
ThIs fosf faIIs If hydrogon af fho nIfrogon afom Is ropIacod by an aIkyI or aryI group,
fhon an amIno Is producod.
(b) Hydroxamic acid test
BoII approxImafoIy 0.1 g of fho unknown wIfh 2 mI of 1N hydroxyIamIno hydrochIorIdo and
2 mI of 1N pofassIum hydroxIdo soIufIon for 3-4 mIn In a boIIIng fubo. CooI and add a fow
drops of forrIc chIorIdo. A rod coIorafIon Is obsorvod duo fo fho formafIon of forrIc
hydroxymafo.
ChemicuI reucIions·
A nIfrIIo can aIso bo hydroIyzod fo a carboxyIIc acId saIf sImIIar fo a prImary amIdo.
TESTS FOR FUNCTIONAL GROUPS 57
Nltrlles aro sIowIy hydroIyzod fhan amIdos. Thoy can bo rafhor oasIIy hydroIyzod In conc.
suIfurIc acId.

A nIfrIIo group aIso undorgoos fho hydroxamIc acId fosf fo form fho foIIowIng rod
coIorod spocIos of forrIc hydroxymafo.
4.10 ANILIDE GROUP
An anIIIdo Is formod by subsfIfufIng a mofhyI or an aryI group af fho nIfrogon afom of an
amIdo. Mosf of fho fosfs for fhIs funcfIonaI group, usuaIIy InvoIvo Ifs hydroIysIs fo an amIno
and fhon porformIng a fosf or fho rosuIfIng amIno subsfanco.
(a) Diazotisation and coupling test
ThIs fosf Is appIIcabIo fo acofanIIIdo and bonzanIIIdo
, I.o. fhoso whIch yIoId a prImary aromafIc amIno on hydroIysIs.
Nofo If shouId bo porformod onIy In fho absonco of an aromafIc prImary amIno group.
58 LABORATORY MANUAL OF ORGANIC CHEMISTRY
PIaco 0.2 g of fho compound In a boIIIng fubo. Add 5÷6 mI of 75% suIfurIc acId fo If and
boII fho confonfs for 5 mInufos. ÐIIufo If wIfh 3 mI dIsfIIIod wafor and fIIfor. CooI fho
fIIfrafo In Ico fo 0 ÷ 5
o
C. In fho coId soIufIon add 2 mI of 10% sodIum nIfrIfo soIufIon. To fhIs
mIxfuro add a procooIod 50 mg soIufIon of >-naphfhoI In 2 mI of 10% sodIum hydroxIdo.
soIufIon. !ormafIon of an orango fo rod dyo IndIcafos an anIIIdo group.
4.11 HYDROCARBONS
Hydrocarbons aro noufraI compounds and do nof confaIn any funcfIonaI group. AromafIc
hydrocarbons possoss characforIsfIc odor and burn wIfh a smoky fIamo. Thoso aro InsoIubIo
In wafor buf dIssoIvo In many organIc soIvonfs. Tho foIIowIng fwo coIor fosfs may bo appIIod
for fhoIr IdonfIfIcafIon. Tho coIors abfaInod aro usuaIIy Infonso. A IIghf yoIIow coIor Is
InconcIusIvo or nogafIvo.
(a) Formalin test
If Is a sonsIfIvo fosf for aromafIc hydrocarbons and coIorod rosInous subsfancos aro formod.
To a mIxfuro of 2 drops of formaIIn and 2 mI of conc. suIfurIc acId add, 2 drops of fho
unknown soIufIon In 2 mI carbon fofrachIorIdo. Nofo fho appoaranco of coIor tTabIo 4.3).
Table 4.3: Colored Reactions of Aromatic Reactions
Cluss oI Compound Color
Bonzono tb.p. 110
o
C) and Ðark rod coIor twIfh somo bIack
monoaIkyIafod dorIvafIvos procIpIfafo)
o-XyIono tb.p. 144
o
C) Ðark brown procIpIfafo
n-XyIono tb.p. 139
o
C) VIoIof coIor twIfh bIack procIpIfafo)
p-XyIono tb.p. 138°C) Samo as n-xyIono
ÐIphonyI tm.p. 69
o
C) Ðark rod coIor twIfh bIack procIpIfafo)
NaphfhaIono tm.p. 80
o
C) Samo as for dIphonyI
Anfhracono tm.p. 216
o
C) Ðark yoIIow coIor twIfh bIack procIpIfafo)
TESTS FOR FUNCTIONAL GROUPS 59
(b) Aluminum chloride-chloroform test
ÐIssoIvo 0.1 g tor 3 drops of IIquId) of fho unknown In 1 mI chIoroform In a cIoan dry fosf
fubo. Shako fho fubo vIgorousIy. Add a pInch of anhydrous aIumInum chIorIdo wIfh a spafuIa
aIong fho wof sIdos of fho fubo. Tho foIIowIng characforIsfIc coIor dovoIop tTabIo 4.4)
Table 4.4: Color Development in the AlCl
3
– CHCl
3
Test
Cluss oI compound Color
Bonzono AICI
3
crysfaIs affaIn a yoIIow coIor buf soon furn
dark orango. Tho CHCI
3
Iayor Is coIorIoss.
ToIuono AICI
3
crysfaIs furn orango
o-XyIono Orango coIor, chIoroform Iayor InIfIaIIy coIorIoss
buf furns yoIIow on koopIng.
n-XyIono Orango coIor, chIoroform Iayor coIorIoss.
p-XyIono Ðark rod coIor, chIoroform Iayor coIorIoss.
ÐIphonyI PurpIo coIor, chIoroform Iayor coIorIoss.
NaphfhaIono Groon coIor In fho bogInnIng furns bIuo on
koopIng.
Phonanfhrono PurpIo coIor
Anfhracono LIghf yoIIow fo groon coIor, chIoroform Iayor
coIorIoss.
A !rIodoI-Craffs roacfIon probabIy fakos pIaco fo form coIorod dorIvafIvos. ThIs fosf
shouId bo porformod on aromafIc hydrocarbons fhaf havo boon shown InsoIubIo In conc.
suIfurIc acId.
4.12 UNSATURATION
Tho prosonco of a bond can bo ascorfaInod by fho foIIowIng
fosfs.
(a) Addition of bromine
ÐIssoIvo 50 mg tor 2 drops) of fho unknown In 1 mI of dIchIoromofhano or acofIc acId. To
fhIs add dropwIso a 2% soIufIon of bromIno aIso In carbon fofrachIorIdo. ÐocoIorIzafIon of
fho brown coIor duo fo fho formafIon of an addIfIon compound Is a posIfIvo fosf for
unsafurafIon.
60 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuI reucIion·
(b) Baeyer’s test
ÐIssoIvo 50 mg tor 2 drops) of fho unknown compound In acofono or wafor. ÐropwIso add a
2% aquoous soIufIon of pofassIum pormanganafo t2÷3 drops) and shako. Tho dIsappoaranco
of purpIo coIor of pofassIum pormanganafo and appoaranco of a sparIngIy soIubIo brown
manganoso dIoxIdo Is a posIfIvo fosf for unsafurafIon.
ChemicuI reucIion·
ThIs fosf may somofImos Ioad fo wrong concIusIons bocauso corfaIn ofhor compounds
such as aIdohydos, phonoIs, aryIamInos, prImary and socondary aIcohoIs aIso docoIorIzo
pofassIum pormanganafo soIufIon. Thoroforo, If shouId bo carrIod ouf judIcIousIy. ThIs fosf
Is fhus moro gonoraI and Ioss spocIfIc fhan fho addIfIon of bromIno.
Questions
4.27 How wIII you dIfforonfIafo bofwoon cycIohoxono and bonzono7
4.28 Namo an aromafIc compound whIch roacfs roadIIy wIfh bromIno bofh by addIfIon and
subsfIfufIon.
4.29 Whaf Is Baoyor`s roagonf7
4.30 How wIII you dIsfInguIsh bofwoon propono and propyno7
4.13 CARBONIC ACID DERIVATIVES
CarbonIc acId COtOH)
2
on ropIacomonf of fho oxygon afom or bofh fho OH groups by groups
such as N, S or haIogons forms Imporfanf compounds. Howovor, IndIvIduaI fosfs for onIy
fwo of fhoso, i.c., uroa and fhIouroa wIII bo dIscussod horo.
TESTS FOR FUNCTIONAL GROUPS 61
A. Urea (NH
2
CONH
2
), m.p. 132
o
C
!roa Is a dIamIdo of carbonIc acId tH
2
CO
3
). An aquoous soIufIon of uroa Is vIrfuaIIy
noufraI.
(a) Biuret test
GonfIy hoaf 0.2 g of fho unknown In a dry fosf fubo unfII fho moIfod subsfanco jusf soIIdIfIos.
AmmonIa gas Is ovoIvod and whIfo soIId romaIns whIch Is known as bluret. ÐIssoIvo fho
rosIduo In 1 mI of warm wafor and 1 mI of 10% sodIum hydroxIdo soIufIon. CooI and add 1-
2 drops of vory dIIufo coppor suIfafo soIufIon. A vIoIof or purpIo coIor Is a posIfIvo fosf for
uroa.
ChemicuI reucIions·
(b) Urea nitrate
ÐIssoIvo 50 mg of uroa In 1.5 mI wafor. Warm, If nocossary. Add 1.5 mI of conc. nIfrIc acId
and cooI. !IIfor and wash fho soIId carofuIIy wIfh coId wafor and dry, m.p. 163
o
C.
ThIouroa aIso ovoIvos ammonIa gas on hoafIng aIono or In fho prosonco of baso sImIIar
fo uroa.
(a) Potassium ferrocyanide test
In a fosf fubo pIaco 25 mg of fho subsfanco and dIssoIvo In 2 mI of dII. acofIc acId. Hoaf unfII
fho soIufIon Is compIofo. To fho hof soIufIon add 2 mI of pofassIum forrocyanIdo soIufIon, a
groon coIor changIng fo bIuo Is producod. Tho bIuo coIor Is obfaInod ImmodIafoIy If fho
mIxfuro Is hoafod.
62 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(b) Ferric chloride test
In a fosf fubo hoaf 25 mg of fho subsfanco on a fIamo unfII fho soIId moIfs. CooI and dIssoIvo
fho soIId In 2 mI wafor. Add 2 mI of forrIc chIorIdo soIufIon. !III fho fosf fubo wIfh wafor
and Invorf, a doop rod soIufIon Is obfaInod.
Questions
4.31 Whaf happons whon uroa Is
ta) roacfod wIfh hydrazIno.
tb) hoafod aIono.
tc) rofIuxod wIfh a baso.
4.32 Whaf happons whon uroa Is hoafod wIfh aIkaIIno KMnO
4
soIufIon7
ChupIer 5
TESTS FOR COMMON ORGANIC
COMPOUNDS
A Iargo numbor of organIc compounds confaIn moro fhan ono funcfIonaI groups, and fho
proporfIos of ono group may bo maskod by fho ofhor. Thoroforo, fo cIassIfy fho compound
corrocfIy, addIfIonaI fosfs nood fo bo porformod. Tho fInaI docIsIon, howovor, wouId rosf on
fho proparafIon and IdonfIfIcafIon of Ifs dorIvafIvo tChapfor 6). In somo casos such fosfs fo
bo doscrIbod In fhIs chapfor may ovon assIsf In IdonfIfyIng fho compound IfsoIf.
5.1 ALCOHOLS AND PHENOLS
b.p. (°C)
65 Methyl ulcohol CH
3
OH
If Is a coIorIoss IIquId mIscIbIo wIfh wafor In aII proporfIons and has a characforIsfIc smoII.
ta) PIaco 2 drops of fho compound In a fosf fubo. Bond a coppor wIro Info a compacf
form. Hoaf If fo rod hof and drop Info fho fubo ÷ a pungonf odor of formaIdohydo.
tb) 3, 5-ÐInIfrobonzoafo, m.p. 10?°C.
?8 Kthyl ulcohol CH
3
CH
2
OH
If Is a coIorIoss IIquId, mIscIbIo wIfh wafor and has a characforIsfIc spIrIf IIko odor.
ta) If rosponds fo Iodoform fosf.
tb) If gIvos a characforIsfIc sfrong smoII of acofaIdohydo on hoafIng wIfh coppor wIro.
tc) 3, 5-ÐInIfrobonzoafo, m.p. 92°C.
64 LABORATORY MANUAL OF ORGANIC CHEMISTRY
82 ¡sopropyl ulcohol tCH
3
)
2
CHOH
If Is a coIorIoss IIquId and mIscIbIo wIfh wafor.
ta) In a fosf fubo pIaco 2 mI of IodIno soIufIon and add 1 drop of aIcohoI. Now add dII.
sodIum hydroxIdo soIufIon dropwIso fIII fho doop brown coIor of IodIno furns paIo
yoIIow. Shako fho fubo÷a yoIIow procIpIfafo of Iodoform appoars.
tb) !If up an apparafus consIsfIng of a 50 mI dIsfIIIIng fIask and a wafor condonsor.
PIaco 1 mI of fho compound Info fho fIask and 20 mI of fho dIchromafo soIufIon.
ÐIsfII fho mIxfuro unfII 5 mI of fho dIsfIIIafo has boon coIIocfod. ThIs dIsfIIIafo
confaIns acofono; mako a 2, 4-dInIfrophonyIhydrazono, m.p. 125°C.
83 IerI-Butyl ulcohol tCH
3
)
3
COH
Tako 1 mI of fho aquoous soIufIon and 4 mI of conc. hydrochIorIdo acId In a fosf fubo and
shako. Thoro Is an ImmodIafo formafIon of an InsoIubIo IIquId, aIkyI chIorIdo whIch forms
an oIIy Iayor.
96 Allyl ulcohol CH
2
=CHCH
2
OH
If possossos an IrrIfafIng odor and Is soIubIo In wafor.
ta) Add 2 drops of fho aquoous soIufIon of fho aIcohoI In 4 mI of bromIno wafor.
Thoro Is an ImmodIafo dIsappoaranco of bromIno coIor duo fo fho formafIon of a
dIbromIdo, b.p. 212°C.
tb) On oxIdafIon wIfh pofassIum dIchromafo and dII. suIfurIc acId, aIIyI aIcohoI forms
acroIoIn whIch has a moro IrrIfafIng odor fhan fho aIcohoI IfsoIf.
9? n-Propyl ulcohol CH
3
CH
2
CH
2
OH
If Is a coIorIoss IIquId, mIscIbIo wIfh wafor.
If Is oxIdIzod by hof pofassIum dIchromafo and dII. suIfurIc acId fo propIonaIdohydo.
ThIs can bo fosfod by fho addIfIon of SchIff`s roagonf fo fho dIsfIIIafo÷a doop vIoIof-rod
coIor Is obfaInod.
100 sec-Butyl ulcohol
If Is soIubIo In wafor.
ta) Add 1 drop of fho aquoous soIufIon of aIcohoI fo 2 mI of IodIno soIufIon foIIowod by
fho addIfIon of dII. sodIum hydroxIdo soIufIon dropwIso, fIII fho doop brown coIor
of IodIno changos fo paIo yoIIow. Shako÷yoIIow procIpIfafo of Iodoform appoars.
tb) On boIIIng wIfh conc. hydrochIorIc acId If yIoIds IA? bufyI chIorIdo, b.p. 6?°C.
108 ¡sobutyl ulcohol
If Is a coIorIoss IIquId and Is soIubIo In wafor.
TESTS FOR COMMON ORGANIC COMPOUNDS 65
On boIIIng wIfh hof pofassIum dIchromafo and dII. suIfurIc acId, IsobufyraIdohydo dIsfIIs
ovor. ThIs can bo fosfod by fho SchIff`s roagonf.
11? n-Butyl ulcohol CH
3
CH
2
CH
2
CH
2
OH
On boIIIng wIfh hof pofassIum dIchromafo and dII. suIfurIc acId, bufyraIdohydo Is formod
whIch can bo confIrmod by fosfIng wIfh fho SchIff`s roagonf.
160 Cyclohexunol
If Is soIubIo In wafor.
ta) On boIIIng wIfh pofassIum dIchromafo and dII. suIfurIc acId, If forms cycIohoxanono,
b.p. 115°C, buf on oxIdafIon wIfh hof conc. nIfrIc acId, adIpIc acId m.p. 149°C Is
obfaInod.
tb) ÐIsfIIIafIon of cycIohoxanoI In fho prosonco of cafaIyfIc amounf of phosphorIc acId
or conc. suIfurIc acId yIoIds cycIohoxono, b.p. 83°C.
1?6 o-Chlorophenol
If Is sIIghfIy soIubIo In wafor buf compIofoIy so In aIcohoI and ofhor. If gIvos vIoIof coIor
wIfh forrIc chIorIdo soIufIon.
196 o-Bromophenol
If gIvos vIoIof coIor wIfh forrIc chIorIdo soIufIon.
On froafmonf wIfh bromIno wafor If yIoIds frIbromophonoI, m.p. 95°C.
19? Kthylene glycol
If Is a coIorIoss and pIoasanf odor IIquId InsoIubIo In wafor, soIubIo In ofhor.
=-NaphfhyI carbamafo, m.p. 53°C.
19? Llnulool
If possossos a pIoasanf odor and Is soIubIo In wafor.
66 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ta) Add 2 drops of fho aquoous soIufIon of fho aIcohoI fo 3 mI of bromIno wafor In a
fosf fubo. Tho bromIno coIor ImmodIafoIy dIsappoars. ThIs shows fho prosonco of
unsafurafIon In IInaIooI.
tb) Acofafo, b.p. 103°C/30 mm.
tc) =-NaphfhyI carbamafo, m.p. 53°C.
202 m-Cresol
If Is donsor fhan wafor and Is onIy sIIghfIy soIubIo In If.
ta) WIfh forrIc chIorIdo soIufIon If gIvos a bIuo-vIoIof coIor.
tb) Bonzoafo, m.p. 54°C and pIcrafo, m.p. 88°C.
205 Benzyl ulcohol C
6
H
5
CH
2
OH
If has a faInf aromafIc ordor.
ta) To 2 mI of dII. nIfrIc acId In a fosf fubo and add 1 drop of fho aIcohoI and aIIow fho
fosf fubo fo sfand In a boakor of boIIIng wafor. A paIo yoIIow omuIsIon and a
sfrong odor of bIffor aImonds dovoIops duo fo fho formafIon of bonzaIdohydo.
tb) In a 100 mI round-boffomod fIask fako, 0.25 g of pofassIum pormanganafo and
dIssoIvo In 2.5 mI of wafor. Hoaf fho soIufIon fo boIIIng and add 0.5 g of bonzyI
aIcohoI. Thon aIIow fho fIask fo sfand af room fomporafuro wIfh froquonf shakIng
fIII fho purpIo coIor dIsappoars. !IIfor and acIdIfy fho fIIfrafo wIfh conc. hydrochIorIc
acId, bonzoIc acId Is formod, fIIfor wash wIfh coId wafor and dry.
m.p. 121°C.
214 m-Chlorophenol
On roacfIon wIfh 50% nIfrIc acId In fho coId If yIoIds a 4-nIfro dorIvafIvo, m.p. 133°C.
220 =-Phenylethyl ulcohol
If Is soIubIo In wafor and fho aquoous soIufIon has fho odor of roso oII.
ta) On oxIdafIon tdoscrIbod abovo undor bonzyI aIcohoI) If yIoIds bonzoIc acId, m.p.
121°C.
tb) AcId phfhaIafo, m.p. 188°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 67
222 Cltronellol
ta) If possossos a pIoasanf odor and unsafurafIon whIch can bo dofocfod by bromIno
wafor.
tb) Acofafo, b.p. 120°C/15 mm.
230 Gerunlol
If possossos fho odor of rosos as woII as unsafurafIon.
ta) WIfh bromIno If forms a fofrabromo dorIvafIvo, m.p. ?0°C.
tb) Acofafo, b.p. 244°C.
m.p. (°C)
30 o-Cresol
If has a carboIIc acId odor and gIvos vIoIof coIor wIfh forrIc chIorIdo soIufIon.
ta) In a dry fosf fubo pIaco a fow mIIIIgrams of phfhaIIc anhydrIdo and fwIco fho
amounf of fho compound. Add 2 drops of conc. suIfurIc acId and hoaf fho mIxfuro
on a fIamo gonfIy fIII fho mIxfuro affaIns a rod-brown coIor. CooI and add a fow
drops of wafor fo fho mIxfuro foIIowod by dII. sodIum hydroxIdo soIufIon dropwIso
fIII fho soIufIon Is aIkaIIno.
Appoaranco of rod coIor IndIcafos -crosoI or phonoI.
tb) To 2 mI of conc. ammonIum hydroxIdo soIufIon add a pInch of fho compound. If
fho compound Is undIssoIvod fhon If shows -crosoI, buf If a cIoar soIufIon Is
obfaInod fhon If Is phonoI.
33 Clnnumyl ulcohol
ta) To 1 drop of bromIno soIufIon In 2 mI carbon fofrachIorIdo add 2 drops of fho
68 LABORATORY MANUAL OF ORGANIC CHEMISTRY
compound and shako. Tho brown coIor of bromIno dIsappoars formIng a dIbromIdo
tm.p. ?4°C).
tb) On oxIdafIon wIfh pofassIum pormaganafo If yIoIds bonzoIc acId, m.p. 121°C.
35 Terplneol
If aIso confaIns unsafurafIon and docoIorIzos bromIno coIor.
ta) On froafmonf wIfh gasoous hydrochIorIc acId If forms a dIponfono dIhydrochIorIdo,
m.p. 50°C.
tb) Acofafo, m.p. 195°C.
36 p-Cresol
If Is a coIorIoss IIquId buf bocomos coIorod on koopIng. If Is soIubIo In organIc soIvonfs.
LIko fho HJD Isomor If has a carboIIc acId odor as woII.
ta) If yIoIds bIuo coIor wIfh forrIc chIorIdo soIufIon.
tb) WIfh oxcoss bromIno If forms a fofrabromo dorIvafIvo, m.p. 109°C.
42 Phenol
If forms an omuIsIon wIfh wafor.
ta) WIfh forrIc chIorIdo soIufIon If gIvos a vIoIof coIor.
tb) If can bo confIrmod by fho fosf IIsfod undor -crosoI.
tc) WIfh bromIno wafor If Is roadIIy bromInafod fo yIoId a frIbromo dorIvafIvo, m.p.
93°C.
43 p-Chlorophenol
If Is InsoIubIo In wafor buf soIubIo In ofhyI aIcohoI.
ta) If gIvos vIoIof coIor wIfh forrIc chIorIdo soIufIon.
tb) On roacfIon wIfh conc. nIfrIc acId If yIoIds a 2, 6-dInIfro dorIvafIvo, m.p. 81°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 69
45 o-Nltrophenol
If Is yoIIow In coIor and has a farry odor. If Is roadIIy soIubIo In hof wafor and mosf organIc
soIvonfs. If gIvos no coIor wIfh forrIc chIorIdo soIufIon.
ta) ÐIssoIvo 25 mg of fho compound In wafor and add 2 mI of dII. sodIum hydroxIdo
soIufIon. Shako÷doop rod coIor.
tb) WIfh conc. nIfrIc acId and suIfurIc acId If Is nIfrafod fo gIvo yIoIds pIcrIc acId, m.p.
114°C.
64 p-Bromophenol
WIfh bromIno wafor If yIoIds frIbromophonoI, m.p. 95°C.
69 Dlphenyl curblnol (Benzhydrol)
CoIorIoss crysfaIIIno soIId, InsoIubIo In wafor
ta) 3, 5-ÐInIfrobonzoafo, m.p. 142°C.
94 =-Nuphthol
If gIvos no coIor wIfh noufraI forrIc chIorIdo soIufIon buf a whIfo procIpIfafo.
ta) PIaco 0.5 mI of fho compound In a fosf fubo. Add 2 mI of dII. sodIum hydroxIdo
soIufIon, and 1 drop of chIoroform. Warm fho mIxfuro÷a bIuo coIor Is obfaInod
wIfh bofh =- and >-napfhfhoIs.
Tako a mIxfuro of 10 mI of IodIno soIufIon and dII. sodIum hydroxIdo soIufIon In a
fosf fubo and add 50 mg of fho compound. A vIoIof procIpIfafo appoars whIch
darkons rapIdIy÷=-naphfhoI. If fhoro Is no chango In fho soIufIon÷>-naphfhoI.
tb) Warm a pInch of fho subsfanco wIfh dII. sodIum hydroxIdo soIufIon, carbon
fofrachIorIdo and somo coppor powdor In a fosf fubo÷a bIuo coIor appoars.
70 LABORATORY MANUAL OF ORGANIC CHEMISTRY
9? m-Nltrophenol
If Is paIo yoIIow In coIor buf odorIoss and Is soIubIo In hof wafor and mosf organIc soIvonfs.
ta) ÐIssoIvo 25 mg of fho compound In hof wafor, add 2 mI dII. sodIum hydroxIdo
soIufIon÷orango-rod coIor.
tb) ÐIssoIvo 25 mg of fho compound In 5 mI of wafor and hoaf fo boIIIng. CooI and
add a fow drops of forrIc chIorIdo soIufIon ÷ vIoIof-rod coIor.
105 Cutechol
If Is roadIIy soIubIo In wafor and yIoIds groon coIor wIfh forrIc chIorIdo soIufIon.
ta) To fho aquoous soIufIon of fho aIcohoI In a fosf fubo, add an oquaI voIumo of Ioad
acofafo soIufIon ÷ a whIfo procIpIfafo appoars ImmodIafoIy.
tb) WIfh bromIno If yIoIds a fofrabromo dorIvafIvo, m.p. 192°C.
110 Resorclnol
If Is roadIIy soIubIo In wafor and gIvos bIuo-vIoIof coIor wIfh forrIc chIorIdo soIufIon.
ta) In a dry fosf fubo pIaco 25 mg of phfhaIIc anhydrIdo, 50 mg of fho compound and
2 drops of conc. suIfurIc acId. Hoaf gonfIy on a fIamo unfII fho mIxfuro Is rod-
brown In coIor. CooI and add a fow drops of wafor foIIowod by dII. sodIum hydroxIdo
soIufIon fIII fho soIufIon Is aIkaIIno. PIaco ono drop of fhIs soIufIon In a socond
fubo and fIII If up wIfh wafor÷ a yoIIow groon fIuorosconco.
tb) Warm 50 mg of fho aIcohoI wIfh dII. sodIum hydroxIdo soIufIon and chIoroform÷
rod coIor wIfh groon fIuorosconco.
114 p-Nltrophenol
If Is paIo yoIIow In coIor buf odorIoss. If Is soIubIo In hof wafor, aIcohoI and ofhor.
ta) To 25 mg of fho compound In a fosf fubo add 1 mI of wafor foIIowod by 2 mI of dII.
sodIum hydroxIdo soIufIon ÷ an Infonso yoIIow coIor.
tb) ÐIssoIvo 25 mg of fho compound In 5 mI of wafor and add 2 drops of forrIc chIorIdo
soIufIon ÷ vIoIof rod coIor.
TESTS FOR COMMON ORGANIC COMPOUNDS 71
122 Plcrlc ucld
If Is IIghf yoIIow In coIor and soIubIo In hof wafor, aIcohoI and bonzono.
ta) To 5 mI of dII. sodIum hydroxIdo soIufIon, add 25 mI of fho compound and hoaf
jusf fo boIIIng. To fho Infonso yoIIow coIorod soIufIon obfaInod, add a drop of
ammonIum suIfIdo soIufIon ÷ a doop rod coIor.
123 >-Nuphthol
If gIvos groon coIor wIfh noufraI forrIc chIorIdo soIufIon.
ta) Porform fho fosf as In =-naphfhoI.
tb) ÐIssoIvo a pInch of fho subsfanco In a fosf fubo In conc. sodIum hydroxIdo soIufIon
and chIoroform. Warm fho mIxfuro ÷ a IIghf bIuIsh groon coIor wIfh a hoavy
procIpIfafo. =-NaphfhoI gIvos a dark bIuo coIor.
133 Pyrogullol
If Is a whIfo crysfaIIIno subsfanco whIch furns bIack on oxposuro fo aIr. If Is roadIIy soIubIo
In wafor.
ta) To 2 mI of fho aquoous soIufIon add a pInch of forrous suIfafo and shako ÷ a bIuo-
vIoIof coIor.
tb) TrIacofafo, m.p. 161°C.
165 Trlphenylmethunol tC
6
H
5
)
3
COH
Tho aIcohoI Is InsoIubIo In wafor.
ta) Add 0.2 g of fho subsfanco In 2 mI of conc. suIfurIc acId and shako ÷ Infonso
yoIIow coIor.
tb) AcIfafo, m.p. 88°C.
166 D-Munnltol CH
2
OHtCHOH)
4
CH
2
OH
If Is a coIorIoss soIId, soIubIo In wafor buf InsoIubIo In ofhor and aIcohoI.
72 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ta) To 1 mI of coppor suIfafo soIufIon In a fosf fubo, add ammonIum hydroxIdo soIufIon
fIII fho bIuo coIor InIfIaIIy obfaInod bocomos coIorIoss. To fhIs ammonIacaI coppor
suIfafo soIufIon add 0.1 g of fho subsfanco and shako ÷ bIuo procIpIfafo Is formod.
tb) Hoxaacofafo, m.p. 119°C.
tc) Hoxabonzoafo, m.p. 124°C.
1?0 Qulnol
If Is soIubIo In wafor and gIvos a fransIonf bIuo coIor wIfh forrIc chIorIdo soIufIon.
ta) ÐIssoIvo 50 mg of fho compound In 2 mI dII. suIfurIc acId In a fosf fubo by warmIng.
CooI fho soIufIon and add 25 mg of pofassIum dIchromafo ÷ ImmodIafo procIpIfafo
of qulnhydrone consIsfIng of groon noodIos.
tb) ÐIacofafo, m.p. 123°C.
1?4 o- Amlnophenol
If Is sparIngIy soIubIo In coId wafor buf roadIIy so In ofhor.
ta) If gIvos a dark brown procIpIfafo wIfh forrIc chIorIdo soIufIon.
tb) WIfh sIIvor nIfrafo soIufIon, a yoIIow brown coIor Is obfaInod sIowIy buf rapIdIy
on warmIng.
186 p-Amlnophenol
If Is soIubIo In coId wafor buf sparIngIy soIubIo In ofhor.
If gIvos a purpIo coIor wIfh forrIc chIorIdo soIufIon.
218 Phlorogluclnol
If Is soIubIo In wafor and gIvos a fransIonf bIuo coIor wIfh forrIc chIorIdo soIufIon.
ta) TrIacofafo, m.p. 105°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 73
5.2 CARBOXYLIC ACIDS
b.p. (°C)
100 Formlc ucld HCOOH
If Is mIcIbIo wIfh wafor and has a ponofrafIng odor.
ta) To 2 mI of fho noufraI aquoous soIufIon of fho acId add an oquaI voIumo of forrIc
chIorIdo soIufIon÷a wIno rod-coIor.
tb) In a fosf fubo pIaco 2 mI of noufraI soIufIon of fho acId and 1 mI of morcurIc
chIorIdo soIufIon. BoII for 30 soc ÷ appoaranco of a whIfo procIpIfafo duo fo fho
formafIon of morcurous chIorIdo duo fo roducfIon.
118 Acetlc ucld CH
3
COOH
If Is mIscIbIo wIfh wafor and rosponds sImIIarIy fo fosf ta) for formIc acId.
In a porcoIaIn dIsh fako 0.5 g of fho acId and 2 g of phosphorus ponfachIorIdo. GrInd
fho mIxfuro unfII If bocomos IIquId. To fhIs crudo acId chIorIdo add 10 mI of conc. ammonIum
hydroxIdo. Whon fho vIgorous roacfIon has coasod, sfIr, cooI and fIIfor fho amIdo. Wash If
wIfh coId wafor and dry ÷ acofamIdo, m.p. 82°C.
140 Proplonlc ucld CH
3
CH
2
COOH
If Is mIscIbIo wIfh wafor and aIso gIvos fho coIor fosf IIsfod In ta) for formIc acId.
AmId, m.p. ?9°C.
155 ¡sobutyrlc ucld tCH
3
)
2
CHCOOH
If Is a coIorIoss IIquId wIfh unpIoasanf smoII. If Is sparIngIy soIubIo In wafor buf soIubIo In
aIcohoI and ofhor.
ta) On hoafIng wIfh conc. suIfurIc acId, carbon monoxIdo and suIfur dIoxIdo aro ovoIvod.
tb) AmIdo, m.p. 129°C.
tc) HydrazIdo, m.p. 104 °C.
162 n-Butyrlc ucld CH
3
CH
2
CH
2
COOH
If Is mIscIbIo wIfh wafor and has fho odor of rancId buffor.
AmIdo, m.p. 129°C.
m.p. (°C)
?2 Crotonlc ucld CH
3
CH=CHCOOH
If Is soIubIo In wafor.
To 2 mI of bromIno wafor add 1 mI of fho aquoous soIufIon of fho acId ÷ bromIno coIor
Is docoIorIzod.
74 LABORATORY MANUAL OF ORGANIC CHEMISTRY
?6 Phenylucetlc ucld
If Is soIubIo In hof wafor.
If Is oxIdIzod by pofassIum dIchromafo and suIfurIc acId fo bonzoIc acId tm.p. 121°C).
100 Cltrlc ucld
If Is soIubIo In wafor and Iosos wafor of crysfaIIIzafIon af 130°C, formIng anhydrous acId
tm.p. 153°C).
ta) To 3 mI of fho noufraI soIufIon add 1 mI of caIcIum chIorIdo soIufIon and hoaf fho
mIxfuro fo boIIIng for 1-2 mIn ÷ a hoavy whIfo procIpIfafo of caIcIum cIfrafo.
tb) To 1 mI of fho noufraI soIufIon add 2 drops of sodIum InfroprussIdo soIufIon ÷ a
rod coIor whIch changos fo vIoIof on addIng acofIc acId.
tc) AmIdo, m.p. 215°C
101 Oxullc ucld
If Is soIubIo In wafor.
ta) PIaco 50 mg of fho acId In a fosf fubo and add 5 drops of conc. suIfurIc acId. GonfIy
warm fho fubo on fho fIamo and furn fho moufh of fho fubo porIodIcaIIy fo fho
fIamo ÷ carbon monoxIdo burns wIfh a bIuo fIamo.
tb) In a fosf fubo pIaco ono crysfaI of oxaIIc acId and a smaII amounf of dIphonyIamIno
and hoaf fho mIxfuro wIfh fwIco fho amounf of zInc chIorIdo. Tho mIxfuro fIrsf
moIfs and fhon furns bIuo duo fo fho formafIon of a frIphonyImofhano dyo.
tc) ÐImofhyI oxaIafo, m.p. 54°C.
105 o-Tolulc ucld
If Is sparIngIy soIubIo In wafor.
In a morfar grInd 20 mg of fho acId wIfh an oquaI amounf of soda IImo. Pour fho
mIxfuro In an IgnIfIon fubo and hoaf ÷ smoII of foIuono.
TESTS FOR COMMON ORGANIC COMPOUNDS 75
110 m-Tolulc ucld
If Is sparIngIy soIubIo In wafor.
ta) If aIso yIoIds foIuono on hoafIng wIfh soda IImo.
tb) AmIdo, m.p. 94°C.
118 Mundellc ucld
If Is soIubIo In wafor.
To 50 mg of fho compound In a fosf fubo add oquaI voIumos of aquoous pofassIum
pormanganafo and suIfurIc acId and hoaf ÷ odor of bonzaIdohydo.
121 Benzolc ucld
If Is soIubIo In hof wafor, buf sparIngIy soIubIo In coId wafor.
On hoafIng wIfh soda IImo If yIoIds bonzono.
133 Clnnumlc ucld
If Is sparIngIy soIubIo In wafor.
ta) On oxIdafIon wIfh pofassIum pormanganafo If forms bonzoIc acId, tm.p. 121.2°C).
tb) AmIdo, m.p. 146°C.
135 Acetylsullcyllc ucld (Asplrln)
If Is sparIngIy soIubIo In wafor and gIvos no coIor wIfh forrIc chIorIdo soIufIon.
To 50 mg of fho subsfanco In a dry fosf fubo add 10 drops oach of mofhyI aIcohoI and
conc. suIfurIc acId and hoaf gonfIy. CooI and pour Info 5 mI of wafor fakon In a boakor ÷
smoII of mofhyI saIIcyIafo toII of wInforgroon).
ta) AmIdo, m.p. 138°C.
76 LABORATORY MANUAL OF ORGANIC CHEMISTRY
13? o-Chlorobenzolc ucld
If Is soIubIo In hof wafor.
ta) AmIdo, m.p. 106°C.
139 o-Nltrobenzolc ucld
If Is a coIorIoss soIId and soIubIo In boIIIng wafor.
ta) GrInd 20 mg of fho acId and an oquaI amounf of soda IImo In a morfar. Infroduco
fho mIxfuro In an IgnIfIon fubo. Hoaf ÷ smoII of nIfrobonzono tbIffor aImonds).
tb) AmIdo, m.p.142°C.
141 m-Nltrobenzolc ucld
If Is paIo yoIIow In coIor and onIy sIIghfIy soIubIo In wafor. GIvos fho fosf ta) as In
-nIfrobonzoIc acId.
144 Anthrunlllc ucld
If Is soIubIo In wafor and In aIcohoI wIfh a bIuo fIuorosconco.
ta) WIfh bromIno If yIoIds a 2,6-dIbromo dorIvafIvo, m.p. 22?°C
tb) To 100 mg of fho compound In a fosf fubo add 3 mI of acofono, shako fo dIssoIvo
fho soIId, fhon add 1 mI of acofIc anhydrIdo. AIIow fo sfand for 2 mIn fhon add 5
mI of aquoous sodIum hydroxIdo soIufIon. SodIum hydroxIdo soIufIon Is addod fo
parfIaIIy noufraIIzo fho oxcoss acId, fho soIufIon shouId romaIn acIdIc af fhIs
sfago. CooI and shako. !IIfor fho soIId and wash wIfh coId wafor fho acofyI
dorIvafIvo, m.p. 185°C.
150 o-Bromobenzolc ucld
If Is soIubIo In hof wafor.
AmIdo, m.p. 155°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 77
152 Adlplc ucld
If Is soIubIo In wafor
ta) PIaco 20 mg of fho compound In a fosf fubo and add fwIco fho amounf of rosorcInoI
and 2 drops of conc. suIfurIc acId. Hoaf fho mIxfuro gonfIy fIII If furns roddIsh-
brown. CooI and add sovoraI drops of wafor and fhon dII. sodIum hydroxIdo soIufIon
fIII aIkaIIno. Tako 1 mI of fhIs soIufIon Info anofhor fosf fubo and fIII If up wIfh
wafor ÷ vIoIof-rod coIor.
tb) AmIdo, m.p. 220°C.
155 m-Bromobenzolc ucld
If Is sparIngIy soIubIo In wafor.
ta) On fusIon wIfh pofassIum hydroxIdo fhIs acId gIvos -hydroxybonzoIc acId tm.p.
200°C).
tb) AmIdo, m.p. 155°C.
158 Sullcyllc ucld
If Is nof soIubIo In coId wafor.
ta) Add 20 mg of fho acId fo 2 mI of wafor and shako. Add 1 drop of forrIc chIorIdo
soIufIon ÷ a vIoIof coIor.
tb) To 50 mg of fho acId fakon In a dry fosf fubo, add 10 drops oach of mofhyI aIcohoI
and conc. suIfurIc acId and hoaf gonfIy on a fIamo. CooI and pour fho mIxfuro Info
5 mI of wafor fakon In a smaII boakor ÷ odor of mofhyI saIIcyIafo toII of wInfor-
groon).
162 =-Nuphtholc ucld
If Is a crysfaIIIno soIId, InsoIubIo In coId wafor buf soIubIo In hof wafor.
ta) Hoaf 0.2 g of fho acId wIfh soda IImo ÷ characforIsfIc smoII of napfhaIono.
tb) AmIdo, m.p. 202°C
tc) AnIIIdo, m.p. 163°C
78 LABORATORY MANUAL OF ORGANIC CHEMISTRY
169 Turturlc ucld HOOCCHOHCHOHCOOH
If Is a whIfo crysfaIIIno compound. If Is roadIy soIubIo In wafor and aIcohoI.
ta) In a fosf fubo, fako 0.2 g of fho acId and dIssoIvo In 2 mI of wafor. To fhIs add a
fow crysfaIs of forrous suIfafo and shako. To fhIs soIufIon add 2 drops of hydrogon
poroxIdo and 2 mI of 5% sodIum hydroxIdo soIufIon ÷ a doop vIoIof coIor appoars.
tb) In a fosf fubo mIx 0.2 g of fho acId, 0.2 g rosorcInoI and 2 mI conc. suIfurIc acId
mIx woII and hoaf fho mIxfuro ÷ a vIoIof coIor appoars.
tc) AmIdo, m.p. 195°C
td) F-ToIuIdIdo, m.p. 264°C.
1?8 p-Tolulc ucld
If Is soIubIo In hof wafor and yIoIds foIuono on hoafIng wIfh soda IImo.
AmIdo, m.p. 158° C.
184 Anlslc ucld
If Is sIIghfIy soIubIo In wafor. On hoafIng wIfh soda IImo If yIoIds anIsoIo, m.p. 154°C.
185 Succlnlc ucld
If Is soIubIo In wafor.
PIaco 20 mg of fho subsfanco In dry fosf fubo and add fwIco fho amounf of rosorcInoI
and 2 drops of conc. suIfurIc acId. GonfIy hoaf fho mIxfuro fIII If Is roddIsh-brown. CooI and
add sovoraI drops of wafor foIIowod by dII. sodIum hydroxIdo soIufIon fIII aIkaIIno. Tako
1 mI of fhIs soIufIon Info anofhor fosf fubo and fIII If wIfh wafor ÷ a yoIIow groon
fIuorosconco.
186 p-Amlnobenzolc ucld
If has yoIIowIsh-rod crysfaIs and Is soIubIo In hof wafor.
Hoaf a pInch of fho subsfanco wIfh an oquaI amounf of caIcIum chIorIdo In a fosf fubo.
CooI and add 2 mI of ofhanoI ÷ a rod soIufIon.
195 Phthullc ucld
If Is a whIfo soIId, soIubIo In hof wafor and sparIngIy soIubIo In ofhor and aIcohoI.
ta) On hoafIng abovo 150°C, If forms phfhaIIc anhydrIdo, m.p. 132°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 79
tb) MIx 0.2 g of fho acId wIfh 0.4 g of rosorcInoI and add 1 mI of conc. suIfurIc acId In
a fosf fubo. Hoaf fho mIxfuro on a fIamo fIII a rod-brown In coIor. CooI and pour
In coId wafor. Add a fow drops of 10% sodIum hydroxIdo soIufIon ÷ orango-groon
fIuorosconco.
tc) AmIdo, m.p. 220°C.
201 m-Hydroxybenzolc ucld
If Is a coIorIoss crysfaIIIno soIId. If Is InsoIubIo In wafor buf soIubIo In aIcohoI. If gIvos no
coIor wIfh forrIc chIorIdo soIufIon.
ta) Tho acId on hoafIng wIfh soda IImo gIvos fho smoII of phonoI.
tb) AmIdo, m.p. 16?° C
tc) Acofafo, m.p. 12?° C
td) F-ToIuIdIdo, m.p. 163°C
214 p-Hydroxybenzolc ucld
If Is a coIorIoss soIId and has noodIo-IIko crysfaIs. If Is InsoIubIo In wafor buf soIubIo In
aIcohoI and acofono. If gIvos a vIoIof or rod coIor wIfh forrIc chIorIdo soIufIon.
ta) AmIdo, m.p. 162°C
tb) Acofafo, m.p. 185°C
tc) F-ToIuIdIdo, m.p. 208°C
236 p-Chlorobenzolc ucld
If Is a whIfo soIId and sparIngIy soIubIo In wafor.
AmIdo, m.p. 1?9°C.
239 p-Nltrobenzolc ucld
If Is a coIorIoss subsfanco soIubIo In organIc soIvonfs.
80 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Hoaf 20 mg of fho acId wIfh fwIco fho amounf of soda-IImo In a dry fosf fubo ÷ odor of
nIfrobonzono.
251 p-Bromobenzolc ucld
If Is coIorIoss and sparIngIy soIubIo In hof wafor.
AmIdo, m.p. 189°C.
5.3 ALDEHYDES AND KETONES
b.p. (°C)
21 Acetuldehyde CH
3
CHO
If Is mIscIbIo wIfh wafor and has a pungonf smoII. In dIIufo aquoous soIufIon fho odor
rosombIos fhaf of appIos.
ta) To 20 mI of fho aquoous soIufIon add 2 mI of fho 20% pofassIum hydroxIdo soIufIon.
Hoaf fo boIIIng for 30 soc ÷ fho soIufIon furns yoIIow and fhon yoIIow procIpIfafos
appoar changIng fo orango.
tb) To 2 mI of fho aquoous soIufIon and 2 mI of sodIum nIfroprussIdo soIufIon fhon
add 5 drops of sodIum hydroxIdo soIufIon ÷ a doop wIno rod coIor.
49 Proplonuldehyde CH
3
CH
2
CHO
If Is soIubIo In wafor and has an odor rosombIIng fhaf of acofaIdohydo.
ta) To 2 mI of fho aquoous soIufIon add 1 mI of dII. sodIum hydroxIdo soIufIon. BoII
for 1 mIn ÷ a whIfo procIpIfafo appoars whIch dIssoIvos fo gIvo a cIoar paIo yoIIow
soIufIon.
tb) 2,4-ÐInIfrophonyIhydrazono, m.p. 155°C.
56 Acetone
If Is mIscIbIo wIfh wafor and has a pIoasanf odor.
ta) WIfh IodIno soIufIon and dII. sodIum hydroxIdo soIufIon, If yIoIds Iodoform tm.p.
119°C) In coId.
tb) To 1 mI of aquoous soIufIon of fho subsfanco add a fow drops of sodIum nIfroprusIdo
soIufIon ÷ a rod coIor.
tc) 2, 4-ÐInIfrophonyIhydrazono, m.p. 128°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 81
63 ¡sobutyruldehyde
If Is soIubIo In coId wafor.
2,4-ÐInIfrophonyIhydrazono, m.p. 182°C.
?5 n-Butyruldehyde CH
3
CH
2
CH
2
CHO
If Is soIubIo In coId wafor.
2,4-ÐInIfrophonyIhydrazono tm.p. 122°C)
80 Methy ethyl ketone
If Is mIscIbIo wIfh wafor.
2,4-ÐInIfrophonyIhydrazono, m.p. 111°C.
102 Dlethyl ketone
If Is soIubIo In coId wafor
2,4-ÐInIfrophonyIhydrazono, m.p. 143°C.
104 Crotonuldehyde CH
3
CH = CHCHO
If Is faIrIy soIubIo In coId wafor and has a pungonf odor.
ta) To 2 mI of fho aquoous soIufIon add 2 mI of dII. sodIum hydroxIdo soIufIon and
boII for 30 soc ÷ a yoIIow soIufIon foIIowod by a yoIIow procIpIfafo furnIng fo
orango.
tb) To 2 mI of fho aquoous soIufIon add 2 mI of sodIum nIfroprussIdo soIufIon foIIowod
by 1 drop of sodIum hydroxIdo soIufIon ÷ a doop wIno rod coIor.
tc) 2,4-ÐInIfrophonyIhydrazono, m.p. 190°C.
115 p-Hydroxybenzuldehyde
If Is sparIngIy soIubIo In wafor.
To 1 mI of aquoous soIufIon In a fosf fubo add 1 drop of forrIc chIorIdo soIufIon ÷ a
faInf vIoIof coIor.
SomIcarbazono, m.p. 224°C.
130 Cyclopentunone
2,4-ÐInIfrophonyIhydrazono, m.p. 146°C.
82 LABORATORY MANUAL OF ORGANIC CHEMISTRY
139 Acetyl ucetone
If Is soIubIo In wafor and yIoIds an orango-rod coIor wIfh forrIc chIorIdo soIufIon.
On passIng ammonIa gas fhrough fho ofhoroaI soIufIon of fho kofono, ammonIum saIf
Is formod, m.p. 65°C.
155 Cyclohexunone
If Is soIubIo In coId wafor.
In a 100 mI round-boffomod fIask add 1 mI of fho subsfanco and 30 mI pofassIum
dIchromafo soIufIon. Hoaf fo boIIIng for 5 mIn. CooI and fIIfor and acIdIfy fho fIIfrafo wIfh
conc. hydrochIorIc acId. !IIfor fho adIpIc acId formod, m.p. 150°C.
1?9 Benzuldehyde
If Is sfrongIy soIubIo In wafor and has an odor of bIffor aImonds.
ta) If Is oxIdIzod by pofassIum pormanganafo fo bonzoIc acId, m.p. 121°C.
tb) If doos nof roduco !ohIIng`s soIufIon.
tc) In a boIIIng fubo pIaco 1 mI of bonzaIdohydo, 5 drops of acofono and 5 mI of
aIcohoI and 2 mI of dII. sodIum hydroxIdo soIufIon. BoII fho confonfs for 1 mIn. CooI and
shako vIgorousIy and fhon dIIufo wIfh 20 mI of wafor. Shako and fIIfor fho yoIIow soIId ÷
dIbonzaIacofono tC
6
H
5
CH=CH
2
)
2
CO, m.p. 112°C.
196 Sullcyldehyde
If Is sparIngIy soIubIo In wafor and gIvos a vIoIof coIor wIfh forrIc chIorIdo soIufIon.
If Is oxIdIzod by aIkaIIno pofassIum pormanganafo soIufIon fo saIIcyIIc acId, m.p. 155°C.
202 Acetophenone
If Is sparIngIy soIubIo In wafor.
On oxIdafIon wIfh aIkaIIno pofassIum pormanganafo soIufIon If yIoIds bonzoIc acId,
m.p. 121°C.
Add 2 drops of fho kofono fo 2 mI of sodIum nIfroprussIdo soIufIon foIIowod by 2 drops
of sodIum hydroxIdo soIufIon ÷ a wIno rod coIor.
TESTS FOR COMMON ORGANIC COMPOUNDS 83
20? Menthone
If Is mIscIbIo wIfh wafor and has an odor of poppormInf.
SomIcarbazono, m.p. 184°C.
210 Proplophenone
SomIcarbazono, m.p. 1?4°C.
220 Clnnumuldehyde
If Is InsoIubIo In wafor and has fho odor of cInnamon.
ta) On warmIng wIfh conc. pofassIum hydroxIdo soIufIon, If yIoIds cInnamIc acId
tm.p. 133°C) and cInnamyI aIcohoI tb.p. 254°C). CInnamyI aIcohoI can bo soparafod
by oxfracfIng fho mIxfuro wIfh ofhor and fho acId Is rocovorod by acIdIfyIng fho
aquoous soIufIon.
tb) If Is oxIdIzod by aIkaIIno pofassIum pormanganafo soIufIon fo bonzoIc acId, m.p.
121°C.
225 p-Methylucetophenone
ta) If gIvos fho samo fosf ta) as undor acofophonono.
tb) SomIcarbazono, m.p. 205°C.
232 p-Chloroucetophenone
If Is oxIdIzod fo F-chIorobonzoIc acId, m.p. 236°C.
84 LABORATORY MANUAL OF ORGANIC CHEMISTRY
248 Cltrul
If possossos an odor of Iomon and forms an addIfIon compound on shakIng wIfh an aquoous
soIufIon of sodIum bIsuIfIfo.
SomIcarbazono, m.p. 164°C.
248 p-Anlsuldehyde
If Is InsoIubIo In wafor.
In a 250 mI round-boffomod fIask pIaco 250 mg of pofassIum pormanganafo and 50 mI
of wafor. Hoaf fo dIssoIvo and cooI fho soIufIon. Add 1 mI of fho aIdohydo. GonfIy shako
unfII fho coIor of pofassIum pormanganafo dIsappoars. CooI, fIIfor and acIdIfy fho fIIfrafo
wIfh conc. hydrochIorIc acId. !IIfor fho anIsIc acId, wash wIfh coId wafor and dry, m.p.
184°C.
252 Clnnumuldehyde
If Is a coIorIoss oIIy IIquId. If possossos cInnamon odor. If Is InsoIubIo In wafor buf soIubIo
In ofhor.
ta) Tako 2 mI of fho ToIIons` roagonf In a fosf fubo and fo If add 0.1 g of fho aIdohydo.
Shako and pIaco In boIIIng wafor for 5 mIn ÷ appoaranco of sIIvor mIrror aIong
fho sIdos of fho fubo.
tb) To 2 mI of bromIno wafor In a fosf fubo, add 0.1 g of fho subsfanco and shako ÷
dIsappoaranco of bromIno coIor.
tc) OxImo, m.p. 138°C.
td) PhonyI hydrazono, m.p. 168°C.
m.p. (°C)
44 o-Nltrobenzuldehyde
If Is yoIIow In coIor, sIIghfIy soIubIo In wafor buf soIubIo In mosf organIc soIvonfs.
WIfh pofassIum pormanganafo If Is oxIdIzod fo -nIfrobonzoIc acId, m.p. 14?°C.
OxImo, m.p. 58°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 85
4? p-Chlorobenzuldehyde
OxIdafIon wIfh pofassIum pormanganafo soIufIon yIoIds F-chIorobonzoIc acId, m.p. 236°C,
2, 4-dInIfrophonyIhydrazono m.p. 265°C.
48 Benzophenone
If Is InsoIubIo In wafor and forms a yoIIow soIufIon In conc. suIfurIc acId.
ta) !uso a pInch of fho compound wIfh a smaII pIoco of sodIum mofaI ÷ bIuo coIor.
tb) 2, 4-ÐInIfrophonyIhydrazono, m.p. 265°C.
56 Chlorul hydrute CI
3
CCHtOH)
2
If has an odor rosombIIng fhaf of cucumbor.
In a fosf fubo pIaco ?0 mg of rosorcInoI, 2 mI of dII. sodIum hydroxIdo soIufIon and
20 mg of fho subsfanco and hoaf fo boIIIng ÷ rod coIor.
58 m-Nltrobenzuldehyde
If Is paIo yoIIow, sIIghfIy soIubIo In wafor.
ta) WIfh pofassIum pormanganafo If yIoIds -nIfrobonzoIc acId, m.p. 140°C
tb) OxImo, m.p. 140°C.
134 Benzoln
If Is InsoIubIo In wafor.
To 100 mg of fho subsfanco In a fosf fubo add 1 mI of !ohIIng`s soIufIon and 1 mI of
wafor. Hoaf fo boIIIng for 30 soc ÷ a rod procIpIfafo of cuprIc oxIdo.
1?9 Cumphor
If Is InsoIubIo In wafor and possossos a characforIsfIc odor.
OxImo, m.p. 118°C.
86 LABORATORY MANUAL OF ORGANIC CHEMISTRY
5.4 ESTERS
b.p. (°C)
5? Methyl ucetute
If Is coIorIoss IIquId. If has fruIfy smoII, soIubIo In coId wafor and aIcohoI.
@ 0.939
?? Kthyl ucetute
If Is coIorIoss and soIubIo In coId wafor and aIcohoI.
In a 50 mI round-boffomod fIask pIaco 1 g of fho compound and 20 mI of pofassIum
hydroxIdo soIufIon. RofIux for 20 mIn. ÐIsfII off fho ofhyI aIcohoI and porform fho Iodoform
fosf wIfh fho dIsfIIIafo.
?9 Methyl proplonute
ta) 3, 5-ÐInIfrobonzoafo, m.p. 108°C.
98 Kthyl proplonute
ta) 3, 5-ÐInIfrobonzoafo, m.p. 88°C.
120 Kthyl n-butyrute
126 n-Butyl ucetute
140 n-Butyl proplonute
TESTS FOR COMMON ORGANIC COMPOUNDS 87
148 n-Amyl ucetute
If Is a coIorIoss, InsoIubIo In wafor buf soIubIo In aIcohoI.
@ 0.8?5
1?0 Kthyl ucetoucetute
If Is coIorIoss has pIoasanf odor. SparIngIy soIubIo In wafor buf soIubIo In ofhor and aIcohoI.
@ 1.028
ÐIssoIvo 0.1 g of fho osfor In wafor by shakIng. Add 1 drop of forrIc chIorIdo
soIufIon ÷ rod coIor.
185 Dlethyl oxulute
If Is sIIghfIy soIubIo In wafor. WIfh oxcoss ammonIum hydroxIdo If yIoIds an oxamIdo whIch
subIImos wIfhouf moIfIng.
195 Methyl succlnute
If Is soIubIo In coId wafor.
@ 1.120
19? Phenyl ucetute
If Is InsoIubIo In wafor and possossos a swoof smoII.
To 20 mg of fho subsfanco add 2 mI of wafor, boII and add 1 drop of forrIc chIorIdo
soIufIon ÷ bIuo coIor.
199 Methyl benzoute
If Is coIorIoss, In soIubIo In wafor.
On hydroIysIs wIfh dII. hydrochIorIc acId If yIoIds bonzoIc acId, m.p. 121°C
@ 1.089
88 LABORATORY MANUAL OF ORGANIC CHEMISTRY
213 Kthyl benzoute
If Is a coIorIoss swoof-smoIIIng IIquId.
On addIfIon of conc. nIfrIc acId fo a coId soIufIon In conc. suIfurIc acId of fho osfor,
ofhyI -nIfrobonzoafo Is formod, m.p. 21?° C.
@ 1.04?
218 Dlethyl succlnute
If Is coIorIoss soIubIo In aIcohoI.
@ 1.042
220 Methyl phenylucetute
If Is coIorIoss, soIubIo In aIcohoI.
@ 1.068
223 Methyl sullcylute
If Is a coIorIoss compound. If smoIIs IIko wInfor groon oII tan aromafIc IIquId dIsfIIIod from
fho Ioavos of wInforgroon pIanf). If Is InsoIubIo In wafor buf soIubIo In aIcohoI and ofhor.
228 Kthyl phenylucetute
2?1 Kthyl clnnumute
If Is a coIorIoss, InsoIubIo In wafor buf soIubIo In aIcohoI.
@ 1.049
If docoIorIzos bromIno wafor.
TESTS FOR COMMON ORGANIC COMPOUNDS 89
m.p. (°C)
36 Methyl clnnumute
If Is coIorIoss, InsoIubIo In wafor, soIubIo In hof aIcohoI. If docoIorIzos aquoous bromIno
soIufIon.
3? Kthyl mundelute
WIfh ammonIum hydroxIdo If yIoIds an amIdo, m.p. 131°C
42 Phenyl sullcylute (Sulol)
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In hof aIcohoI.
If gIvos no coIor wIfh forrIc chIorIdo soIufIon.
AcofyI dorIvafIvo tm.p. 9?°C).
45 Methyl unlsute
51 Methyl oxulute
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In hof aIcohoI.
58 Methyl mundelute
WIfh conc. ammonIum hydroxIdo If yIoIds amIdo, m.p. 131°C.
90 LABORATORY MANUAL OF ORGANIC CHEMISTRY
68 Phenyl benzoute
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In hof aIcohoI.
?0 Methyl p-hydroxybenzoute
If gIvos a rod coIor wIfh forrIc chIorIdo soIufIon.
?8 Phenyl clnnumute
116 Kthyl p-hydroxybenzoute
If gIvos vIoIof coIor wIfh forrIc chIorIdo soIufIon.
BonzoyI dorIvafIvo, m.p. 89°C.
5.5 AMINES
b.p. (°C)
1? Kthylumlne C
2
H
5
NH
2
If Is soIubIo In wafor, aIcohoI and ofhor. If has an ammonIacaI odor.
ta) BonzoyI dorIvafIvo, m.p. ?1°C.
49 n-Propylumlne CH
3
CH
2
CH
2
NH
2
If Is mIscIbIo wIfh wafor, aIcohoI and ofhor.
ta) HydrochIorIdo, m.p. 159°C.
55 Dlethylumlne
If possossos a fIsh-IIko odor. If Is soIubIo In wafor and aIcohoI.
Add ono drop of fho compound fo 2 mI of sodIum nIfroprusIdo soIufIon foIIowod by 1 mI
froshIy proparod soIufIon of acofaIdohydo In wafor ÷ a doop bIuo coIor.
TESTS FOR COMMON ORGANIC COMPOUNDS 91
?? n-Butylumlne CH
3
CH
2
CH
2
CH
2
NH
2
If Is mIscIbIo wIfh wafor.
@ 0.?41
HydrochIorIdo, m.p. 195°C.
89 Trlethylumlne
If Is mIscIbIo wIfh wafor In aII proporfIons.
PIcrafo, m.p. 1?3° C.
105 Plperldlne
If Is mIscIbIo wIfh wafor and has an unpIoasanf odor.
F-ToIuonosuIfonyI dorIvafIvo, m.p. 100°C.
184 Anlllne
If Is InsoIubIo In wafor.
ta) If rosponds fo carbyIamIno fosf wIfh pofassIum hydroxIdo and chIoroform.
tb) AcofyI dorIvafIvo, m.p. 113°C.
185 Benzylumlne C
6
H
5
CH
2
NH
2
If Is mIscIbIo wIfh wafor.
AcofyI dorIvafIvo, m.p. 60°C.
193 Methyl unlllne C
6
H
5
NHCH
3
HydrochIorIdo, m.p. 121°C.
199 m-Toluldlne
ta) ÐIssoIvo 2 drops of fho subsfanco In 2 mI of 50% suIfurIc acId and add a fow drops
of pofassIum dIchromafo soIufIon ÷ a yoIIow-brown coIor.
tb) AcofyI dorIvafIvo, m.p. 65°C.
92 LABORATORY MANUAL OF ORGANIC CHEMISTRY
200 o-Toluldlne
If Is soIubIo In coId wafor.
ta) In a fosf fubo dIssoIvo 2 drops of fho subsfanco In 2 mI of 50% suIfurIc acId. Add a
fow drops of pofassIum dIchromafo soIufIon ÷ a bIuo coIor.
tb) AcofyI dorIvafIvo, m.p. 112°C.
209 o-Chlorounlllne
If Is a coIorIoss, InsoIubIo In wafor, soIubIo In aIcohoI. If rosponds fo fho dyo fosf.
ta) If forms a dyo wIfh >-naphfhoI on dIazofIsafIon.
tb) BonzoyI dorIvafIvo, m.p. 99°C.
230 m-Chlorounlllne
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In aIcohoI and gIvos fho dyo fosf wIfh
>-naphfhoI.
AcofyI dorIvafIvo, m.p. ?2°C.
251 m-Bromounlllne
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In aIcohoI. If gIvos fho dyo fosf wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 8?°C.
m.p. (°C)
32 o-Bromounlllne
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In aIcohoI and ofhor. If rosponds fo fho dyo
fosf wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 99°C.
TESTS FOR COMMON ORGANIC COMPOUNDS 93
45 p-Toluldlne
If has a poworfuI characforIsfIc odor and Is soIubIo In wafor.
ta) To 1 mI of 50% suIfurIc acId In a fosf fubo add a pInch of fho compound ÷ yoIIow
coIor.
tb) WIfh bromIno If yIoIds a 2, 6-dIbromo dorIvafIvo, m.p. ?3°C.
51 p-Anlsldlne
If Is sparIngIy soIubIo In wafor buf soIubIo In aIcohoI. If gIvos fho dyo fosf wIfh >-naphfhoI.
ta) SoIufIon of Ifs hydrochIorIdo In wafor yIoIds vIoIof coIor wIfh forrIc chIorIdo
soIufIon.
tb) AcofyI dorIvafIvo, m.p. 12?°C.
54 Dlphenylumlne C
6
H
5
NHC
6
H
5
If Is InsoIubIo In wafor buf soIubIo In aIcohoI.
ta) ÐIssoIvo 20 mg of fho compound In conc. suIfurIc acId fhon add a drop of sodIum
nIfrIfo soIufIon ÷ a bIuo coIor.
tb) ÐIssoIvo anofhor 20 mg of fho subsfanco In 1 mI hydrochIorIc acId and add a fow
drops of HNO
3
÷ a doop bIuo coIorafIon.
60 =-Nuphthylumlne
If possossos a bad odor and Is sIIghfIy soIubIo In hof wafor.
ta) Ifs hydrochIorIdo dIssoIvos In wafor fo gIvo a bIuo procIpIfafo wIfh forrIc chIorIdo
soIufIon.
tb) PIcrafo, m.p. 161°C.
66 p-Bromounlllne
If Is a coIorIoss subsfanco InsoIubIo In wafor, soIubIo In aIcohoI. If rosponds fo fho dyo fosf
wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 16?°C.
94 LABORATORY MANUAL OF ORGANIC CHEMISTRY
?0 p-Chlorounlllne
If Is soIubIo In hof wafor and aIcohoI. If gIvos fho dyo fosf wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 1?9°C.
?1 o-Nltrounlllne
If Is orango yoIIow In coIor.
If Is soIubIo In hof wafor, aIcohoI and ofhor. If gIvos fho dyo fosf wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 92°C.
?8 s-Trlchlorounlllne
If Is coIorIoss, soIubIo In aIcohoI and ofhor.
ta) If rosponds fo fho dyo fosf.
113 >-Nuphthylumlne
If Is an odorIoss buf pInk coIorod compound and sparIngIy soIubIo In hof wafor wIfh >-
naphfhoI.
ta) If doos nof gIvo a bIuo procIpIfafo wIfh forrIc chIorIdo soIufIon.
tb) AcofyI dorIvafIvo, m.p. 132°C.
114 m-Nltrounlllne
If possossos a yoIIow coIor and soIubIo In hof wafor. If rosponds fo fho dyo fosf.
AcofyI dorIvafIvo, m.p. 155°C.
140 p-Phenylenedlumlne
If Is coIorIoss and darkons on oxposuro. SparIngIy soIubIo In wafor buf soIubIo In aIcohoI.
TESTS FOR COMMON ORGANIC COMPOUNDS 95
ta) If rosponds fo fho dyo fosf wIfh >-naphfhoI.
tb) AcofyI dorIvafIvo, m.p. 305°C.
14? p-Nltrounlllne
If Is yoIIow In coIor and soIubIo In hof wafor. If gIvos fho dyo fosf wIfh >-naphfhoI.
AcofyI dorIvafIvo, m.p. 215°C.
5.6 AMIDES AND ANILIDES
b.p. (°C)
105 Formumlde
If Is soIubIo In wafor. On hoafIng If docomposos ovoIvIng ammonIa gas.
ta) To 2 mI of morcurIc chIorIdo soIufIon add 1 drop of fho compound and hoaf fo
boIIIng for 30 soc ÷ a whIfo procIpIfafo of morcurous chIorIdo Is obfaInod.
tb) ÐIssoIvo 25 mg of fho subsfanco In 2 mI of wafor and fhon add 2 drops of forrIc
chIorIdo soIufIon ÷ a wIno-rod coIor whIch on hoafIng forms a brown procIpIfafo.
m.p. (°C)
?9 Proplonumlde
If Is soIubIo In wafor and ofhor.
ta) WIfh ?5% suIfurIc acId af 120°C If yIoIds propIonIc acId, b.p. 140°C.
tb) Ono hoafIng wIfh anIIIno If yIoIds propIonanIIIdo, m.p. 103°C.
82 Acetumlde
If Is roadIIy soIubIo In wafor and aIcohoI.
ta) To 2 mI of fho aquoous soIufIon, add an oquaI voIumo of forrIc chIorIdo soIufIon
÷ a wIno rod coIor yIoIdIng a roddIsh brown procIpIfafo on warmIng.
tb) PIcrafo, m.p. 10?°C.
96 LABORATORY MANUAL OF ORGANIC CHEMISTRY
114 Acetunlllde
If Is soIubIo In hof wafor.
WIfh 1 moIo of bromIno In acofIc acId If yIoIds F-bromo dorIvafIvo, m.p. 16?°C.
115 n-Butyrumlde
If Is roadIIy soIubIo In wafor, aIcohoI and ofhor.
On hoafIng wIfh anIIIno If yIoIds -bufyranIIIdo, m.p. 90°C.
129 Benzumlde
If Is sparIngIy soIubIo In coId wafor.
MIx 50 mg of fho subsfanco wIfh fhroo fImos Ifs amounf of soda IImo. Infroduco fho
mIxfuro In an IgnIfIon fubo and hoaf ÷ odor of bonzonIfrIIo tbIffor aImonds).
133 Sullcylumlde
If Is a yoIIow crysfaIIIno soIId, sparIngIy soIubIo In coId wafor.
ta) If gIvos vIoIof coIor wIfh forrIc chIorIdo soIufIon.
tb) AcofyI dorIvafIvo, m.p. 143°C.
15? Phenylucetumlde
If Is a coIorIoss subsfanco and sparIngIy soIubIo In wafor.
In a boIIIng fubo pIaco 50 mg of fho compound and 2 mI of dII. hydrochIorIc acId. BoII
and cooI fho soIufIon. NoufraIIzo wIfh sodIum hydroxIdo soIufIon and fIIfor fho phonyIacofIc
acId, m.p. ?6°C.
162 Benzunlllde
If Is coIorIoss or roddIsh compound, sparIngIy soIubIo In aIcohoI.
ta) In a fosf fubo boII 0.5 g of fho soIId wIfh dII. hydrochIorIc acId ÷ bonzoIc acId Is
formod.
TESTS FOR COMMON ORGANIC COMPOUNDS 97
tb) Add bromIno soIufIon fo 0.5 g of fho anIIIdo In a fosf fubo ÷ F-bromoanIIIdo, m.p.
204°C.
1?6 o-Nltrobenzumlde
If Is coIorIoss and soIubIo In hof wafor and aIcohoI.
ta) Hoaf 0.5 g of fho amIdo wIfh sodIum hydroxIdo soIufIon and acIdIfy, -NIfrobonzoIc
acId, m.p. 14?°C.
tb) BoII 0.5 g of fho amIdo In fho prosonco of Sn/HCI ÷ anfhranIIIc acId, m.p. 144° C.
192 Bluret NH
2
CONHCONH
2
If Is soIubIo In coId wafor.
ta) Hoaf 50 mg of fho compound In a dry fosf fubo abovo fho moIfIng poInf ÷ sfrong
smoII of ammonIa gas.
tb) To 1 mI of fho aquoous soIufIon add an oquaI voIumo of coppor suIfafo soIufIon÷
vIoIof coIor.
201 p-Nltrobenzumlde
If Is coIorIoss, soIubIo In hof wafor and aIcohoI.
ta) Hoaf 0.5 g of fho amIdo wIfh sodIum hydroxIdo soIufIon and acIdIfy÷F-nIfrobonzoIc
acId, m.p. 186°C.
tb) On roducfIon, yIoIds F-amInobonzoIc acId, m.p. 186°C.
219 J-Phthulumlde
If Is a coIorIoss subsfanco, sparIngIy soIubIo In wafor.
ta) On hoafIng abovo Ifs moIfIng poInf ammonIa gas Is ovoIvod.
tb) PIaco 25 mg of fho subsfanco In a dry fosf fubo, add 2 drops of conc. suIfurIc acId
and warm. Add 50 mg of rosorcInoI and agaIn hoaf fho mIxfuro gonfIy fIII If affaIns
a roddIsh-brown coIor. CooI and add a fow drops of wafor foIIowod by dII. sodIum
hydroxIdo soIufIon fIII aIkaIIno. Tako 1 mI of fhIs soIufIon Info anofhor fosf fubo
and fIII If up wIfh wafor ÷ a groon fIuorosconco.
98 LABORATORY MANUAL OF ORGANIC CHEMISTRY
233 Phthullmlde
If Is a coIorIoss compound, InsoIubIo In wafor buf soIubIo In absoIufo aIcohoI.
ta) If rosponds fo fIuorosconco fosf.
tb) N-acofafo dorIvafIvo, m.p. 133°C.
tc) N-bonzoafo dorIvafIvo, m.p. 115°C.
242 Succlnumlde
If Is soIubIo In hof wafor buf InsoIubIo In aIcohoI and ofhor.
ta) If rosponds fo fosf ta) as IIsfod for phfhaIamIdo.
tb) On hoafIng If docomposos fo gIvo ammonIa and succInImIdo, m.p. 125°C.
418 Oxumlde
If Is InsoIubIo In wafor, aIcohoI or ofhor.
ta) In a fosf fubo pIaco 25 mg of fho compound and 5 mI of dII. sodIum hydroxIdo
soIufIon. BoII for 30 soc. AcIdIfy fho warm soIufIon wIfh gIacIaI acofIc acId. Add
2÷3 drops of caIcIum chIorIdo soIufIon ÷ ImmodIafoIy a whIfo procIpIfafo tcaIcIum
oxaIafo) appoars.
tb) In a fosf fubo pIaco ?5 mg of fho compound and 2 mI of dII. sodIum hydroxIdo
soIufIon, foIIowod by 2 drops of coppor suIfafo soIufIon t!ohIIng`s soIufIon No. 1)
and shako ÷ pInk coIor.
5.7 ARYL HALIDES
b.p. (°C)
132 Chlorobenzene
If Is a coIorIoss, pIoasanf smoIIIng IIquId, InsoIubIo In wafor buf soIubIo In aIcohoI,
ofhor or bonzono. ChIorbonzono rosponds fo fho BoIIsfoIn fosf.
TESTS FOR COMMON ORGANIC COMPOUNDS 99
On warmIng fo 80°C wIfh conc. nIfrIc acId t1 moIo) and conc. suIfurIc acId If yIoIds
F-nIfro dorIvafIvo tm.p. 83°C).
15? Bromobenzene
If Is sIIghfIy coIorod and pIoasanf smoIIIng IIquId. InsoIubIo In wafor buf soIubIo In aIcohoI
and ofhor.
WIfh conc. nIfrIc acId and suIfurIc acId af room fomporafuro, If yIoIds a F-nIfro dorIvafIvo,
m.p. 120°C.
Bromobonzono rosponds fo fho BoIIsfoIn fosf.
159 o-Chlorotoluene
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In bonzono and ofhor.
On oxIdafIon wIfh pofassIum pormanganafo soIufIon, If yIoIds -chIorobonzoIc acId,
m.p. 140°C.
162 m-Chlorotoluene
If Is coIorIoss and InsoIubIo In wafor buf soIubIo In bonzono and ofhor.
On oxIdafIon wIfh aIkaIIno pofassIum pormanganafo soIufIon yIoIds, -chIorobonzoIc
acId, m.p. 153°C.
162 p-Chlorotoluene
If Is a coIorIoss IIquId, InsoIubIo In wafor, buf soIubIo In bonzono and ofhor.
On oxIdafIon wIfh aIkaIIno pofassIum pormanganafo soIufIon, If gIvos F-chIorobonzoIc
acId, m.p. 236°C.
181 o-Bromotoluene
If Is coIorIoss, InsoIubIo In wafor buf soIubIo In ofhor and aIcohoI.
ta) On oxIdafIon wIfh aIkaIIno pofassIum pormanganafo soIufIon, If yIoIds -
bromobonzoIc acId, m.p. 14?°C.
In a 100 mI round-boffomod fIask pIaco 1 mI of fho compound and 2.5 g soIId
pofassIum pormanganafo. To fho mIxfuro add 40 mI of wafor, 5 drops of sodIum
100 LABORATORY MANUAL OF ORGANIC CHEMISTRY
hydroxIdo soIufIon. and rofIux for 3 hr. CooI and pass suIfur dIoxIdo gas unfII any
purpIo coIor and brown procIpIfafo havo dIsappoarod. !IIfor off fho whIfo soIId,
wash wIfh coId wafor) -bromobonzoIc acId Is obfaInod, m.p. 14?°C.
183 m-Bromotoluene
If Is coIorIoss, InsoIubIo In wafor, soIubIo In aIcohoI.
If Is oxIdIzod fo -bromobonzoIc acId, m.p. 251°C.
m.p. (°C)
53 p-Dlchlorobenzene
If has a characforIsfIc odor.
If Is coIorIoss soIId and InsoIubIo In wafor, soIubIo In aIcohoI and ofhor.
NIfrafIon wIfh conc. nIfrIc acId yIoIds, 1,4-dIchIoro-2-nIfrobonzono, m.p. 54°C.
89 p-Dlbromobenzene
If Is a whIfo crysfaIIIno soIId, possossos characforIsfIc aromafIc odor and InsoIubIo In wafor
buf soIubIo In bonzono and ofhor.
Immorso a 50 mI round-boffomod fIask In Ico-coId wafor and chargo If wIfh 1 mI of fho
subsfanco, add 2 mI oach of Ico-coId conc. nIfrIc acId and conc. suIfurIc acId fhrough a
droppIng funnoI dropwIso. Affor fho addIfIon Is compIofo koop fho fIask In a hof wafor-bafh
for 15 mIn. CooI and pour fho mIxfuro on Ico coId wafor. CrysfaIIIzo fho soIId 1,4-dIbromo-
2-nIfrobonzono from ofhanoI, m.p. 126° C.
119 ¡odoIorm CHI
3
If has a characforIsfIc yoIIow coIor and possossos an unpIoasanf odor. If Is InsoIubIo In
wafor buf soIubIo In aIcohoI and ofhor.
ta) Hoaf 0.1 g of fho compound In a fosf fubo ÷ vIoIof coIor duo fo fho ovoIufIon of
IodIno appoars.
tb) To 0.1 g of fho compound In a fosf fubo add 1 mI of aIcohoI and 2 drops of sIIvor
nIfrafo soIufIon ÷ a yoIIow procIpIfafo.
tc) Tako 0.2 g of fho compound In a fosf fubo, add 1 g of rosorcInoI and 2 mI of
aIcohoIIc sodIum hydroxIdo soIufIon and warm In a boakor of hof wafor ÷ a rod
coIor changIng fo vIoIof.
TESTS FOR COMMON ORGANIC COMPOUNDS 101
5.8 MISCELLANEOUS COMPOUNDS
b.p. (°C)
83 Cyclohexene
To 1 mI soIufIon of bromIno soIufIon In carbon fofrachIorIdo In a fosf fubo, add 2 drops of
fho compound ÷ ImmodIafo docoIorIzafIon of bromIno coIor.
On oxIdafIon wIfh conc. nIfrIc acId If yIoIds adIpIc acId, m.p. 152°C.
210 Nltrobenzene
If Is yoIIow IIquId wIfh odor of bIffor aImonds and InsoIubIo In wafor. If Is soIubIo In organIc
soIvonfs.
ta) On warmIng wIfh fummIng nIfrIc acId and conc. suIfurIc acId If yIoIds
-dInIfrobonzono, m.p. 90°C.
tb) BoII 1 mI of fho compound wIfh 4 mI of sfannous chIorIdo soIufIon In conc.
hydrochIorIc acId. To 2 mI of fho rosuIfIng anIIIno soIufIon add sodIum nIfrIfo
soIufIon. CooI and add aIkaIIno soIufIon of >-naphfhoI÷a scarIof rod dyo.
220 o-Nltrotoluene
If Is a paIo yoIIow IIquId, smoIIs IIko nIfrobonzono and InsoIubIo In wafor.
ta) In a fosf fubo pIaco 2 drops of fho subsfanco and 2 drops of dII. sodIum hydroxIdo
soIufIon ÷ a doop rod coIor.
tb) On oxIdafIon wIfh pofassIum pormanganafo soIufIon, If yIoIds -nIfrobonzoIc acId,
m.p. 14?°C.
265 o-Nltrounlsole
If Is InsoIubIo In wafor buf mIscIbIo wIfh organIc soIvonfs.
WIfh conc. nIfrIc acId and suIfurIc acId af 0°C, If yIoIds 2,4-dInIfro dorIvafIvo, m.p.
88°C.
102 LABORATORY MANUAL OF ORGANIC CHEMISTRY
268 o-Nltrophenetol
If Is InsoIubIo In wafor buf mIscIbIo wIfh organIc soIvonfs. WIfh conc. nIfrIc acId and suIfurIc
acId, If yIoIds, 2, 4-dInIfro dorIvafIvo, m.p. 86°C.
m.p. (°C)
36 Azoxybenzene
If has brIghf yoIIow noodIos, InsoIubIo In wafor buf soIubIo In aIcohoI and ofhor.
In aquoous aIcohoIIc soIufIon, wIfh zInc dusf ÷ forms orango-rod coIorod azobonzono,
m.p. 68°C and fhon hydrazobonzono, m.p. 131°C.
54 p-Nltrounlsole
InsoIubIo In wafor buf soIubIo In aIcohoI and ofhor.
WIfh fumIng nIfrIc acId, If yIoIds a 2, 4-dInIfro dorIvafIvo, m.p. 88°C.
54 p-Nltrotoluene
If Is vory paIo yoIIow soIId and has an odor IIko nIfrobonzono.
If Is InsoIubIo In wafor buf soIubIo In aIcohoI.
59 p-Nltrophenetol
If Is InsoIubIo In wafor, sparIngIy soIubIo In coId aIcohoI buf roadIIy soIubIo In ofhor.
WIfh conc. nIfrIc acId and suIfurIc acId In coId, If yIoIds a 2, 4-dInIfro dorIvafIvo, m.p.
?6°C.
65 BenzenesulIonlc ucld
If Is roadIIy soIubIo In wafor.
BonzonosuIfonamIdo, m.p. 153°C.
68 Azobenzene C
6
H
5
N=NC
6
N
5
If Is orango-rod In coIor and sparIngIy soIubIo In wafor.
TESTS FOR COMMON ORGANIC COMPOUNDS 103
ta) Whon froafod wIfh bromIno In acofIc acId If gIvos a dIbromo dorIvafIvo, m.p.
18?°C.
tb) WIfh zInc dusf and sodIum hydroxIdo If yIoIds hydrazobonzono, m.p. 131°C.
69 p-ToluenesulIonyl chlorlde
On boIIIng wIfh wafor, If yIoIds F-foIuonosuIfonIc acId, m.p. 92°C.
115 p-Benzoqulnone
If has a characforIsfIc pungonf odor.
ta) ÐIssoIvo 20 mg of fho compound In 1 mI of pofassIum hydroxIdo soIufIon, fho
soIufIon furns brown on sfandIng.
tb) If roducos ammonIacaI sIIvor nIfrafo soIufIon, formIng a sIIvor mIrror.
tc) In a fosf fubo pIaco 20 mg of fho compound and an oquaI amounf of forous suIfafo.
Add 2 mI of dII. suIfurIc acId and shako. Add 5 mI of wafor and warm. A cIoar
yoIIow soIufIon Is obfaInod. AIIow fho fosf fubo fo sfand In coId wafor for somo
fImo ÷ groon noodIos of hydroquInono aro formod.
13? p-ToluenesulIonumlde
If Is sparIngIy soIubIo In coId wafor buf soIubIo In dII. sodIum hydroxIdo soIufIon, ofhor or
aIcohoI.
ta) On froafmonf wIfh a mIxfuro of bonzyI chIorIdo and sodIum hydroxIdo In aIcohoI,
If yIoIds a bonzyI dorIvafIvo, m.p. 116°C.
tb) On oxIdafIon wIfh pofassIum pormanganafo soIufIon If producos
F-suIfonamIdobonzoIc acId, m.p. 280°C.
153 BenzenesulIonumlde
If Is sparIngIy soIubIo In wafor buf soIubIo In aIcohoI and ofhor.
ta) WIfh bonzyI chIorIdo t1 moI) and sodIum hydroxIdo In aIcohoI, If yIoIds fho bonzyI
dorIvafIvo, m.p. 88°C.
104 LABORATORY MANUAL OF ORGANIC CHEMISTRY
153 o-ToluenesulIonumlde
If Is sparIngIy soIubIo In coId wafor buf soIubIo In aIcohoI and ofhor.
WIfh ?5% suIfurIc acId If yIoIds foIuono, b.p. 110°C.
198 Anlllne hydrochlorlde
If Is a coIorIoss subsfanco buf furns bIack on sforago. If Is soIubIo In wafor buf InsoIubIo In
bonzono or ofhor.
ÐIssoIvo 25 mg of fho subsfanco In dIsfIIIod wafor In a fosf fubo and a fow drops of
sIIvor nIfrafo soIufIon and shako ÷ hoavy whIfo procIpIfafo of sIIvor chIorIdo.
300 SulIunlllc ucld
If Is a whIfo crysfaIIIno soIId, soIubIo In hof wafor.
ta) To 25 mg of fho subsfanco add 2 mI of pofassIum dIchromafo soIufIon and dII.
suIfurIc acId and hoaf fo boIIIng ÷ pungonf odor of F-bonzoquInono.
tb) To a soIufIon of 50 mg of fho compound In hof wafor add bromIno soIufIon t10 mI
bromIno) and 1.5 g pofassIum bromIdo In 100 mI wafor. SfIr fIII fho IIquId Is paIo
yoIIow. !IIfor fho soIId, wash wIfh coId wafor and dry, 2,4,6-frIbromoanIIIno, m.p.
199°C.
ChupIer 6
PREPARATION OF DERIVATIVES
Tho fosfs In fho procodIng chapfors hoIp fo rocognIzo fho unknown Info Ifs spocIfIc cIass
such as an aIdohydo, amIno or a carboxyIIc acId. Thon fho physIcaI proporfIos of fho unknown
aro comparod wIfh fhoso of fho roprosonfafIvo compounds. Such a comparIson offon prosonfs
sovoraI possIbIIIfIos. Tho choIco, howovor, can bo narrowod down by proparIng a dorIvafIvo.
A JeriruIire Is usuaIIy a soIId maforIaI whIch can roadIIy bo proparod from fho unknown
and can bo oasIIy IsoIafod and purIfIod. Moroovor, If shouId bo crysfaIIIno and dIffor In
physIcaI proporfIos from fho unknown. !ormafIon of a dorIvafIvo InvoIvos a roacfIon bofwoon
fho funcfIonaI group and anofhor roagonf. If Is fhus dosIrabIo fhaf fho roacfIon bo
accompIIshod In a shorf porIod and condIfIons aro confroIIabIo. Proparo fho dorIvafIvos
carofuIIy bocauso you aro workIng wIfh smaII amounfs of compounds. AIways rocrysfaIIIzo
fIII a consfanf moIfIng poInf Is obfaInod. Tho moIfIng poInf of a dorIvafIvo can bo usod as a
proof for fho IdonfIfy of fho unknown. A doscrIpfIon of varIous dorIvafIvos Is Infondod In
fhIs chapfor.
6.1 DERIVATIVES OF ALCOHOLS
SovoraI fypos of dorIvafIvos can bo proparod for fho characforIzafIon of bofh aIcohoIs and
phonoIs.
(a) Acetates
Acofafo osfors aro parfIcuIarIy usofuI In fho characforIzafIon of poIyhydrIc aIcohoIs and aro
usuaIIy oasy fo proparo.
106 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a boIIIng fubo pIaco 0.5 g t10 drops of fho IIquId) of aIcohoI sampIo, 4 mI
pyrIdIno and add 2 mI of froshIy dIsfIIIod acofIc anhydrIdo wIfh shakIng. Hoaf fho mIxfuro
on a wafor-bafh for 5 mIn. Pour fho confonfs onfo Ico fakon In a boakor and fIIfor off fho
soIId, wash If wIfh dII. hydrochIorIc acId fo romovo pyrIdIno. !InaIIy wash wIfh coId wafor.
RocrysfaIIIzo from hof aquoous ofhanoI. Tako fho moIfIng poInf and comparo from fho
fabIos.
(b) p-Nitrobenzoates
ThIs Is gonoraIIy fho mosf usofuI osfor dorIvafIvo for fho characforIzafIon of aIcohoIs.
Procedure: In a smaII fosf fubo pIaco 0.5 g t10 drops of fho IIquId) of aIcohoI sampIo, 4 mI
pyrIdIno and 1 g p-nIfrobonzoyI chIorIdo. Hoaf fho confonfs for 10 mIn and pour fho mIxfuro
on Ico wafor. !IIfor off fho soIId on a Buchnor funnoI, wash wIfh dII. hydrochIorIc acId fo
romovo pyrIdIno. RocrysfaIIIzo from aquoous ofhanoI.
Bofh fho abovo roacfIons procood woII wIfh prImary and socondary aIcohoIs buf nof
wIfh forfIary aIcohoIs.
Question
6.1 Why do forfIary aIcohoIs nof roacf wIfh p-nIfrobonzoyI chIorIdo7
(c) =-Naphthylcarbamates (urethane)
=-NaphfhyI urofhano Is anofhor usofuI dorIvafIvo for fho characforIzafIon of aIcohoIs.
Procedure: Tako fho unknown aIcohoI 1 g t1 mI If IIquId) In a dry fosf fubo and fo If add
0.5mI of =-naphfhyI Isocyanafo. Shako fho confonfs and aIIow fho fubo sfand af room
fomporafuro for 5 mIn wIfh occasIonaI shakIng. A soIId shouId appoar affor fhIs porIod. In
caso no soIId Is formod warm on a wafor-bafh and cooI agaIn. Scrafch fho sIdos of fho fubo
If nocossary. !IIfor fho soIId and rocrysfaIIIzo from IIghf pofroIoum.
PREPARATION OF DERIVATIVES 107
6.2 DERIVATIVES OF PHENOLS
As a gonoraI ruIo fho dorIvafIvos proparod for aIcohoIs can bo proparod and aro usofuI for
phonoIs as woII. Acofafos and p-nIfrobonzoafos can bo proparod as In fho caso of aIcohoIs.
In addIfIon, fho foIIowIng dorIvafIvo may aIso bo usofuI.
(a) Benzoates
Tho hydroxyI group of phonoIs can bo osforIfIod by fho Schöffon-Baumann roacfIon usIng
bonzoyI chIorIdo and a baso.
Procedure: PIaco 0.5 mI of fho phonoI In 2.5 mI of wafor In a fosf fubo. To fhIs add 2.5 mI
of 10% of sodIum hydroxIdo soIufIon foIIowod by 0.3 mI of bonzoyI chIorIdo. Sfoppor fho
fubo and shako for sovoraI mInufos. Tho odor of bonzoyI chIorIdo shouId dIsappoar. CoIIocf
fho soIId on a Buchnor funnoI and wash wIfh coId wafor. RocrysfaIIIzo from hof aIcohoI.
Question
6.2 WrIfo a mochanIsm for fho Schöffon-Baumann roacfIon.
(b) 3, 5-Dinitrobenzoates
3, 5-ÐInIfrobonzoafo osfors aro usofuI for bofh phonoIs and aIcohoIs.
Procedure: In a 100 mI round boffomod fIask oquIppod wIfh a rofIux condonsor, pIaco 0.5 g
of phonoI, 5 mI of pyrIdIno and 1.3 g of 3, 5-dInIfrobonzoyI chIorIdo and rofIux fho mIxfuro
gonfIy for 30 mIn. CooI fho confonfs and pour onfo 50 mI of 5% suIfurIc acId. Shako fho
mIxfuro, fIIfor fho soIId and wash wIfh wafor. Suspond fho soIId In 50 mI of 5% sodIum
hydroxIdo soIufIon fo romovo any 3, 5-dInIfrobonzoIc acId and fIIfor agaIn. RocrysfaIIIzo fho
dorIvafIvo from hof aquoous ofhanoI.
108 LABORATORY MANUAL OF ORGANIC CHEMISTRY
6.3 DERIVATIVES OF ALDEHYDES AND KETONES
Thoso fwo cIassos of compounds roacf wIfh sImIIar roagonfs fo form crysfaIIIno soIIds.
(a) 2, 4-Dinitrophenylhydrazones
2, 4-ÐInIfrophonyIhydrazonos, somIcarbazonos, oxImos, ofc. aro coIorod soIIds and havo
sharp moIfIng poInfs.
Procedure: PIaco 0.2 g of 2, 4-dInIfrophonyIhydrazIno and 10 mI of ofhanoI In an ÐrIonmoyor
fIask. To fhIs add 5 drops of conc. suIfurIc acId and warm fo compIofo fho soIufIon. CooI and
add 0.2 g of unknown aIdohydo tor kofono) dIssoIvod In 1 mI ofhanoI. Warm fho confonfs In
wafor-bafh for 1÷2 mIn. and fhon aIIow fo sfand for 15-30 mIn af room fomporafuro. If no
soIId soparafos fhon add wafor fIII procIpIfafIon Is compIofo. !IIfor and rocrysfaIIIzo fho
soIId from aquoous ofhanoI.
AIfornafIvoIy If 2, 4-dInIfrophonyIhydrazIno roagonf Is provIdod fhon procood as foIIows:
ÐIssoIvo 0.2 g of aIdohydo tkofono) In 2 mI of 95% ofhanoI. To fhIs add 2 mI of fho
roagonf. Shako fho mIxfuro vIgorousIy. If a procIpIfafo doos nof form ImmodIafoIy aIIow fo
sfand for 15 mIn. !IIfor and crysfaIIIzo fho soIId from aquoous ofhanoI.
To mako a 2, 4-ÐNP dorIvafIvo of acofono, Insfoad add acofono dropwIso fo 2, 4-ÐNP
soIufIon In a fosf fubo, us the derlvutlve ls soluble ln ucetone.
In fho caso of acofophonono If an oIIy Iayor porsIsfs, koop fho fubo In Ico and sfIr. Tho
dorIvafIvo wIII procIpIfafo ouf.
Question
6.3 Why Is adjusfmonf of pH ossonfIaI In fho abovo roacfIon7
(b) Semicarbazones
SomIcarbazonos aro oasIIy formod and havo sharp moIfIng poInfs.
Procedure: PIaco 0.5 g of somIcarbazIdo hydrochIorIdo, 0.8 g of sodIum acofafo, 5 mI of
wafor and 1 mI of ofhanoI In a fosf fubo. To fhIs add 500 mg t0.5 mI) of aIdohydo or kofono.
PREPARATION OF DERIVATIVES 109
Shako fho mIxfuro for a fow mInufos fhon warm In a boakor confaInIng wafor af 70÷75°C
for 10 mIn. and fhon aIIow fo cooI. Tho somIcarbazono procIpIfafos ouf from fho coId soIufIon
on sfandIng. RocrysfaIIIzo fho dorIvafIvo from hof aquoous ofhanoI.
(c) Phenylhydrazones
Procedure: ÐIssoIvo 0.4 g of phonyIhydrazIno In 1.5 mI of wafor and add soIufIon of 0.2 g of
aIdohydo or kofono dIssoIvod In 5 mI ofhanoI. BoII fho mIxfuro for 1 mIn, add 2 drops of
gIacIaI acofIc acId and boII agaIn for 5 mIn. CooI and add wafor fIII a soIId soparafos ouf.
!IIfor fho soIId and rocrysfaIIIzo from hof ofhanoI.
(d) Oximes
AIdohydos and kofonos form crysfaIIIno oxImo dorIvafIvos on roacfIon wIfh hydroxyIamIno
hydrochIorIdo.
Procedure: In a fosf fubo, dIssoIvo 0.5 g hydroxyIamIno hydrochIorIdo and 1 g of sodIum
acofafo In 2 mI wafor. To fho soIufIon add 0.2 g of fho unknown carbonyI compound. In caso
fho compound Is nof soIubIo In wafor add ofhanoI dropwIso fIII a cIoar soIufIon Is obfaInod.
Warm fho confonfs on a wafor-bafh for 15 mIn and fhon cooI In Ico. If a soIId doos nof
appoar scrafch fho sIdos of fho fubo wIfh a gIass rod. !IIfor fho soIId and rocrysfaIIIzo from
hof aquoous ofhanoI.
6.4 DERIVATIVES OF CARBOXYLIC ACIDS
(a) s-Benzylisothiouronium salts
ThIs roacfIon shouId nof bo porformod If fho soIufIon Is aIkaIIno, ofhorwIso bonzyIfhIoI Is
IIborafod whIch has obnoxIous odor.
Procedure: ÐIssoIvo or suspond 0.25 g of fho acId In 1 mI of wafor In a fosf fubo. Add 1 drop
of phonoIphfhaIoIn IndIcafor and fhon noufraIIzo wIfh 1 N sodIum hydroxIdo soIufIon fIII a
110 LABORATORY MANUAL OF ORGANIC CHEMISTRY
pInk coIor Is obfaInod. Add 3 drops of 0.1 N hydrochIorIc acId fIII fho soIufIon Is noufraI.
Now add 1 g of s-bonzyIIsofhIouronIum chIorIdo dIssoIvod In 3 mI of wafor. CooI fho mIxfuro
In an Ico-bafh. !IIfor fho soIId and rocrysfaIIIzo from hof aquoous ofhanoI. Tho soIufIon af
fhIs sfago shouId bocomo faInfIy pInk. Mako suro fho soIufIon Is noufraI.
(b) Amides
AmIdos aro usofuI drIvafIvos of carboxyIIc acIds and can bo oasIIy proparod.
Procedure: In a morfar, grInd fogofhor 0.5 g of fho unknown acId and 2 g of phosphorus
ponfachIorIdo unfII fho mIxfuro bocomos IIquId. To fho crudo acId chIorIdo so obfaInod add
sIowIy 10 mI of IIquor ammonIa. Affor fho vIgorous roacfIon has sfoppod, sfIr and cooI.
!IIfor fho soIId and wash wIfh coId wafor and rocrysfaIIIzo from hof ofhanoI.
Question
6.4 Why aro amIdos proforabIy proparod by fho abovo mofhod and nof by froafmonf of
acIds wIfh NH
3
foIIowod by hoafIng7
(c) Anilides and p-toluids
Thoso fwo dorIvafIvos can bo proparod by roacfIng an acId chIorIdo wIfh anIIIno or p-foIuIdIno.
Procedure: Tako 1 g of fho unknown acId and proparo fho acId chIorIdo oIfhor by usIng
PCI
5
as In fho abovo oxporImonf or fho acId for 30 mInufos wIfh 2.5 mI of fhIonyI chIorIdo
In a smaII round boffom fIask.
CooI fho acId chIorIdo soIufIon and fo fhIs add 2 g of amIno soIufIon In 20 mI bonzono
and warm fho mIxfuro In a hof wafor-bafh. CooI and fransfor fho soIufIon In a soparafory
funnoI. Wash fho bonzono Iayor succossIvoIy wIfh 2 mI wafor, 5 mI of 5 % hydrochIorIc acId,
PREPARATION OF DERIVATIVES 111
5 mI of 5% sodIum hydroxIdo soIufIon and fInaIIy wIfh 5 mI wafor. ÐIsfII bonzono and
rocrysfaIIIzo fho rosIduo from aIcohoI.
(d) p-Bromophenacyl esters
Procedure: NoufraIIzo wIfh 10% sodIum hydroxIdo soIufIon, a 0.5 g of fho acId suspondod
In 3 mI of wafor. To fhIs add 5 mI of ofhyI aIcohoI and 0.5 g of p-bromophonacyI bromIdo and
rofIux for 1 hr. CooI and coIIocf fho soIId, wash wIfh wafor and rocrysfaIIIzo from hof ofhanoI.
6.5 DERIVATIVES OF ESTERS
In fho IdonfIfIcafIon of an osfor wo aro facod wIfh fho probIom of IdonfIfyIng fho acId as woII
as fho aIcohoIIc compononf. Tho osfor can, fhoroforo, bo hydroIyzod wIfh dII. sodIum
hydroxIdo soIufIon and fho acId as woII as fho aIcohoI porfIons aro soparafod and fhoIr
dorIvafIvos proparod. AIfornafIvoIy, fho 3,5-dInIfrobonzoafo dorIvafIvo of fho unknown osfor
may bo proparod.
Procedure: MIx 2 mI of fho osfor wIfh 1.5 g of 3,5-dInIfrobonzoIc acId and 2 drops of conc.
suIfurIc acId In a 50 mI round boffom fIask fIfod wIfh a rofIux condonsor. Hoaf fho mIxfuro
In an oII-bafh af 150°C for 45 mIn. CooI and add 25 mI ofhor and fransfor fho soIufIon fo a
soparafary funnoI. Wash fho ofhoroaI soIufIon wIfh 5% sodIum carbonafo soIufIon fo romovo
fho acId. Wash fho ofhor soIufIon wIfh wafor fwIco. Ðry ofhor soIufIon on sodIum suIfafo.
!IIfor and ovaporafo ofhor. RocrysfaIIIzo fho soIId from hof aquoous ofhanoI.
6.6 DERIVATIVES OF CARBOHYDRATES
(a) Osazones
Carbohydrafos boarIng an aIdohydo or kofo group roacf wIfh oxcoss phonyIhydrazIno fo
produco osazonos. In fho formafIon of osazonos ono carbonyI group Is oxIdIzod, fhoroforo, a
numbor of IsomorIc sugars tof fho fypo OCH÷CHOH÷R and CH
2
OH÷CO÷R, I.o., Ð-gIucoso,
Ð-mannoso and Ð-frucfoso) form osazonos.
112 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a fosf fubo pIaco 0.2 g sugar, 0.4 g phonyIhydrazIno, 0.6 g sodIum acofafo
and 4 mI dIsfIIIod wafor. PIaco fho fubo In a boakor of boIIIng wafor. Nofo fho fImo of
ImmorsIon and fho fImo of procIpIfafIon of fho osazono. Shako fho fubo occasIonaIIy. Tho
fImo roquIrod for fho procIpIfafIon of fho osazono may bo fakon as ovIdonco for fho
IdonfIfIcafIon of fho unknown sugar. Tho moIfIng poInfs of fho osazonos boIng foo cIoso aro
gonoraIIy of no vaIuo.
Table 6.1: Some physical properties of carbohydrates
Sugur SpeclIlc Tlme Ior m.p. Derlvutlves (°C)
rotutlon osuzone oI
ln wuter Iormutlon osuzone
ut 20°C (mln) (°C)
Ð-GIucoso thydrafos) +48 4÷5 205 Ponfaacofafo,
=-112, >-132
Ð-GIucoso tanhydrous) +53 4÷5 205 Ponfabonzoafo, 179
Ð-!rucfoso ÷92 2 205 Ponfaacofafo
=-70, >-109
Ponfabonzoafo, 79
MaIfoso thydrafod) +129 SoIubIo ÷
MaIfoso tanhydrous) +129 SoIubIo Ocfaacofafo,
=-125, =-169
Ð-GaIacfoso tanhydrous) +82 15 201 ÷
Lacfoso tanhydrous) +52 SoIubIo ÷
Sucroso +66 30 205 Ocfaacofafo, 69
L-ArabInoso +105 9 166 Ponfaacofafo,
=-94, >-86
Ð-XyIoso +19 7 164 Ponfaacofafo,
=-59, >-126
Question
6.5 Why Is If oasy fo IsoIafo an osazono fhan a sugar IfsoIf7
PREPARATION OF DERIVATIVES 113
(b) Acetates
A carbohydrafo nood fo bo compIofoIy acofyIafod In ordor fo avoId any confamInafIon. !or
fhIs purposo an oxcoss of fho acofyIafIng agonf, i.c., acofIc anhydrIdo Is usod. Tho = - or fho
> - form of fho acofafo may bo obfaInod dopondIng on fho cafaIysf ompIoyod.
>-Acetate
Procedure: ÐIssoIvo 1 g of powdorod unknown carbohydrafo and 1 g of powdorod fusod
sodIum acofafo In 10 mI of acofIc anhydrIdo by warmIng undor rofIux In a round-boffomod
fIask. Tho dIssoIufIon may fako 30-35 mIn. Affor a cIoar soIufIon Is obfaInod hoaf for a
furfhor porIod of 2 hr. Pour fho hof roacfIon mIxfuro carofuIIy Info 50 mI of Ico-coId wafor
wIfh sfIrrIng. SfIr vIgorousIy wIfh a gIass rod fo docomposo fho oxcoss acofIc anhydrIdo.
!IIfor fho soIId and wash wIfh coId wafor. RocrysfaIIIzo from hof ofhanoI.
=-Acetate
>-Acofafo may bo convorfod Info =-acofafo as foIIows:
Procedure: ÐIssoIvo 0.5 g of fho >-acofafo In 2.5 mI 2% anhyd. zInc chIorIdo In acofIc
anhydrIdo In a 100 mI round-boffomod fIask. RofIux fho mIxfuro on a wafor-bafh for 30 mIn.
CooI and pour fho confonfs Info 25 mI Ico-coId wafor and sfIr vIgorousIy. !IIfor fho soIId and
wash wIfh coId wafor. RocrysfaIIIzo from hof ofhanoI.
(c) Benzoates
CrysfaIIIno bonzoafo dorIvafIvos of gIucoso and frucfoso aro proparod usIng bonzoyI chIorIdo.
Procedure: Tho proporfIos of carbohydrafos aro IIsfod In fabIo 6.1. In a 100 mI ÐrIonmoyor
fIask, dIssoIvo 0.5 g gIucoso In 5 mI wafor. To fhIs soIufIon add 15 mI of 10% sodIum hydroxIdo
soIufIon and 1 mI of bonzoyI chIorIdo. Sfoppor fho fIask and shako unfII fho odor of bonzoyI
chIorIdo has dIsappoarod and a crysfaIIIno soIId has soparafod. !IIfor fho soIId and wash If
wIfh a smaII quanfIfy of wafor. RocrysfaIIIzo from hof ofhanoI.
114 LABORATORY MANUAL OF ORGANIC CHEMISTRY
6.7 DERIVATIVES OF AMINES
A. Primary and secondary amines
(a) Benzamides
Tho bonzoyIafIon of a prImary or socondary amIno Is froquonfIy achIovod by fho Schöffon÷
Baumann roacfIon.
ThIs roacfIon shouId bo porformod In fho hood.
Procedure: In a boIIIng fubo hoaf abouf 0.3 g t0.2 mI for IIquId) of amIno, 3 mI of 10%
sodIum hydroxIdo soIufIon. To fho mIxfuro add 0.8 mI of bonzoyI chIorIdo sIowIy wIfh vIgorous
shakIng. Hoaf on a sfoam-bafh for 15 mIn. CooI and add an oxcoss of 10% sodIum hydroxIdo
soIufIon fo mako fho soIufIon aIkaIIno. CoIIocf fho soIId and rocrysfaIIIzo from hof aquoous
ofhanoI.
Question
6.6 Why do forfIary amInos faII fo roacf In fhIs roacfIon7
(b) p-Toluenesulfonamides
p-ToIuonosuIfonyI chIorIdo roacfs wIfh amInos fo form a p-foIuono suIfonamIdo.
Procedure: In a 50 mI round-boffomod fIask rofIux a mIxfuro of 0.5 mI t0.5 g) amIno and
0.75 mI of p-foIuonosuIfonyI chIorIdo In 4 mI of pyrIdIno for 30 mIn. Pour fho hof soIufIon In
25 mI of 5% hydrochIorIc acId fakon Info a boakor. SfIr fho mIxfuro woII wIfh a gIass rod fIII
soIId crysfaIIIzos ouf. !IIfor fho soIId and wash wIfh 10 mI wafor. RocrysfaIIIzo from aquoous
ofhanoI.
PREPARATION OF DERIVATIVES 115
B. Tertiary amines
PIcrafos aro froquonfIy ompIoyod as dorIvafIvos of fho forfIary amInos usIng pIcrIc acId.
PIcrafos aro coIorod soIIds.
Procedure: In a fosf fubo dIssoIvo 1 g of fho amIno In a mInImum amounf of ofhanoI and
add a soIufIon of 0.5 g of pIcrIc acId aIso dIssoIvod In a mInImum amounf of ofhanoI. Hoaf on
a wafor-bafh af 80°C for 5÷10 mIn and shako occasIonaIIy. CooI and pour fho confonfs onfo
Ico wafor. CoIIocf fho soIId, wash fhoroughIy wIfh wafor and rocrysfaIIIzo from hof ofhanoI.
6.8 DERIVATIVES OF HYDROCARBONS
(a) Picrates
A Iargo numbor of hydrocarbons aIso roacf wIfh pIcrIc acId fo form addIfIon producfs, caIIod
picruIes and aro usofuI In fho IdonfIfIcafIon of aromafIc hydrocarbons.
Procedure: ÐIssoIvo oquImoIar quanfIfIos of fho hydrocarbon t1 g anfhracono) and pIcrIc
acId t1.6 g) In fwo soparafo fosf fubos In 3 mI of boIIIng bonzono or ofhanoI. MIx fho soIufIons
whIIo hof and hoaf af 50 fo 60°C for 5 mIn. AIIow fho mIxfuro fo cooI. !IIfor fho pIcrafo and
wash wIfh Ico coId bonzono or ofhanoI. ÐoformIno fho moIfIng poInfs.
NaphfhaIono 150°C tYoIIow)
Anfhracono 142°C tRod)
Phonanfhrono 145°C tYoIIow)
Aconaphfhono 162°C tOrango)
Bonzono forms onIy a IabIIo pIcrafo.
(b) 1, 3, 5 - Trinitrobenzene adducts
Procedure: ÐIssoIvo 0.2 g of fho aromafIc hydrocarbon In 1 mI ofhanoI. To fhIs add 0.2 g of
1, 3, 5-frInIfrobonzono dIssoIvod In 2 mI of coId ofhanoI. CooI fho mIxfuro In Ico fIII procIpIfafo
forms. !IIfor and rocrysfaIIIzo fho soIId from ofhanoI.
116 LABORATORY MANUAL OF ORGANIC CHEMISTRY
6.9 DERIVATIVES OF ALKENES AND ALKYNES
Bofh fho unsafurafod aIkonos and aIkynos may bo characforIzod by proparIng fhoIr adducfs
wIfh 2, 4-dInIfrobonzonosuIfonyI chIorIdo. ThIs roagonf adds fo fho C÷C unsafurafod bonds
fo form crysfaIIIno dorIvafIvos.
Preparation of derivative for Alkenes
Procedure: In a fosf fubo, fako 0.2 g of 2, 4-dInIfrobonzonosuIfonyI chIorIdo and 0.3 g of
fho unknown aIkono In 2.5 mI of gIacIaI acofIc acId. Hoaf fho soIufIon for 15 mIn on a
sfoam-bafh. CooI and pour onfo crushod Ico fakon In a boakor and sfIr wIfh a gIass rod fIII
a soIId Is obfaInod. !IIfor fho crudo soIId and rocrysfaIIIzo from ofhanoI.
Preparation of derivative for Alkynes
Procedure: In a 50 mI ÐrIonmoyor fIask, dIssoIvo 1.5 g of 2, 4-dInIfrobonzonosuIfonyI
chIorIdo In 1.2 mI of 1,1-dIchIoroofhano. CooI fho soIufIon In Ico for 15 mn. Add 3 mI of fho
unknown aIkyno, shako and aIIow fho mIxfuro fo sfand af 0°C for 2 hr or unfII a soIId Is
obfaInod. !IIfor fho crudo soIId and rocrysfaIIIzo from ofhanoI. Nofo If fho crudo producf Is
dark In coIor, docoIorIzo If wIfh acfIvafod charcoaI.
6.10 PHYSICAL CONSTANTS
To osfabIIsh fho IdonfIfy of fho unknown and Ifs dorIvafIvo fho physIcaI consfanfs aro
doformInod and fho vaIuos comparod wIfh fho known dafa. Wo aro horo concornod maInIy
PREPARATION OF DERIVATIVES 117
wIfh fho moIfIng and boIIIng poInfs. Bofh fhoso consfanfs parfIcuIarIy fho moIfIng poInf
roprosonf Imporfanf crIforIa for purIfy of fho subsfanco.
6.10.1 Melting Point
Tho meIIing poinI of a compound may bo doscrIbod as fho fomporafuro af whIch fho soIId
and fho IIquId phasos oxIsf In oquIIIbrIum. In IdoaI casos If hoaf Is provIdod fo a crysfaIIIno
soIId no rIso In fomporafuro shouId fako pIaco fIII aII fho soIId has moIfod tmoIfIng poInf).
ConvorsoIy, If hoaf Is romovod from such a mIxfuro, fho fomporafuro wIII nof drop unfII aII
fho IIquId has boon convorfod fo soIId tfroozIng poInf). Thoroforo, fho moIfIng and froozIng
poInfs of a puro subsfanco shouId bo IdonfIcaI. A numbor of physIcaI proporfIos such as
coIor, odor, crysfaIIIno sfafo, rofracfIvo Indox, spocIfIc rofafIon aro moasurod In ordor fo
IdonfIfy an unknown organIc compound. MoIfIng poInf and boIIIng poInf, howovor, aro fho
mosf froquonfIy doformInod physIcaI dafa. !or soIId subsfancos fho mosf Imporfanf
characforIsfIc Is fho moIfIng poInf. If can bo doformInod In fho Iaborafory rapIdIy and mosf
accurafoIy usIng sImpIo apparafus and moroovor, by usIng onIy smaII quanfIfIos of fho
unknown sampIo. !urfhormoro, If furnIshos vaIuabIo InformafIon rogardIng fho IdonfIfy
and purIfy of fho compound undor oxamInafIon.
If fho subsfanco Is compIofoIy puro and dry If wIII havo a sharp moIfIng poInf whIch Is
nof raIsod by furfhor purIfIcafIon. As a maffor of facf fhIs Is aIso a convonfIonaIIy accopfod
crIforIon for purIfIcafIon. Buf mosf apparafus ompIoyod for fho moasuromonf of moIfIng
poInf aro dosIgnod for fho oaso of uso rafhor fhan accurafo doformInafIon. In pracfIco,
fhoroforo, a moIfIng poInf rango Is acfuaIIy moasurod rafhor fhan a sharp moIfIng poInf of
fho subsfanco. If a subsfanco Is roIafIvoIy puro, Ifs moIfIng poInf rango Is narrow and fho
fop of fho rango Is vory noar fo fho accurafo moIfIng poInf. Is confrasf, If a subsfanco Is
Impuro fhon If wIII havo a broad rango and moroovor, fho fop of fho rango Is Iowor fhan
fhaf of fho fruo moIfIng poInf. In ofhor words, fho purIfIcafIon of an Impuro subsfanco may
bo accompIIshod by fho doformInafIon of fho moIfIng poInf and whon fhIs bocomos sharp
and affaIns a consfanf vaIuo, fho subsfanco Is consIdorod puro.
If Is Imporfanf fo poInf ouf horo fhaf fho rango of moIfIng poInf bo roporfod If a sharp
moIfIng poInf Is nof obsorvabIo. Tho moIfIng rango of a compound doformInod for many
compounds may bo bofwoon 1-2°C. A puro subsfanco wIII moIf In a narrow moIfIng rango.
!urfhormoro, supposo fho moIfIng poInf of an unknown compound Is doformInod fo bo
122°C. A IIforafuro survoy rovoaIs fhaf fhoro may bo sovoraI compounds whIch havo a
moIfIng poInf of 122°C. Thoroforo fo, docIdo fho IdonfIfy of fho unknown compound, a smaII
sampIo of fho unknown compound Is mIxod wIfh a smaII quanfIfy of fho compound from fho
boffIo and fho moIfIng poInf of fho mIxfuro popuIarIy known as fho mlxed meltlng polnt
Is doformInod. If fhoso fwo compounds aro samo fhon fho mIxfuro wIII moIf af fho samo
fomporafuro as oach compound doos soparafoIy. On fho ofhor hand, If fho compounds aro
dIfforonf, fho moIfIng poInf of fho mIxfuro wIII bo Iowor and aIso havo a broad rango.
118 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: A smaII amounf t0.1-0.2 g) of fho compound tbonzoIc acId or uroa) Is fIrsf
powdorod wIfh a spafuIa on a porous pIafo usIng a gIass rod. Tho subsfanco Is fhon Infroducod
Info a capIIIary fubo t5 cm Iong) fo pack If fo a hoIghf of 3 mm. Tho capIIIary Is now
affachod fo a fhormomofor by moans of a smaII rubbor band. Nofo fhaf fho fop of fho
fhormomofor and fho capIIIary fubo aro af fho samo IovoI. Tho fhormomofor aIong wIfh fho
fubo Is now Immorsod In a hoafIng bafh. A ThieIe Iube or a KjeIJuhI's jIush wIfh an
approprIafo IIquId may bo usod. A ThIoIo fubo cIampod on Iron-sfand confaInIng IIquId paraffIn
or conc. suIphurIc acId Is shown In !Ig. 6.1. Hoaf fho bafh sIowIy. Tho fomporafuro af
whIch fho compound commoncos fo IIquofy and af whIch If Is compIofoIy IIquId Is rocordod
as fho moIfIng poInf rango.
A numbor of commorcIaIIy avaIIabIo apparafus aro avaIIabIo nowadays. Tho ono shown
In !Ig. 6.2 roquIros no IIquId and hoafIng Is dono oIocfrIcaIIy. Such sysfoms gIvo moro
roIIabIo moIfIng poInfs.
Fig. 6.1: Assembly for the determination of melting point.
PREPARATION OF DERIVATIVES 119
Fig. 6.2: A melting point block.
Questions
6.7 Tho sampIo for fho doformInafIon of moIfIng poInf shouId nof bo powdorod on fho
fIIfor papor. Why7
6.8 WouId a puro compound aIways gIvo a sharp moIfIng poInf7
6.9 Whaf doos a mIxod moIfIng poInf doformInafIon IndIcafo7
6.10.2 Boiling Point
Tho boiIing poinI of a puro IIquId Is dofInod as fho fomporafuro af whIch fho prossuro on
fho IIquId oquaIs fho vapor prossuro. Tho obsorvod boIIIng poInf Is dIrocfIy proporfIonaI fo
fho prossuro. As fho fomporafuro rIsos fho vapor prossuro rIsos. If Is nocossary fo sfafo fho
prossuro aIso whIIo wrIfIng fho b.p., for Insfanco, ¯b.p. 165°C/700 mm¨. Tho sfandard boIIIng
poInf Is fypIcaIIy moasurod af afmosphorIc prossuro, i.c., 760 mm of Hg. Prosonco of
ImpurIfIos sImIIar fo moIfIng poInf InfIuonco fho boIIIng poInf of a IIquId and If doponds on
fho nafuro of fho ImpurIfy A non-voIafIIo ImpurIfy may gonoraIIy Ioad fo sharp boIIIng
poInf, whoroas voIafIIo ImpurIfIos raIso fho boIIIng poInf. PoIar IIquIds offon boII hIghor
fhom non-poIar IIquIds of fho samo moIocuIar woIghf. AssocIafod IIquIds boII sfIII hIghor
fhon unassocIafod onos. A doformInafIon of boIIIng poInf Is usofuI for fho IdonfIfIcafIon of a
120 LABORATORY MANUAL OF ORGANIC CHEMISTRY
puro IIquId. A IIquId as a ruIo, wIII boII af a consfanf fomporafuro provIdod fho prossuro
romaIns consfanf. Bocauso of Ifs dopondonco on prossuro and Ifs orrafIc rosponso fo
ImpurIfIos fho boIIIng poInf Is gonoraIIy Ioss roIIabIo fhan Is fho m.p. of soIIds. Howovor,
mosf mIxfuro of IIquId boII ovor a faIrIy wIdo fomporafuro rango ovon af consfanf
fomporafuro.
Fig. 6.3: Assembly for the determination of boiling point.
A mIxfuro of fwo dIfforonf subsfancos of fho samo moIfIng poInf wIII show a moIfIng
poInf boIow fhaf of oach puro subsfanco of fho mIxfuro. In confrasf, a mIxfuro of fwo IIquIds
of fho samo boIIIng poInf wIII havo fho samo boIIIng poInf as oach IndIvIduaI ono. Thus fho
boIIIng poInf Is Ioss usofuI for IdonfIfIcafIon fhan fho moIfIng poInf. BoIIIng poInf can bo
doformInod In an apparafus shown In !Ig. 6.3.
Procedure : PIaco 3-4 drops of fho IIquId whoso boIIIng poInf Is fo bo doformInod In an
IgnIfIon fubo. Immorso a capIIIary fubo soaIod af fho ofhor ond In fho IIquId tIf fho IIquId
rIsos In fho fubo In moans fhaf If Is nof proporIy soaIod). Affach fho IgnIfIon fubo fo a
fhormomofor by moans of a rubbor band. Suspond fho fhormomofor In a Iong-nockod fIask
confaInIng paraffIn oII or In a ThoIIo fubo. Hoaf fho fIask unIformIy wIfh a burnor, unfII a
rapId sfroam of bubbIos sfarfs comIng ouf of fho capIIIary fubo tbocauso fho aIr InsIdo fho
fubo warms and oxpands). Af fhIs poInf romovo fho burnor and pormIf fho fIask fo cooI.
Tho sfoam of bubbIos bocomo sIowor and fho fomporafuro drops unfII a poInf Is roachod
PREPARATION OF DERIVATIVES 121
whon fho bubbIIng coasos, and fho IIquId commoncos fo rIso In fho capIIIary fubo. ThIs Is
fho boIIIng poInf of fho IIquId.
Question
6.10 If fwo mIscIbIo IIquIds aro found fo boII af oxacfIy fho samo fomporafuro, couId fho
concIusIon bo drawn fhaf fhoy aro IdonfIcaI7
6.11 SEPARATION OF BINARY MIXTURES
Af somo sfago durIng a Iaborafory courso In organIc quaIIfafIvo anaIysIs, fho sfudonf wouId
bo roquIrod fo soparafo and IdonfIfy fho compononfs of a mIxfuro of organIc compounds. A
succossfuI characforIzafIon doponds on a wIso soparafIon of fho mIxfuro Info suffIcIonfIy
puro sfafo fo pormIf corrocf IdonfIfIcafIon. Tho soparafIon Is basod on fho dIfforonco In
somo physIcaI proporfIos of fho compononfs af fho fImo of soparafIon. Tho Imporfanf proporfy
fhaf wo aro offon concornod wIfh Is fho dIfforonco In soIubIIIfIos of fho consfIfuonfs In
dIfforonf soIvonfs. In ofhor words, wIfh fho oxporImonf InvoIvIng a soparafIon by oxfracfIon
procoduro. In compIIcafod casos, fochnIquos IIko fracfIonaI dIsfIIIafIon or fracfIonaI
rocrysfaIIIzafIon may bo ompIoyod.
Tho fIrsf sfop Is a vIsuaI InspocfIon; In caso fwo Iayors or phasos aro obsorvod, fhoy
shouId bo soparafod by mochanIcaI moans, i.c., a sImpIo fIIfrafIon or uso of a soparafory
funnoI. Tho soparafIon Is facIIIfafod by doformInIng fho acId-baso characfor of fho mIxfuro.
ThIs InformafIon, howovor, may nof bo roIIabIo wIfh rogard fo fho composIfIon of fho mIxfuro.
Thon soparafIon may bo affompfod by usIng any ono of fho foIIowIng soIvonfs:
ta) CoId wafor
tb) Hof wafor
tc) HydrochIorIc acId t10%)
td) SodIum bIcarbonafo t10%)
to) SodIum hydroxIdo t10%)
tf) OrganIc soIvonfs.
Tho choIco of a soIvonf may bo narrowod down by makIng an oIomonfaI anaIysIs on fho
mIxfuro. !or Insfanco, If nIfrogon Is absonf, fhon fhoro Is no nood fo uso hydrochIorIc acId
for dIssoIufIon. If an acId Is found fo bo a succossfuI roagonf, fhon fho basIc compononf can
bo rocovorod from fho soIufIon by noufraIIzIng If wIfh a baso, on fho ofhor band, If If
dIssoIvos In sodIum bIcarbonafo soIufIon fhon fho acId from fho sodIum saIf Is rogonorafod
by acIdIfyIng wIfh hydrochIorIc acId. ¡n short, un ucld ls regeneruted by uslng un ucld
und u buse ls regeneruted by neutrullzlng the solutlon wlth u buse.
A brIof dIscussIon for fho soparafIon of sovoraI bInary mIxfuros wIII IIIusfrafo fho
appIIcafIon of fho gonoraI procoduro InvoIvod.
122 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(a) Aniline and m-nitrotoluene
Nono of fhoso Is soIubIo In wafor buf bofh aro soIubIo In ofhor. An oIomonfaI anaIysIs
shows fho prosonco of nIfrogon and fho mIxfuro Is basIc fo IIfmus. Tho addIfIon of 10%
hydrochIorIc acId wouId convorf anIIIno Info Ifs saIf buf wIII nof affocf n-nIfrofoIuono. Tho
Iaffor compound can fhus bo soparafod by oxfracfIon of fho mIxfuro wIfh ofhor. Tho aquoous
soIufIon Is basIfIod wIfh 10% sodIum hydroxIdo soIufIon fo obfaIn anIIIno.
(b) Bezophenone and benzoic acid
Nono of fhoso Is soIubIo In wafor buf bofh dIssoIvo In ofhor. NIfrogon Is absonf and fho
mIxfuro Is acIdIc fo IIfmus. Thoroforo, shako fho mIxfuro wIfh 10% sodIum hydroxIdo
soIufIon. BonzoIc acId wouId dIssoIvo as Ifs sodIum saIf buf bonzophonono wouId bo InsoIubIo.
Bonzophonono can bo obfaInod by oxfracfIon of fho mIxfuro wIfh ofhor. Tho acId by acIdIfyIng
fho aquoous soIufIon wIfh 10% hydrochIorIc acId.
(c) Salicylic acid and succinic acid
Bofh fhoso subsfancos aro poIar and soIubIo In wafor. SuccInIc acId, howovor, Is nof oxpocfod
fo bo approcIabIy soIubIo In ofhor bocauso of Ifs hIghor poIarIfy tfwo carboxyI groups). Tho
compononfs can fhus bo soparafod by oxfracfIon of bonzoIc acId wIfh ofhor.
SovoraI addIfIonaI oxampIo of bInary mIxfuros and fho soIvonfs suggosfod for fhoIr soparafIon
aro IIsfod boIow:
Table 6.2: Suggested solution for some mixture dissolution
Mlxture Suggested Solvents
BonzoIc acId + anfhracono ÐII. sodIum bIcarbonafo
=-NaphfhoI + naphfhaIono ÐII. sodIum hydroxIdo
!roa + phonyI bonzoafo Wafor
p-ToIuIdIno + bonzophonono ÐII. hydrochIorIc acId
p-NIfroanIIIno + succInIc acId Wafor
p-NIfrofoIuonco + bonzamIdo Hof wafor
p-ChIorobonzoIc acId + bonzophonono ÐII. sodIum bIcarbonafo
AnIIIno + acofophonono ÐII. hydrochIorIc acId
MannIfoI + =-naphfhoI Wafor
!roa + Iodoform Ðfhor
Sucroso + saIIcyIaIdohydo Ðfhor
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6.12 PHYSICAL CONSTANTS OF SOME COMMON ORGANIC COMPOUNDS AND
THEIR DERIVATIVES
Table 6.3: Alcohols and Phenols
Derlvutlves
Compound m.p. b.p. Solublllty 3-5-Dlnltro- F-Nltro- Acetutes Benzoutes
(°C) (°C) Wuter benzoutes benzoutes m.p. (°C) m.p. (°C)
m.p. (°C) m.p. (°C)
(1) (2) (3) (4) (5) (6) (?) (8)
n-IropyI aIcohoI ÷ 9? SoI ?5 35
tert-BufyI aIcohoI 25 83 SoI 142 116
o-CrosoI 30 191 SoI 138 94
p-CrosoI 26 202 SoI 189 98
IhonoI 43 182 SoI 146 126 69
p-ChIorophonoI 43 21? 186 158
o-NIfrophonoI 45 216 Hof wafor 155 141 42
p-EfhyIphonoI 4? 130 81 60
ThymoI 51 Hof wafor 103 ?0
p-MofhoxyphonoI 55
p-BromophonoI 64 235 191 180
BonzhydroI 68 141
=-NaphfhoI 94 21? 143 56
tConfd...)
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(1) (2) (3) (4) (5) (6) (?) (8)
n-NIfrophonoI 9? 159 1?4 56
CafochoI 105 SoI 152 169 63
RosorcInoI 110 SoI 201 182
J-SorbIfoI 110 SoI 99 129
p-NIfrophonoI 114 Hof wafor 186 159 83
2,4-ÐInIfrophonoI 114
IIcrIc acId 122 SoI 143 ?6
Bonzono pIcrafo m.p.84°C
>-NaphfhoI 123 InsoI 186 169 ?0
IyrogaIIoI 133 SoI 205 230 149
MannIfoI 166 SoI 121
HydroquInono 1?0 SoI 31? 263
o-ChIorophonoI 1?6 143 115
o-BromophonoI 195
n-CrosoI 202 165 90
n-ChIorophonoI 214 159 99
n-BromophonoI 236
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Table 6.4: Carboxylic Acids
Derlvutlves
Compound m.p. b.p. Solublllty Amldes F-Tolu- I-Benzoyllso- F-Bromo-
(°C) (°C) Wuter m.p. (°C) ldes thlouronlum phenyl
m.p. (°C) sults esters
m.p. (°C) m.p. (°C)
(1) (2) (3) (4) (5) (6) (?) (8)
AcofoacofIc acId 3? 54 95
2-IhonyIbufanoIc acId 42 85
BromoacofIc acId 50 91 91
ChIoroacofIc acId 63 118 162
CyanoacofIc acId 66 120
IhonyIacofIc acId ?6 Hof wafor 15? 165 89
OIycoIIc acId ?9 120 143
IodoacofIc acId 83 95
IhonoxyacofIc acId 99 102
CIfrIc acId 100 SoI 215 189
OxaIIc acId 101 SoI 268 198 242
o-ToIuIc acId 105 Sp. soI 143 144 146
n-ToIuIc acId 112 95 118
4-IhonyIbonzoIc acId 113 131
2-AcofyIbonzoIc acId 115 116
BonzoIc acId 121 Hof wafor 129 158 16? 119
tConfd...)
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(1) (2) (3) (4) (5) (6) (?) (8)
3-IuroIc acId 121 169
o-BonzyIbonzoIc acId 12? 165
CInnamIc acId 133 Sp. SoI 141 256
2-IuroIc acId 133 143 108
AcofyIsaIIcyIIc acId 135 Hof wafor 138
IhonyIpropIoIIc acId 136 InsoIubIo 109 142
n-NIfrobonzoIc acId 140 143 162
o-ChIorobonzoIc acId 141 Hof wafor 141 10?
p-ChIorobonzoIc acId 142 142 131
AnfhranIIIc acId 146 SoI 109 149 1?2
o-NIfrobonzoIc acId 14? Hof wafor 1?5 109 10?
o-BromobonzoIc acId 150 Sp. soI 155 1?1
BonzIIIc acId 150 154 190
AdIpIc acId 152 SoI 220 163 165
2, 5-ÐIchIorobonzoIc acId 153 155
n-BromobonzoIc acId 155 SoI 155 168 126
n-ChIorobonzoIc acId 158 134
SaIIcyIIc acId 158 SoI 139 156 148 140
1-NaphfhoIc acId 162 205
o-IodobonzoIc acId 162 110
tConfd...)
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(1) (2) (3) (4) (5) (6) (?) (8)
2, 4-ÐIchIorobonzoIc acId 164 194
J-TarfarIc acId 1?0 196
n-AmInobonzoIc acId 1?4 111
p-ToIuIc acId 1?8 Hof wafor 159 160 190 153
2, 4-ÐInIfrobonzoIc acId 183 203
AnIsIc acId 184 Sp. soI 162
2-NaphfhoIc acId 185 192 192
SuccInIc acId 186 SoI 260 154 211
n-IodobonzoIc acId 18? 186
p-AmInobonzoIc acId 188 Hof wafor 114
CoumarIn-1-carboxyIIc acId 188 236
IhfhaIIc acId 195 Hof wafor 220 158 154
L-TarfarIc acId 204 226
3, 4-ÐIhydroxybonzoIc acId 209 268
2, 4-ÐIhydroxybonzoIc acId 213 222
4-HydroxybonzoIc acId 215 162 204
4-IhonyIbonzoIc acId 226 223
p-NIfrobonzoIc acId 241 Sp. soI 1?9
p-ChIorobonzoIc acId 236 Sp. soI 201 182 136
p-BromobonzoIc acId 251 190
1
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Table 6.5: Aldehydes
Derlvutlves
Compound m.p. b.p. Solublllty Phenylhydru- 2, 4-Dlnltrophe- Semlcurbu-
(°C) (°C) (wuter) zones nylhydruzones zones
m.p. (°C) m.p. (°C) m.p. (°C)
(1) (2) (3) (4) (5) (6) (?)
1-NaphfhaIdohydo 34 221
IIpornaI 3? 266 234
o-MofhoxybonzaIdohydo 39 221 254 215
o-AmInobonzaIdohydo 40 24?
o-NIfrobonzaIdohydo 44 13? 265 256
ChIoraI hydrafo 56 SoI
n-NIfrobonzaIdohydo 58 293 246
2-NaphfhaIdohydo 60 2?0 245
3, 5-ÐIchIorobonzaIdohydo 65
2, 4-ÐIchIorobonzaIdohydo ?4
p-BromobonzaIdohydo 6? 113
p-AmInobonzaIdohydo ?2 SoI 156 126 1?3
n-BufyraIdohydo ?4 131
ChIoraI 96
IonfanaI 103
tConfd...)
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(1) (2) (3) (4) (5) (6) (?)
n-HydroxybonzaIdohydo 104 98 322
p-NIfrobonzaIdohydo 106 280 221
p-HydroxybonzaIdohydo 116 Sp soI 1?8 104
HoxanaI 131 230 106
IuIuraI 162 23? 206
BonzaIdohydo 1?9 Sp soI 158 252
SaIIcyIadohydo 196 Sp soI 143 252 100
n-MofhyIbonzaIdhydo 199 195 204
o-MofhyIbonzaIdohydo 200 104 209
p-MofhyIbonzaIdohydo 205 234 234
o-ChIorobonzaIdohydo 213 86 209
p-ChIorobonzaIdohydo 214 1?2 265
o-BromobonzaIdohydo 230
n-MofhoxybonzaIdohydo 230 233
n-BromobonzaIdohydo 234 228
p-MofhoxybonzaIdohydo 248 253 210
CInnamaIdohydo 252 255 216
1
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Table 6.6: Ketones
Derlvutlves
Compound m.p. b.p. Solublllty Phenylhydr- 2, 4-Dlnltro- Semlcur-
(°C) (°C) (wuter) uzones phenyl- buzones
m.p. (°C) hydruzones m.p. (°C)
m.p. (°C)
(1) (2) (3) (4) (5) (6) (?)
MofhyI ofhyI kofono 80 SoI 115 146
2-Bufanono 82 11? 136
CycIobufanono 100 146
ÐIofhyIacofono 102 SoI 156 139
3-Ionfanono 102 156 1?9
2-Ionfanono 102 144 112
IInacoIono 106 125 158
ChIoroacofono 119 125 150
3-Hoxanono 125 1?0 113
2-Hoxanono 128 100
CycIoponfanono 131 206 164
3-Hopfanono 148 103
2-Hopfanono 151 89 123
tConfd...)
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(1) (2) (3) (4) (5) (6) (?)
CycIohoxanono 155 SoI 160 166
BonzoquInono 115 InsoI 243
Bonzophonono 49 InsoI 238
Acofophonono 202 InsoI 105 250
Monfhono 209 146 189
IropIophonono 220 191 1?4
Bufyrophonono 222 163 181
J-Carvono 230 190 188
p-ChIoroacofophonono 232 231 204
o-Mofhoxyacofophonono 239 183
n-Mofhoxyacofophonono 240 196
n-VoIorophonono 248 166 160
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Table 6.7: Esters
Compound m.p. (°C) b.p. (°C) 3, 5-Dlnltrobenzoute m.p. (°C)
(1) (2) (3) (4)
ÐImofhyI succInafo 18
ÐIofhyI farfarafo 18
BonzyI bonzoafo 18
t+) BornyI acofafo 2? 154
MofhyI cInnamafo 36 108
EIhyI mandoIafo 3?
IhonyI saIIcyIafo 42
ÐImofhyI farfarafo 49
MofhyI mandoIafo 53
ÐImofhyI oxaIafo 45
IhonyI bonzoafo 69 93
2-NaphfhyI acofafo ?1 210
MofhyI p-nIfrobonzoafo 96 108
EfhyI Iormafo 54 93
MofhyI acofafo 5? 108
EfhyI acofafo ?? 108
MofhyI propIonafo 80 108
iso-IropyI acofafo 90 123
tConfd...) tConfd...)
P
R
E
P
A
R
A
T
I
O
N

O
F

D
E
R
I
V
A
T
I
V
E
S
1
3
3
(1) (2) (3) (4)
tert-BufyI acofafo 98 142
MofhyI acryIafo 80 108
EfhyI propIonafo 100 93
IropyI acofafo 102
MofhyI bufyrafo 102
AIIyI acofafo 104
ChoIosfryI acofafo 114
MofhyI crofonafo 119
HydroquInono dIacofafo 124
MofhyI pyruvafo 13?
EfhyI crofonafo 138
ÐImofhyI forophfhaIafo 141 93
EfhyI chIoroacofafo 145
EfhyI pyruvafo 155
MofhyI acofoacofafo 1?0
CycIohoxyI acofafo 1?2 58
IurIuyI acofafo 1?6
EfhyI acofoacofafo 181
ÐIofhyI oxaIafo 185 93
ÐImofhyI succInafo 196
tConfd...)
1
3
4
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
(1) (2) (3) (4)
IhonyI acofafo 19? 146
ÐIofhyI maIonafo 199 93
MofhyI bonzoafo 199 108
C-BufyroIacfono 204
EfhyI bonzoafo 212 93
BonzyI acofafo 21? 113
ÐIofhyI succInafo 218 206
MofhyI phonyIacofafo 220 108
MofhyI saIIcyIafo 224
EfhyI phonyIacofafo 228 93
IropyI bonzoafo 231 ?4
EfhyI saIIcyIafo 234
ÐIofhyI adIpafo 245 93
EfhyI cInnamafo 2?1
ÐIofhyI farfarafo 280
ÐImofhyI phfhaIafo 284 108
ÐIofhyI phfhaIafo 290
ÐIIsobufyI phfhaIafo 32?
ÐIbufyI phfhaIafo 340
P
R
E
P
A
R
A
T
I
O
N

O
F

D
E
R
I
V
A
T
I
V
E
S
1
3
5
Table 6.8: Amines
Derlvutlves
Compound m.p. b.p. Solublllty Acetyl Benzoyl Plcrutes F-Toluene
(°C) (°C) (wuter) m.p. (°C) m.p. (°C) m.p. (°C) sulIonu-
mldes
m.p. (°C)
(1) (2) (3) (4) (5) (6) (?) (8)
EfhyIamIno 1? SoI 165 63
EfhyImofhyIamIno 36
N-BonzyIamIno 3?
2, 6-ÐIchIoroanIIIno 39
IropyIamIno 48 SoI 135 52
IndoIo 52
ÐIofhyIamIno 56 SoI 155 55
8-HydroxyquInoIIno ?5
n-BufyIamIno ?? SoI 151
IyrroIIdIno ?5
TrIofhyIamIno 90 SoI 1?3
2, 4-ÐIamInofoIuono 99
o-BromoanIIIno 32 229 InsoI 99 116 90
p-ToIuIdIno 45 154 158 118
tConfd...)
1
3
6
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
(1) (2) (3) (4) (5) (6) (?) (8)
=-NaphfhyIamIno 50 160 161 15?
ÐIphonyIamIno 54 InsoI 16? 204 180
p-BromoanIIIno 66 Hof wafor 1?9 193 1?8
p-ChIoroanIIIno ?1 Hof wafor 1?9 193 1?8
a-NIfroanIIIno ?1 94 98 ?3 142
o-IhonyIonodIamIno 102
IIporIdIno 106 152 96
>-NaphfhyIamIno 113 Hof wafor 134 162 195 133
n-NIfroanIIIno 114 143 138
EfhyIonodIamIno 116
IyrIdIno 116 16?
p-AmInophonoI 123 SoI 151 234 110
TrIphonyIamIno 12?
2-IIcoIIno 129
IyroIo 131 690
CycIohoxyIamIno 134
p-NIfroanIIIno 14? 110
2-AmInoofhanoI 1?1
tConfd...)
P
R
E
P
A
R
A
T
I
O
N

O
F

D
E
R
I
V
A
T
I
V
E
S
1
3
7
(1) (2) (3) (4) (5) (6) (?) (8)
o-HydroxyanIIIno 1?4
o-AmInophonoI 1?4 Sp soI 124 184 139
n-AmInoanIIIno 180
BonzyIdImofhyIamIno 181
AnIIIno 184 198 d 103
p-AmInophonoI 184
N, N-ÐImofhyIanIIIno 193 163
ÐImofhyIamIno 193 65
2, 4, 6-TrInIfroanIIIno 190
o-ToIuIdIno 200 112 143 124
BonzyIamIno 185 SoI 60 105 199 116
o-ChIoroanIIIno 20? 88 134 105
o-AnsIdIno 218 84 64 12?
2-MofhoxyanIIIno 225 200 136
QuInoIIno 23? 203
p-AnsIdIno 51 246 130 153 114
o-BromoanIIIno 31 250 99 129 90
n-BromoanIIIno 251
ÐIbonzyIamIno 300
1
3
8
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
Table 6.9: Amides
Derlvutlves
Compound m.p. (°C) Plcrutes b.p. (°C) Aclds m.p. (°C)
(1) (2) (3) (4)
N-MofhyIacofamIdo 31 30
MofhyI urofhano 52
IhonyI urofhano 53
AcofoacofamIdo 60 3?
CaproIacfam ?1
IropIonamIdo 81 141
AcofamIdo 82 118
AcryIamIdo 85 140
o-NIfroacofanIIIdo 92
MaIoImIdo 93 130
n-ToIuamIdo 9? 112
IonfanamIdo 106 186
AcofanIIIdo 114 216
BufanamIdo 115 164
SuccInImIdo 126 189
iso-BufyramIdo 129 155
BonzamIdo 130 121
n-ChIorobonzamIdo 134
IhonocofIn 134
SaIIcyIamIdo 142 158
o-ToIuamIdo 143 104
tConfd...)
P
R
E
P
A
R
A
T
I
O
N

O
F

D
E
R
I
V
A
T
I
V
E
S
1
3
9
(1) (2) (3) (4)
n-NIfrobonzamIdo 143 140
CInnamIdo 148 133
n-BromobonzamIdo 155 155
IhonyIacofamIdo 156 ?6
p-ToIuamIdo 159 1?9
o-BromobonzamIdo 161 150
p-HydroxybonzamIdo 162 215
BonzanIIIdo 169 204
p-BromosuccInImIdo 16? 185
p-MofhoxybonzamIdo 16?
n-HydroxybonzamIdo 1?0 200
N-BromosuccInImIdo 1?3
o-NIfrobonzamIdo 1?6 146
p-ChIoroacofanIIIdo 1?9 243
p-AmInobonzamIdo 183 188
3, 5-ÐInIfrobonzamIdo 183 20?
p-BromobonzamIdo 189 251
p-NIfrobonzamIdo 200 241
1-NaphfhamIdo 202 182
2, 6-ÐIchIorobonzamIdo 202 144
2, 4-ÐInIfrobonzamIdo 203 183
IhfhaIImIdo 238 210
SuccInamIdo 260 doc 189
1
4
0
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
Table 6.10: Hydrocarbons
Compound m.p. b.p. Solublllty Nltro derlvutlves Plcrutes
(°C) (°C) (wuter) m.p. (°C) m.p. (°C)
(1) (2) (3) (4) (5) (6)
ÐIphonyImofhano 26 262 InsoI 1?2 t2, 2, 4, 4)
1, 2-ÐIphonyIofhano 53 284 InsoI 180 t2, 4)
IonfamofhyIbonzono 54 232 InsoI 154 t6)
ÐIphonyI 69 234 t4, 4)
NaphfhaIono 80 81 t1)
Bonzono 80 89 t1, 3) 84
TrIphonyImofhano 92 206 t4, 4, 4)
Aconaphfhono 96 101 t5) 161
Ihonanfhrono 100 144 143
ToIuono 111 ?0 t2, 4) 88
IIuorono 114 156 t2) !nsfabIo
trans-SfIIbono 124 120 t1, 3, 5) !nsfabIo
p-XyIono 138 139 t2, 3, 5) !nsfabIo
n-XyIono 139 182 t2, 4, 5) ¨
o-XyIono 144 ?1 t4, 5) ¨
Anfhracono 216 138 tunsfabIo)
P
R
E
P
A
R
A
T
I
O
N

O
F

D
E
R
I
V
A
T
I
V
E
S
1
4
1
Table 6.11: Miscellaneous
Compound m.p. (°C) b.p. (°C)
(1) (2) (3)
n-NIfroanIsoIo 38
BonzoIc anhydrIdo 42
o-BromonIfrobonzono 43
p-ÐIchIorobonzono 53 1?3
p-NIfrofoIuono 54 238
MaIoIc anhydrIdo 54 130
n-ChIorofoIuono ?2
p-Bromobonzono 89
AcofanIIIdo 114
IodoIorm 119
SuccInIc anhydrIdo 120
p-NIfrobromobonzono 12?
IhfhaIIc anhydrIdo 132
o-ChIoronIfrobonzono 246
IhfhaIoyI chIorIdo 280
SuIIanIIIc acId 288 doc
AnIIIno hydrochIorIdo 198
tConfd...)
1
4
2
L
A
B
O
R
A
T
O
R
Y

M
A
N
U
A
L

O
F

O
R
G
A
N
I
C

C
H
E
M
I
S
T
R
Y
(1) (2) (3)
BromoIorm 151
AnIsoIo 155
o-ChIorofoIuono 159
n-ChIorofoIuono 162
p-ChIorofoIuono 162
IhonofoIo 1?2
BonzyI chIorIdo 180
o-ÐIchIorobonzono 180
o-BromofoIuono 182
p-BromofoIuono 184
BonzonIfrIIo 190
BonzoyI chIorIdo 19?
2, 4-ÐIchIorofoIuono 201
IhonacyI chIorIdo 210
NIfrobonzono 211
o-NIfrofoIuono 220
p-ChIorobonzyI chIorIdo 222
n-NIfrofoIuono 233
ChupIer ?
ESTIMATION OF FUNCTIONAL GROUPS
QuaIIfafIvo organIc anaIysIs has boon fho subjocf of fho procodIng chapfors, for fho
IdonfIfIcafIon of organIc compounds. If Is Infondod fo dIscuss and porform somo oxporImonfs
of quanfIfafIvo osfImafIon of funcfIonaI groups. In fhoso oxorcIso ufmosf caro Is noodod for
accurafo workIng and moasuromonf of corrocf dafa. !or fho proparafIon of sfandard
soIufIons, fho amounfs sfafod wIfhIn paronfhosIs roprosonf fho numbor In g/I of fho soIufIon.
7.1 ESTIMATION OF THE NUMBER OF HYDROXYL (–OH) GROUPS IN
ALCOHOLS
Tho numbor of hydroxyI groups In an aIcohoI or phonoI can bo osfImafod by acofyIafIon
wIfh acofIc anhydrIdo. A known woIghf of fho aIcohoI Is acofyIafod wIfh froshIy dIsfIIIod
acofIc anhydrIdo In fho prosonco of dry pyrIdIno and Is usod In oxcoss. Af fho ond of fho
roacfIon oxcoss of fho anhydrIdo Is hydroIysod wIfh wafor. AcofIc acId so producod Is fIfrafod
agaInsf sfandard aIkaII soIufIon In ordor fo doformIno fho amounf of fho unroacfod acofIc
anhydrIdo.
ChemicuIs
º AcofIc anhydrIdo dIsfIIIod.
º ÐfhanoIIc sodIum hydroxIdo soIufIon t0.5 N, 20 g/I).
º Ðry pyrIdIno tpyrIdIno can bo drIod ovor pofassIum hydroxIdo poIIofs).
144 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: !Irsf proparo fho acofyIafIng mIxfuro by mIxIng ono voIumo t11.5 g) of acofIc
anhydrIdo and fhroo voIumos t34.5 mI) of dry pyrIdIno In a cIoan ÐrIonmoyor fIask. !III a
cIoan dry buroffo wIfh fhIs mIxfuro and cork If.
!or fho proparafIon of aIcohoIIc sodIum hydroxIdo soIufIon. Proparo a safurafod soIufIon
of sodIum hydroxIdo In dIsfIIIod wafor In a corkod ÐrIonmoyor fIask. Tako 14 mI of fhIs
soIufIon In a 500 mI voIumofrIc fIask and fIII If If wIfh ofhyI aIcohoI. SfandardIzo fhIs soIufIon
wIfh 0.5 N hydrochIorIc acId or suIfurIc acId or proforabIy oxaIIc acId usIng phonoIphfhaIoIn
IndIcafor.
In a 250 mI ÐrIonmoyor fIask oquIppod wIfh a wafor condonsor, woIgh accurafoIy tby
fransforonco mofhod) 1÷1.3 g sampIo tphonoI, n-hoxanoI, cycIohoxanoI, or bonzyI aIcohoI)
and fo fhIs add 9 mI acofyIafIng mIxfuro from fho buroffo tuso doubIo fho amounf If fho
aIcohoI Is dIhydrIc). Shako and rofIux fho confonfs on a wafor-bafh for 45 mIn affor ropIacIng
fho condonsor. Romovo fho fIask and add 20 mI dIsfIIIod wafor fhrough fho condonsor and
shako fo onsuro compIofo hydroIysIs of fho romaInIng acofIc anhydrIdo. CooI fho fIask and
fIfrafo fho confonfs tNofo I) agaInsf sfandard sodIum hydroxIdo soIufIon usIng
phonoIphfhaIoIn as IndIcafor. Carry ouf a bIank confroI oxporImonf sImuIfanoousIy usIng
fho abovo procoduro wIfh 9 mI of fho acofyIafIng mIxfuro wIfhouf addIng aIcohoI or phonoI.
Tho dIfforonco In fho voIumos of sodIum hydroxIdo soIufIon roquIrod In fho fwo oxporImonfs
Is oquIvaIonf fo fho dIfforonco In fho amounf of acofIc acId formod, i.c., fo fho acofIc acId
dorIvod from fho acofIc anhydrIdo consumod In fho acfuaI acofyIafIon of fho sampIo. If fho
moIocuIar woIghf of fho aIcohoI Is known, fho numbor of ÷OH groups In fho aIcohoI can bo
doformInod. Tho advanfago of confroI oxporImonf Is fhaf fho absoIufo conconfrafIon of fho
roagonf thonco fho oxacf conconfrafIon of acofIc anhydrIdo In pyrIdIno) nood nof bo
doformInod. If fho samo voIumo of roagonf Is usod In fho acfuaI and In fho bIank or confroI
oxporImonf, fho dIfforonco gIvos fho acfuaI amounf usod.
CuIcuIuIions
WoIghf of fho sampIo = W g
Supposo fho sampIo roquIros V mI and fho bIank roquIros V
1
mI of 0.5 N sodIum
hydroxIdo soIufIon.
ÐIfforonco = ) t
1
V V − mI of 0.5 N NaOH
or
2
) t
1
V V −
mI of 1 N NaOH
1000 mI of 1 N NaOH = 1 g moI. wf. of NaOH
= 1 g moI. wf. of acofIc acId
= 1 OH group/moIocuIo of aIcohoI

2
) t
1
V V −
mI of 1 N NaOH =
2 1000
) t
1
×
− V V
OH groups
ESTIMATION OF FUNCTIONAL GROUPS 145
W g of fho aIcohoI sampIo confaIns
2 1000
) t
1
×
− V V
OH groups
94 g tassumIng fho sampIo fo bo phonoI) confaIns
W
V V 94
2 1000
) t
1
×
×

OH groups/moIocuIo
Note ¡: !or boffor rosuIfs fho sampIo affor rofIuxIng may bo dIIufod fo 100 mI In a moasurIng
fIask and 10 mI aIIquof fIfrafod agaInsf a dIIufo soIufIon t0.1 N) of NaOH.
Question
?.1 Whaf Is fho purposo of runnIng a bIank7
7.2 DETERMINATION OF THE PURITY OF PHENOL
Tho purIfy of a phonoI sampIo can bo doformInod by bromInafIon usIng pofassIum bromafo-
bromIdo soIufIon as fho bromInafIng roagonf. Ðxcoss bromIno Is fhon fIfrafod agaInsf
sfandard sodIum fhIosuIfafo soIufIon:
KBrO
3
+ 5 KBr + 6 HCI 6 KCI + 3 Br
2
+ 3 H
2
O

2 KI + Br
2
2 KBr + I
2
I
2
+ 2 Na
2
S
2
O
3
Na
2
S
4
O
6
+ 2 NaI
ChemicuIs
º PofassIum bromafo-bromIdo soIufIon t0.2 N).
º SodIum fhIosuIfafo soIufIon t0.1 N, 25 g/I).
º PofassIum IodIdo soIufIon t20%).
º Sfarch IndIcafor.
Procedure: Proparo fho pofassIum bromafo-bromIdo soIufIon by dIssoIvIng ?5 g pofassIum
bromIdo and 5.6? g pofassIum bromafo In wafor and mako up fho soIufIon fo 1 IIfro In a
voIumofrIc fIask.
146 LABORATORY MANUAL OF ORGANIC CHEMISTRY
WoIgh accurafoIy abouf 0.25÷0.3 g of phonoI sampIo, dIssoIvo In 5 mI of 10% sodIum
hydroxIdo soIufIon and dIIufo fho soIufIon fo 250 mI In a voIumofrIc fIask. In a 500 mI
sfopporod fIask pIpoffo 25 mI of fhIs soIufIon, 25 mI of pofassIum bromafo-bromIdo soIufIon
and add 25 mI of wafor. AIso add 5 mI of conc. hydrochIorIc acId and ImmodIafoIy sfoppor
fho fIask. Shako fhoroughIy for ono mIn and fhon aIIow fo sfand for 30 mIn wIfh occasIonaI
swIrIIng. CooI fho fIask In Ico and add 10% pofassIum IodIdo soIufIon, shako, ropIaco fho
sfoppor and aIIow fo sfand agaIn for 10 mIn. TIfrafo fho froo IodIno agaInsf sfandard sodIum
fhIosuIfafo soIufIon usIng sfarch as IndIcafor. Add fho IndIcafor noar fho ond-poInf,
appoaranco of bIuo coIor IndIcafos fho ond-poInf. Carry ouf a bIank oxporImonf sImuIfanoousIy
usIng 25 mI of fho pofassIum bromafo-bromIdo soIufIon and 25 mI of wafor buf no sampIo,
usIng fho abovo procoduro. Tho bIank doformInafIon Is usod fo doformIno fho fofaI quanfIfy
of bromIno gonorafod and aIso IndoformInafo Iossos of fho roagonf aro IndonfIcaI and fhus
do nof affocf fho rosuIf.
CuIcuIuIions
WoIghf of phonoI fakon = W g
VoIumo of 0.1 N Na
2
S
2
O
3
usod for fho sampIo = V mI
voIumo of 0.1 N Na
2
S
2
O
3
usod for bIank = V
1
mI
VoIumo of 0.1 N Na
2
S
2
O
3
usod for phonoI = tV
1
÷ V) mI
1000 mI of 1 N Na
2
S
2
O
3
soIufIon = 1 g oquIvaIonf woIghf of Na
2
S
2
O
3
soIufIon
tV
1
÷ V) mI 0.I N Na
2
S
2
O
3
= g 1 . 0
1000
) t
1
×
− V V
oquIv. woIghf of Na
2
S
2
O
3
soIufIon
= ÐquIvaIonf woIghf of bromIno =
6
1
1 . 0
1000
) t
1
× ×
− V V
moIo of phonoI tsInco accordIng fo
fho roacfIon abovo, 6 g oquIvaIonf of bromIno = 1 moIo of phonoI)
6
94 1 . 0
1000
) t
1
×
×
− V V
g of phonoI tMoI. wf. of phonoI = 94)
W g of fho sampIo confaIns
6
94 1 . 0
1000
) t
1
×
×
− V V
g of phonoI
100 g of fho sampIo confaIns
W
V V 100
6
94 1 . 0
1000
) t
1
×
×
×

g of phonoI, whIch Is fho porconfago
of phonoI In fho sampIo or porconfago purIfy of fho phonoI sampIo. Tho amounf of puro
phonoI Is doformInod In 100 g sampIo.
Question
?.2 How can monobromInafIon of phonoI bo achIovod7
ESTIMATION OF FUNCTIONAL GROUPS 147
7.3 DETERMINATION OF EQUIVALENT WEIGHT OF A CARBOXYLIC
ACID
Tho oquIvaIonf woIghf of a carboxyIIc acId may bo doscrIbod as fho numbor of grams of fho
acId roquIrod fo noufraIIzo ono IIfro of normaI aIkaII. If fho basIcIfy of fho acId Is known,
fho moIocuIar woIghf may bo caIcuIafod. !oIIowIng fwo mofhods aro ompIoyod for fho
doformInafIon of oquIvaIonf woIghf.
7.3.1 Silver Salt Method (Gravimetric Method)
Tho carboxyIIc acId Is convorfod fo Ifs sIIvor saIf whIch Is IgnIfod and fho mofaIIIc sIIvor
formod Is woIghod.
ChemicuIs
SIIvor nIfrafo soIufIon t10%) AgNO
3
.
ÐIIufo ammonIum hydroxIdo soIufIon t10%).
Procedure: Suspond 0.5÷1 g of a carboxyIIc acId tbonzoIc, phonyIacofIc, succInIc acId, ofc.)
In 20 mI of dIsfIIIod wafor In a 200 mI broakor and sIowIy add dIIufo ammonIum hydroxIdo
soIufIon. SfIr fho mIxfuro fIII fho acId dIssoIvos. ÐxpoI oxcoss ammonIa by warmIng fho
broakor on a wafor-bafh fIII noufraI. CooI and add sIIvor nIfrafo soIufIon fo fho noufraI
warm soIufIon whIIo sfIrrIng tNofo I) fo compIofoIy procIpIfafo fho acId as Ifs sIIvor saIf.
!IIfor fho soIId and wash fhoroughIy wIfh wafor, draIn and dry fho soIId In a vacuum
dosIccafor tNofo II). WoIgh accurafoIy abouf 0.5 g of fho drIod saIf In a woIghod crucIbIo.
Hoaf fho crucIbIo tNofo III) on a Bunson burnor fIrsf gonfIy and fhon rod hof unfII aII
fho sIIvor saIf has docomposod. CooI fho crucIbIo In a dosIccafor and fhon doformIno Ifs
woIghf. Hoaf agaIn fIII a consfanf woIghf of fho crucIbIo and Ifs confonfs Is obfaInod.
ÐoformIno fho woIghf of mofaIIIc sIIvor formod.
CuIcuIuIions
WoIghf of sIIvor saIf fakon = W g
WoIghf of sIIvor affor IgnIfIon = a g
a g of sIIvor Is obfaInod from W g of sIIvor saIf
10?.9 sIIvor wIII bo obfaInod from =
g
9 . 10?
a
W ×
of sIIvor saIf
= ÐquIvaIonf wf. of sIIvor saIf
148 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ÐquIvaIonf wf. of fho acId = ÐquIvaIonf wf. of sIIvor saIf ÷ AfomIc wf. of Ag
+ Tho wf. of H ropIacod by Ag = . 1 9 . 10?
9 . 10?
+ −
×
a
W
Tho moIocuIar woIghf can bo obfaInod by muIfIpIyIng fho basIcIfy wIfh fho oquIvaIonf
woIghf.
Notes ¡: Chock wIfh a IIfmus papor.
¡¡: SIIvor saIf Is sonsIfIvo fo IIghf, dryIng fhoroforo, shouId bo conducfod wIfh mInImum
oxposuro fo IIghf tcovor fho fIask wIfh carbon papor).
¡¡¡: Hoaf fho whoIo crucIbIo fIrsf on fho fIamo fo consfanf woIghf.
7.3.2 Volumetric Method
A known woIghf of fho acId Is dIssoIvod In wafor tor aquoous ofhanoI) and fhon fIfrafod
agaInsf sfandard aIkaII soIufIon. ThIs wIII doformIno fho noufraIIzafIon oquIvaIonf toquIvaIonf
woIghf) of fho acId. Tho moIocuIar woIghf Is obfaInod by muIfIpIyIng If wIfh fho basIcIfy, If
If Is gIvon.
ChemicuIs
º SodIum hydroxIdo soIufIon 0.2 N t8 g/I).
Procedure: WoIgh accurafoIy 1.5÷2 g of an acId In a 100 mI voIumofrIc fIask and dIssoIvo
In wafor or uso onough aIcohoI tNofo I) fo dIssoIvo If. !III fho fIask fo fho affachod mark.
PIpoffo ouf 25 mI of fhIs acId soIufIon In an ÐrIonmoyor fIask, add 2 drops of phonoIphfhaIoIn
IndIcafor and fIfrafo agaInsf sfandard sodIum hydroxIdo soIufIon fo a pInk ond-poInf. Nofo
fho voIumo of sodIum hydroxIdo soIufIon consumod.
CuIcuIuIions
WoIghf of fho acId fakon = W g In 100 mI soIufIon
Assumo 25 mI of fho acId consumos V mI of 0.2 N NaOH
100 mI of fho acId wIII consumo =
25
100 V ×
of 0.2 N NaOH
= 100/25 × V × 1 / 5 N NaOH
= 4 V/5 1 N NaOH
4/5 V mI of 1 N NaOH Is oquIvaIonf fo W g of fho acId
1000 mI of 1 N NaOH Is oquIvaIonf fo = g
4
5 100
V
W × ×
of acId.
ESTIMATION OF FUNCTIONAL GROUPS 149
ThIs Is aIso fho oquIvaIonf woIghf of fho acId. To obfaIn fho moIocuIar woIghf muIfIpIy
by basIcIfy.
Note ¡: !so onIy ofhanoI fo dIssoIvo bonzoIc acId.
7.4 DETERMINATION OF SAPONIFICATION EQUIVALENT OF AN
ESTER
SaponIfIcafIon oquIvaIonf of an osfor Is dofInod as fho oquIvaIonf woIghf of an osfor as
doformInod by fIfrafIon wIfh a sfandard acId. Tho vaIuo Is usofuI In doformInIng fho ompIrIcaI
formuIa of fho osfor.
ChemicuIs
AIcohoIIc pofassIum hydroxIdo soIufIon t0.5 N).
HydrochIorIc acId 0.5 N.
PofassIum hydroxIdo soIufIon t2 g dIssoIvod In 100 mI 95% ofhanoI).
ThIs soIufIon nood nof bo sfandardIzod.
Procedure: !Irsf proparo a sfandard pofassIum hydroxIdo soIufIon In ofhanoI. !or fhIs
dIssoIvo 2 g of pofassIum hydroxIdo poIIofs In 100 mI of 95% ofhanoI In an ÐrIonmoyor
fIask. AIIow fho soIufIon fo soffIo and fhon docanf If In a voIumofrIc fIask. SfandardIzo If
wIfh 0.5 N hydrochIorIc acId soIufIon.
Transfor 10 mI of pofassIum hydroxIdo soIufIon by moans of a pIpoffo Info a 50 mI
gIass-sfopporod ÐrIonmoyor fIask. AccurafoIy woIgh abouf 0.5 g of fho osfor tofhyI bonzoafo
or bonzyI acofafo) Info fho fIask and ropIaco fho sfoppor. SwIrI fho fIask fo mIx fho osfor
wIfh pofassIum hydroxIdo soIufIon. RofIux fho confonfs of fho fIask for 30÷40 mIn. Wash
down fho condonsor wIfh 25 mI wafor and cooI. Add 2 drops of phonoIphfhaIoIn and fIfrafo
agaInsf 0.5 N or 0.25 N hydrochIorIc acId. Nofo fho voIumo of fho acId consumod. AIso run
a bIank undor sImIIar condIfIons.
CuIcuIuIions
WoIghf of fho osfor fakon = W g
SaponIfIcafIon oquIvaIonf =
( ) ( )
×
× − ×
aIkaII acId
W 1000
mI NormaIIfy mI NormaIIfy
!or an osfor of a mono-basIc acId fho vaIuo Is oquaI fo fho moIocuIar woIghf whoroas
for a dIbasIc acId If wIII bo ono haIf fho moIocuIar woIghf.
150 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Questions
?.3 Can ono osforIfy a carboxyIIc acId In fho prosonco of a baso7
?.4 LIsf somo ofhor mofhods of osforIfIcafIon of a carboxyIIc acId.
7.5 ESTIMATION OF A KETO GROUP
MofhyI kofonos can bo osfImafod by froafIng wIfh oxcoss sfandard IodIno In an aIkaIIno
modIum and fhon fIfrafIng fho unroacfod IodIno wIfh sfandard sodIum fhIosuIfafo soIufIon.
ChemicuIs
º IodIno soIufIon 0.1 N tdIssoIvo 20 g pofassIum IodIdo and 6.3 g
IodIno In 100 mI wafor and mako If fo 1000 mI In a
voIumofrIc fIask)
º SodIum fhIosuIfafo soIufIon 0.1 N t24.8 g/I)
º SodIum hydroxIdo soIufIon 1 N t40 g/I)
º SuIfurIc acId 1 N
Procedure: In a 250 mI ÐrIonmoyor fIask fIffod wIfh a ground gIass sfoppor woIgh accurafoIy
0.2÷0.25 g of a kofono tacofono, acofophonono, ofhyI mofhyI kofono, ofc.). To fhIs add 30
mI of 1 N sodIum hydroxIdo soIufIon and shako for 10 mIn. !rom a buroffo run 50 mI of 0.1
N IodIno soIufIon wIfh consfanf sfIrrIng. Shako fhoroughIy for 10÷15 mIn fIII yoIIow crysfaIs
of Iodoform appoar. AcIdIfy fho soIufIon wIfh suIfurIc acId and fIfrafo agaInsf sfandard sodIum
fhIosuIfafo soIufIon usIng sfarch IndIcafor.
ESTIMATION OF FUNCTIONAL GROUPS 151
CuIcuIuIions
WoIghf of fho kofono fakon = W g
VoI. of 0.1 N IodIno soIufIon addod = 50 mI
VoI. of 0.1 N Na
2
S
2
O
3
noodod fo roacf wIfh oxcoss IodIno = V mI
= voIumo of 0.1 N I
2
unusod
VoIumo of IodIno fhaf roacfod wIfh fho kofono = t50 ÷ V) mI.
Now accordIng fo fho abovo roacfIon soquonco 3 moIos of I
2
= ono
moIo of kofono = 120 g tassumIng If fo bo acofophonono)
1 oquIvaIonf of I
2
≡ 1N I
2
soIufIon = M/2 I
2
soIufIon
6 oquIvaIonfs of I
2
≡ 3 MI
2
soIufIon
≡ 6000 mI of 1 N I
2
soIufIon

t6000 × 10) mI of 0.1 N I
2
soIufIon.
t6000 × 10) mI of 0.1 N I
2
soIufIon confaIns 120 g of fho kofono
t50 ÷ V) mI of 0.1 N I
2
soIufIon g
10 6000
) 50 t 120
×
− × V
of fho kofono
W g sampIo confaIns kofono fho of
10 6000
) 50 t 120
g
V
×
− ×
=
100 g sampIo confaIns = g
10 6000
100 ) 50 t 120
× ×
× − ×
W
V
of fho kofono
ThIs Is fho porconfago purIfy of fho kofono, as fho amounf of puro kofono Is doformInod
In 100 g sampIo.
7.6 ESTIMATION OF AN ALDEHYDE GROUP
An aIdohydo Is froafod wIfh an oxcoss of sodIum bIsuIfIfo soIufIon and fho unusod sodIum
bIsuIfIfo soIufIon Is doformInod IdomofrIcaIIy.
152 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuIs
º IodIno soIufIon t0.1 N).
º SodIum bIsuIfIfo soIufIon t12 g/I).
Procedure: In a 250 mI ÐrIonmoyor fIask woIgh accurafoIy 0.2÷0.25 g of fho aIdohydo
tpropIonaIdohydo, n-bufyraIdohydo, ofc.) and dIssoIvo In wafor taIcohoI for wafor InsoIubIo
aIdohydos). Add 50 mI of sodIum bIsuIfIfo soIufIon and shako fho mIxfuro vIgorousIy. Thon
aIIow fo sfand for 20 mIn. TIfrafo fho oxcoss bIsuIfIfo soIufIon agaInsf 0.1 N IodIno soIufIon
usIng sfarch IndIcafor. Nofo fho ond-poInf whIch wIII bo fho appoaranco of a bIuo coIor
tNofo I). AIso fIfrafo 50 mI of sodIum bIsuIfIfo soIufIon agaInsf 0.1 N IodIno soIufIon as
bIank.
CuIcuIuIions
Wf. of fho aIdohydo fakon = W g
Assumo 50 mI of NaHSO
3
soIufIon roquIros V mI of 0.1 N I
2
soIufIon and oxcoss NaHSO
3
soIufIon roquIros V
1
mI of 0.1 N I
2
soIufIon.
tV ÷ V
1
) mI of 0.1 N I
2
soIufIon Is oquaI fo fho IodIno oquIvaIonf fo fho aIdohydo.
1000 mI of 1 N I
2
soIufIon = M/2 oquIvaIonf of fho aIdohydo
tM Is fho moI. wf. of fho aIdohydo)
1000 mI of 0.1 N I
2
soIufIon = M/20 oquIvaIonf of fho aIdohydo
tV ÷ V
1
) mI of 0.1 N I
2
soIufIon =
20 /
1000
) t
1
M
V V
×

oquIvaIonf of fho aIdohydo
Porconfago purIfy of fho aIdohydo =
W M
V V
/ 100 20 /
1000
) t
1
× ×

Note ¡: ConsIdorabIo varIafIons of and fadIng In ond-poInf aro oxporIoncod durIng fIfrafIon. If Is
probabIy duo fo fho rovorsIbIIIfy of fho roacfIon and InsfabIIIfy of fho sodIum bIsuIfIfo
adducf. Tho rosuIf may nof bo vory accurafo.
Question
?.5 Why Is a sharp ond-poInf nof obsorvod In fho osfImafIon of aIdohydos7
ESTIMATION OF FUNCTIONAL GROUPS 153
7.7 ESTIMATION OF SULFUR (MESSENGER’S METHOD) IN THIOUREA
SuIfur In an organIc compound Is osfImafod by fho Mossongor`s mofhod. AccordIng fo fhIs
procoduro suIfur of fho organIc compound Is convorfod Info sufIurIc acId by hoafIng wIfh
aIkaIIno pofassIum pormanganafo soIufIon. SuIfurIc acId Is fhon procIpIfafod wIfh barIum
chIorIdo soIufIon as barIum suIfafo whIch Is fhon osfImafod gravImofrIcaIIy. Tho foIIowIng
roacfIons porfaIn fo fho osfImafIon of suIfur In fhIouroa:
H
2
SO
4
+ BaCI
2
BaSO
4
+ 2 HCl
ChemicuIs
º PofassIum pormanganafo soIufIon t0.5÷1 g soIId).
º BarIum chIorIdo soIufIon t5%).
º SodIum hydroxIdo soIufIon t10%).
Procedure: PIaco accurafoIy woIghod 0.15÷0.25 g sampIo of fhIouroa In a 250 mI round-
boffomod fIask fIffod wIfh an aIr-condonsor. To fhIs add 50 mI of dIsfIIIod wafor and 3 mI of
10% sodIum hydroxIdo soIufIon. Shako fho confonfs fhoroughIy and subsoquonfIy add
0.5÷1 g of pofassIum pormanganafo In smaII Iofs. Add a fow pIocos of boIIIng chIps, ropIaco
fho condonsor and rofIux for 4-5 hrs tNofo I) on a sand-bafh. Affor fhIs durafIon, cooI fho
confonfs fo room fomporafuro and add conc. hydrochIorIc acId t10÷15 mI) dropwIso fo fho
fIask unfII fho purpIo coIor of unroacfod pofassIum pormanganafo Is docoIorIzod. Hoaf fho
fIask agaIn for 10÷15 mIn and fIIfor fho confonfs Info a boakor. Wash fho fIask fhoroughIy
and fransfor washIng on fho fIIfor papor. Conconfrafo fho soIufIon fo abouf 50 mI on a
burnor. Add barIum chIorIdo soIufIon dropwIso wIfh consfanf sfIrrIng In ordor fo procIpIfafo
suIfurIc acId producod fo barIum suIfafo. AIIow fho boakor fo sfand undIsfurbod for 30 mIn.
and fIIfor fho procIpIfafo on a Whafman fIIfor papor. Wash fho procIpIfafo wIfh dIsfIIIod
wafor tNofo II). !oId fho fIIfor papor, pIaco If In a woIghod sIIIcon crucIbIo and hoaf on a
Bunson burnor fo form ash. CooI fho crucIbIo In a dosIccafor and woIgh If agaIn. ÐoformIno
fho woIghf of barIum suIfafo procIpIfafo.
CuIcuIuIions
WoIghf of fhIouroa fakon = W g
WoIghf of barIum suIfafo procIpIfafo = a g
AccordIng fo fho abovo roacfIon = 233.4 g of BaSO
4
confaIns 32 g of 8
Thoroforo, a g of BaSO
4
= 5 M of g
4 . 233
32
×
154 LABORATORY MANUAL OF ORGANIC CHEMISTRY
W g sampIo of fhIouroa confaIns =
32
g of S
233.4
×M
Porconfago of suIfur In fhIouroa =
100
4 . 233
32
× ×
W
a
Notes ¡: If fho coIor of pofassIum pormanganafo dIsappoars durIng hoafIng, add moro of If.
¡¡: Wash fIII chIorIdo Ions aro romovod. Chock fho fIIfrafo wIfh sIIvor nIfrafo soIufIon.
Question
?.6 Why doos fho purpIo coIor dIsappoar on addIng hydrochIorIc acId7
7.8 ESTIMATION OF NITROGEN (KJELDAHL METHOD)
Tho nIfrogon confaInIng compound Is dIgosfod wIfh conc. suIfurIc acId In fho prosonco of a
cafaIysf and nIfrogon of fho sampIo ovoIvod Is convorfod Info ammonIum suIfafo. Thon an
oxcoss sodIum hydroxIdo soIufIon Is addod and ammonIa Is sfoam dIsfIIIod and absorbod In
oxcoss sfandard suIfurIc acId soIufIon. Tho romaInIng mInoraI acId Is back-fIfrafod agaInsf
sfandard sodIum hydroxIdo soIufIon whIch gIvos fho oquIvaIonf of fho ammonIa obfaInod
from fho woIghf of sampIo fakon. Tho foIIowIng roacfIons InvoIvod aro IIIusfrafod by roforonco
fo gIycIno:

tNH
4
)
2
SO
4
+ 2 NaOH 2 NH
3
+ Na
2
SO
4
+ 2 H
2
O
2 NH
3
+ H
2
SO
4
tH
4
)
2
SO
4
ChemicuIs
º SuIfurIc acId soIufIon t0.1 N).
º SodIum hydroxIdo soIufIon t0.1 N, 4 g/I).
º CafaIysf ¦a mIxfuro of K
2
SO
4
t20 g), soIonIum powdor t1 g) and CuSO
4
. 5H
2
O

t1 g)¦
Procedure: WoIgh accurafoIy 0.12÷0.2 g of fho subsfanco tbonzamIdo, dIphonyIamIno,
acofanIIIdo, ofc.) In a cIoan 50 mI KjoIdahI fIask. Add 1.0 g of fho cafaIysf and 5 mI of conc.
suIfurIc acId. PofassIum suIfafo sorvos fo oIovafo fho boIIIng poInf of suIfurIc acId whIIo
ofhors acf as cafaIysf.
Sfoppor fho fIask IoosoIy and dIgosf on a sand-bafh as shown In !Ig. ?.1 In a sIIghfIy
IncIInod posIfIon for 2÷3 hrs tNofo I) In a hood. Affor fho dIgosfIon Is compIofo, cooI fho
ESTIMATION OF FUNCTIONAL GROUPS 155
fIask. In fho moanfImo sof up fho dIsfIIIafIon apparafus as dopIcfod In !Ig. ?.2 tNofo II)
Transfor fho mIxfuro from fho KjoIdahI fIask Info fho chambor C. Pass sfoam Info fho
oufor chambor B by furnIng fho sfopcock A. Infroduco carofuIIy 40 mI of 50% sodIum
hydroxIdo soIufIon fhrough fho funnoI Ð. Tako 50 mI of sfandard sufurIc acId In an ÐrIonmoyor
fIask G. ConfInuo fo pass sfoam for 50÷60 mIn. fo onsuro fhaf aII fho ammonIa ovoIvod has
boon absorbod by fho acId. Turn off fho sfopcock A fo cuf off fho fIow of sfoam. Ðxcoss wafor
can bo romovod from fho oufIof H.
Fig. 7.1: Kjeldahl flask heated on a sand-bath.
Fig. 7.2: Steam distillation and absorption of ammonia.
Tho oxcoss of fho acId In fho ÐrIonmoyor fIask tG) may bo fIfrafod agaInsf sfandard
sodIum hydroxIdo soIufIon, usIng phonoIphfhaIoIn IndIcafor.
156 LABORATORY MANUAL OF ORGANIC CHEMISTRY
CuIcuIuIions
WoIghf of fho nIfrogonous compound fakon = W g
VoIumo of 0.1 N H
2
SO
4
fakon = 50 mI
VoIumo of 0.1 N NaOH soIufIon roquIrod fo back-fIfrafo fho oxcoss acId = V mI
VoIumo of 0.1 N H
2
SO
4
usod up for roacfIon wIfh fho ammonIa ovoIvod = t50 ÷ V) mI
t50 ÷ V) mI 0.1 N H
2
SO
4
= t50 ÷ V) mI of 0.1 N NH
3
1000 mI of 1 N NH
3
= 1? g of ammonIa = 14 g of nIfrogon
1000 mI of 0.1 N NH
3
corrosponds fo 1.4 g of nIfrogon.
t50 ÷ V) mI of 0.1 N NH
3
corrosponds fo
t50 V) 1.4
g of
1000
− ×
nIfrogon.
Porconfago of nIfrogon =
W
V 100
1000
4 . 1 ) 50 t
×
× −
Notes ¡: ThIs Is fho mInImum fImo roquIrod for docomposIfIon and dIgosfIon. Tho durafIon may bo
moro for corfaIn compounds, for oxampIo, nIfrogon confaInIng poIymorIc compounds may
roquIro 10÷12 hrs.
¡¡: In caso such an apparafus Is nof avaIIabIo, fhon sImpIo sfoam dIsfIIIafIon may bo usod.
A wafor condonsor wouId bo Insorfod bofwoon fho IncomIng ammonIa and fho fIask
confaInIng sfandard suIfurIc acId.
7.9 ESTIMATION OF AMINO (–NH
2
) GROUP
Tho osfImafIon of an amIno group can bo accompIIshod In fho samo mannor as of an aIcohoIIc
group, i.c., by acofyIafIon In fho prosonco of acofIc anhydrIdo and dry pyrIdIno, as In fho
caso of aIcohoIs and phonoIs.
ChemicuIs
AcofIc anhydrIdo dIsfIIIod.
SodIum hydroxIdo soIufIon t0.5 N, 20 g/I).
Ðry pyrIdIno.
ESTIMATION OF FUNCTIONAL GROUPS 157
Procedure: Proparo fho acofyIafIng mIxfuro doscrIbod as boforo tSocfIon ?.1.1). In a 250 mI
ÐrIonmoyor fIask fIffod wIfh a wafor condonsor, woIgh accurafoIy abouf 1÷1.5 g of fho
amIno tanIIIno, bonzyIamIno, =-naphfhyIamIno, ofc.) sampIo and add 9 mI of fho acofyIafIng
mIxfuro. RofIux fho confonfs for 45 mInufos wIfh froquonf sfIrrIng. Affor fhIs porIod, cooI
fho fIask undor fap wafor. Add 15 mI of wafor fo fho fIask sIowIy and swIrI fho fIask, cooI In
Ico wafor. TIfrafo agaInsf 0.5 N sodIum hydroxIdo soIufIon ImmodIafoIy. AIso carry ouf a
bIank sImuIfanoousIy usIng 9 mI of fho roagonf onIy.
CuIcuIuIions
CaIcuIafo fho numbor of amIno groups as was dono In fho caso of aIcohoIIc ÷ OH group
osfImafIon.
7.10 ESTIMATION OF THE NUMBER OF AMIDE GROUPS
Tho numbor of groups In an amIdo may bo osfImafod by Ifs hydroIysIs wIfh a
known amounf of aIkaII and back-fIfrafIng fho unusod aIkaII wIfh a sfandard acId.
ChemicuIs
SodIum hydroxIdo soIufIon t2 N, 80 g/I).
HydrochIorIc acId t1 N).
Procedure: WoIgh accurafoIy 0.5÷1 g sampIo of fho amIdo tbonzamIdo, acofamIdo, ofc.) In
a 250 mI round-boffomod fIask and dIssoIvo In a smaII amounf of aquoous ofhanoI. Add
20÷25 mI of 2 N sodIum hydroxIdo soIufIon and shako. !If fho fIask wIfh a wafor condonsor
and hoaf on a sand-bafh fIII fho hydroIysIs Is compIofo tNofo I). ThIs may fako 2÷3 hrs.
CooI and fIfrafo oxcoss aIkaII agaInsf sfandard acId usIng phonoIphfhaIoIn IndIcafor. Nofo
fho voIumo of fho acId consumod.
CuIcuIuIions
WoIghf of fho amId sampIo fakon = W g
VoI. of 1 N HCI usod = V mI
1000 mI of 1 N NaOH = 1 g moI. wf. of NaOH
= 1 g moI. wf. of HCI
= 1 amIdo group
158 LABORATORY MANUAL OF ORGANIC CHEMISTRY
V mI of 1 N NaOH wIII corrospond fo V/1000 amIdo groups
W g of fho amId confaIns V/1000 amIdo groups
M g tmoIocuIar woIghf) of fho amIdo confaIns V/1000 × M/W amIdo groups
Note ¡: HydroIysIs may bo compIofod whon no moro ammonIa gas Is ovoIvod.
Question
?.? WrIfo a chomIcaI roacfIon for fho hydroIysIs of an amIdo In fho prosonco of aquoous
acId.
7.11 ESTIMATION OF GLYCINE (Amino Acid)
GIycIno cannof bo osfImafod dIrocfIy by fIfrafIng wIfh a sfandard aIkaII bocauso of fho
opposIng offocfs of fho basIc and fho acId groups If boIng a bI-funcfIonaI compound. Tho acId
Is, fhoroforo, fIrsf froafod wIfh formaIdohydo tIf Is usod In fho form of an aquoous soIufIon
caIIod formaIIn) foIIowod by fIfrafIon wIfh an aIkaII. Buf sInco gIycIno oxIsfs as a 'zwIfforIon`,
If doos nof roacf wIfh formaIdohydo dIrocfIy. Tho acId Is fhoroforo convorfod Info Ifs sodIum
saIf by froafmonf wIfh sodIum hydroxIdo soIufIon whIch fhon undorgoos roacfIon wIfh
formaIdohydo. Tho foIIowIng chomIcaI roacfIons aro InvoIvod.
If wIII bo nofod fhaf fho carboxyI group Is nof InvoIvod.
ChemicuIs
!ormaIdohydo soIufIon tformaIIn t40%).
SodIum hydroxIdo soIufIon t0.1 N, 4 g/I).
Procedure: WoIgh accurafoIy 2÷2.5 g of gIycIno sampIo In a 250 mI moasurIng fIask, dIssoIvo
If In dIsfIIIod wafor and fIII fo fho ofchod mark. Tako abouf 50 mI of 40% formaIIn from fho
buroffo In an ÐrIonmoyor fIask and add 2÷4 drops of phonoIphfhaIoIn IndIcafor. !rom a
socond buroffo add 0.1 N sodIum hydroxIdo soIufIon, shakIng fIII fho soIufIon Is faInfIy pInk
ESTIMATION OF FUNCTIONAL GROUPS 159
tNofo I). PIpoffo 25 mI of gIycIno soIufIon proparod abovo In a socond ÐrIonmoyor fIask and
add 2 drops of phonoIphfhaIoIn and mako If faInfIy aIkaIIno by fho addIfIon of sodIum
hydroxIdo soIufIon tNofo I). To fhIs add 10 mI of fho abovo noufraIIzod formaIIn soIufIon.
Tho pInk coIor dIsappoars and fho soIufIon bocomos suffIcIonfIy acIdIc. TIfrafo fho mIxfuro
agaInsf 0.1 N sodIum hydroxIdo soIufIon fIII fho pInk coIor Is rosforod and nofo fho voIumo
of aIkaII consumod.
CuIcuIuIions
WoIghf of gIycIno fakon = W g
Assumo 25 mI of fho sfandard gIycIno soIufIon taffor addIng formaIdohydo) roquIro V
mI of 0.1 N NaOH
250 mI wIII roquIro 250/25 × V mI of 0.1 N NaOH or V mI of 1 N NaOH
1000 mI of 1 N NaOH = ?5 g of gIycIno
1 mI of N NaOH =
1000
?5 × V
g of gIycIno
% purIfy of gIycIno =
W
V 100
1000
?5
×
×
Tho caIcuIafIon In basod on fho facf fhaf 1000 mI of 1 N NaOH corrosponds fo 1 moIo of
gIycIno or ?5 g of gIycIno. Thus knowIng fho moIocuIar woIghf of fho acId Ifs purIfy can bo
doformInod, aIso If fho basIcIfy Is gIvon fhon fho moIocuIar woIghf of fho amIno acId can
aIso bo obfaInod.
Note ¡: Thoso oporafIons aro carrIod ouf boforo mIxIng fho fwo soIufIons bocauso formaIIn confaIns
InvarIabIy somo formIc acId whIIo fho amIno acIds aro soIdom compIofoIy noufraI.
Question
?.8 Whaf Is fho funcfIon of addIng formaIIn7
7.12 DETERMINATION OF PERCENTAGE PURITY OF GLUCOSE
(A REDUCING SUGAR)
GIucoso, a roducIng sugar, may bo osfImafod by fIfrafIng wIfh a sfandard !ohIIng`s soIufIon,
ThIs soIufIon shouId bo proparod frosh whon noodod sInco If doforIorafos on koopIng. !nIoss
a groaf caro Is oxorcIsod fhIs osfImafIon may nof yIoId good rosuIfs.
160 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuIs
º !ohIIng`s soIufIon A.
º !ohIIng`s soIufIon B.
º GIucoso tAR grado).
PrepuruIion oj FehIing's SoIuIion
Solutlon A: ÐIssoIvo accurafoIy woIghod 1?.32 g of crysfaIIIno cuprIc suIfafo tCoppor
suIfafo. 5H
2
O) In dIsfIIIod wafor and mako fho soIufIon fo 250 mI In a voIumofrIc fIask.
Solutlon B: ÐIssoIvo 86.5 g of sodIum pofassIum farfarafo tRochoIIo saIf) In warm wafor
In a broakor. AIso dIssoIvo 3.5 g of puro sodIum hydroxIdo In wafor In anofhor boakor. MIx
fho fwo soIufIons and cooI. Transfor fho soIufIon In a 250 mI voIumofrIc fIask and fIII If fo
fho mark.
Procedure: Tho !ohIIng`s soIufIon tcombInod A and B) can bo sfandardIzod by fIfrafIng
wIfh a sfandard soIufIon of gIucoso. !or fhIs woIgh accurafoIy 1.25 g of gIucoso In a 250 mI
moasurIng fIask, dIssoIvo In wafor and mako up fho soIufIon fo fho mark. In an ÐrIonmoyor
fIask pIpoffo oquaI amounfs, i.c., 10 mI of oach soIufIons A and B. TIfrafo fhIs soIufIon
tfofaI 20 mI) wIfh gIucoso soIufIon fakon In a buroffo. Add 1 mI soIufIon of gIucoso af a fImo
In fho bogInnIng and boII fho confonfs affor oach addIfIon. Noar fho ond-poInf add 1÷2 drops
af ono fImo. Tho roacfIon Is compIofo whon fho bIuo coIor has compIofoIy dIsappoarod
tNofo I). Nofo fho voIumo of gIucoso soIufIon. !rom fhIs caIcuIafo fho woIghf of gIucoso
oquIvaIonf fo 1 mI of fho !ohIIng`s soIufIon. NormaIIy If Is found fhaf 1 mI of fho !ohIIng`s
soIufIon Is oquaI fo 0.0051 g of gIucoso and 0.0053 g of frucfoso.
SImIIarIy fako anofhor 20 mI of fho combInod !ohIIng`s soIufIon and fIfrafo wIfh fho
unknown gIucoso sampIo soIufIon tassumo 100 mI sampIo Is provIdod).
CuIcuIuIions
Assumo 20 mI of fho !ohIIng`s soIufIon roquIros V mI of fho unknown gIucoso soIufIon.
SInco 1 mI of fho !ohIIng`s soIufIon = 0.0051g of gIucoso
Thoroforo, 20 mI ¨ ¨ = 20 × 0.0051 g of gIucoso
V mI of unknown gIucoso soIufIon = 20 × 0.0051 g of gIucoso
100 ¨ ¨ ¨ =
V
100 0051 . 0 20 × ×
g of gIucoso
Thoroforo
V
100 0051 . 0 20 × ×
g of gIucoso has boon dIssoIvod In 100 mI unknown soIufIon.
If fho woIghf tW) of fho Impuro gIucoso sampIo Is known, fhon fho porconfago purIfy can bo
caIcuIafod.
ESTIMATION OF FUNCTIONAL GROUPS 161
Porconfago purIfy =
W
V
/ 100
100 0051 . 0 20
×
× ×
Note ¡: To chock for fho compIofIon of fho roacfIon, pIaco a drop of fho soIufIon wIfh fho hoIp of
gIass rod on a gIazod fIIo. Add a drop of ( ) [ ]
6 4
CN !o K soIufIon t5% soIufIon In 10% gIacIaI
acofIc acId). Absonco of any rod procIpIfafo of cuprIc oxIdo IndIcafos fhaf fho ond-poInf
has roachod.
7.13 ESTIMATION OF SAPONIFICATION VALUE OF AN OIL OR FAT
NafuraI oIIs or fafs aro osfors prImarIIy of gIycoroI and corfaIn Iong chaIn carboxyIIc acIds
possossIng an ovon numbor of carbon afoms por moIocuIo. Thoso whIch aro IIquIds af ordInary
fomporafuro aro caIIod oIIs.
SuponijicuIion ruIue oj un oiI or juI may bo doscrIbod as fho numbor of mIIIIgrams
of pofassIum hydroxIdo roquIrod fo hydroIyso ono gram of an oII or faf. If Is an IndIcafIon of
fho avorago moIocuIar woIghf of fho faf or fho Iongfh of fho carbon chaIn of fho faffy acId.
If Is doformInod on a known woIghf of an osfor whIch Is hydroIysod wIfh an oxcoss of aIkaII,
fho unusod aIkaII Is back fIfrafod wIfh a sfandard acId.
ChemicuIs
º AIcohoIIc pofassIum hydroxIdo soIufIon t0.5 N).
º HydrochIorIc acId t0.5 N and 0.1 N).
ProparafIon of aIcohoIIc pofassIum hydroxIdo soIufIon WoIgh 5 g of puro pofassIum
hydroxIdo poIIofs and dIssoIvo In 250 mI of 95% ofhanoI In a sfopporod boffIo. Koop fho
soIufIon ovornIghf. !IIfor and sfandardIzo agaInsf 0.1 N hydrochIorIc acId soIufIon usIng
phonoIphfhaIoIn as IndIcafor.
Procedure: WoIgh accurafoIy 0.5÷1 g of an oII or faf In a 100 mI round boffomod fIask. Add
50 mI of sfandard 0.5 N aIc. pofassIum hydroxIdo soIufIon. RofIux on a sfoam-bafh fIII fho
soIufIon Is cIoar tIf may fako 1.5÷2 hrs). CooI and dIIufo If fo 250 mI In a voIumofrIc fIask.
162 LABORATORY MANUAL OF ORGANIC CHEMISTRY
PIpoffo ouf 25 mI of fhIs soIufIon and fIfrafo agaInsf 0.1 N hydrochIorIc acId usIng
phonoIphfhaIoIn as IndIcafor.
CuIcuIuIions
WoIghf of fho oII or faf fakon = W g
Assumo 25 mI soIufIon roquIros V mI of 0.1 N HCI
and 250 mI soIufIon wouId roquIro = 250/25 × V mI of 0.1 N HCI
= 10 × of V mI 0.1 N HCI
=
5 . 0
1 . 0 10 × ×V
mI of 0.1 N HCI
= 2V mI of 0.1 N HCI
VoIumo of 0.5 N KOH usod = t50 ÷ 2 V) mI
1000 mI of 1 N KOH = 56 g of KOH
1000 mI of 0.5 N KOH = 28 g of KOH
t50 ÷ 2 V) mI of 0.5 N KOH =
t50 2V) 28
1000
− ×
g of KOH
W g of fho faf roquIros =
t50 2V)
28
1000

× g of KOH
1 g of fho faf roquIros =
t50 2V) 28
1000 W

× g of KOH
or
t50 2V) 28
1000
1000 W

× × mg of KOH
Thoroforo, by dofInIfIon fhIs Is fho saponIfIcafIon vaIuo of fho oII or fho faf.
7.14 DETERMINATION OF IODINE NUMBER OF AN UNSATURATED
COMPOUND
Tho numbor of doubIo bonds or oIofInIc unsafurafIon In a compound can bo
doformInod by cafaIyfIc hydrogonafIon, i.c., H
2
wIfh Pf or Ranoy nIckoI as cafaIysf. Tho
voIumo of hydrogon gas absorbod Is moasurod and fho numbor of doubIo bonds can bo
ESTIMATION OF FUNCTIONAL GROUPS 163
osfImafod. Mosf of fho cIassIcaI mofhods for fho doformInafIon of unsafurafIon woro
concornod prImarIIy for fho anaIysIs of anImaI and vogofabIo fafs and oIIs. Tho unsafurafIon
vaIuo so doformInod woro oxprossod as IodIno numbor or bromIno numbor. ThIs vaIuo
roprosonfs fho amounf of froo haIogon In grams roquIrod for 100 g of fho sampIo moIocuIo.
Thoso vaIuo dIspIay consIdorabIo varIafIon by fho uso of dIfforonf haIogons and fhus aro of
IIffIo quanfIfafIvo organIc anaIysIs. NovorfhoIoss, fho doformInafIon of IodIno numbor wIII
bo doscrIbod horo.
ChemicuIs
º WIj`s soIufIon.
º PofassIum IodIdo soIufIon t15%).
º SodIum fhIosuIfafo soIufIon t0.1 N, 24. 8 g/I).
º Sfarch IndIcafor.
Prepurutlon oI Wlj's solutlon: ThIs Is sImpIy IodIno monochIorIdo soIufIon In acofIc
acId. If Is proparod by dIssoIvIng ?.9 g of puro IodIno frIchIorIdo In 100 mI of gIacIaI acofIc
acId In a boakor by warmIng on a wafor-bafh. In anofhor fIask dIssoIvo 8.? g of rosubIImod
IodIno In a socond porfIon of warm gIacIaI acofIc acId. MIx fho fwo soIufIons In a 1000 mI
voIumofrIc fIask and mako up fho soIufIon fo fho mark wIfh gIacIaI acofIc acId. Sforo fho
WIj`s soIufIon In a woII sfopporod ambor boffIo.
Procedure: WoIgh accurafoIy 0.15÷0.3 g oII or faf tcoffon sood oII, corn oII, poanuf oII,
ofc.) In a 250 mI gIass-sfoppod fIask tIodIno fIask). To fhIs add 25÷30 mI of chIoroform or
carbon fofrachIorIdo fo dIssoIvo fho sampIo, warm If nocossary. To fho soIufIon add 25 mI of
fho WIj`s soIufIon, sfoppor fho fIask and shako vIgorousIy for a fow mInufos. AIIow fho fIask
fo sfand for 30 mIn wIfh occasIonaI shakIng. Affor fhIs porIod, add 25 mI of pofassIum IodIdo
soIufIon and dIIufo fho mIxfuro wIfh 50÷100 mI of wafor. TIfrafo If ImmodIafoIy agaInsf
0.1 N sodIum fhIosuIfafo soIufIon fakon In a buroffo. Shako vIgorousIy affor oach addIfIon
and agaIn fIfrafo unfII fho yoIIow coIor aImosf dIsappoars. Add sfarch soIufIon and fIfrafo
agaIn fo fho dIsappoaranco of fho bIuo coIor.
SImuIfanoousIy porform a bIank fIfrafIon usIng 25 mI of fho IodIno monochIorIdo
soIufIon.
CuIcuIuIions
Tho IodIno numbor can bo caIcuIafod from fho foIIowIng formuIa:
IodIno numbor =
( )
l000 W
l00 l2? Þ V V
2 l
×
× × × −
Whoro
W roprosonfs fho woIghf of fho sampIo.
V
1
voIumo of Na
2
S
2
O
3
soIufIon usod for fho sampIo.
V
2
voIumo of Na
2
S
2
O
3
soIufIon usod for bIank.
N normaIIfy of Na
2
S
2
O
3
soIufIon.
164 LABORATORY MANUAL OF ORGANIC CHEMISTRY
7.15 ESTIMATION OF THE REACTION CONSTANT (H)
ConsIdorabIo work has boon dono fo doscrIbo fho offocf of subsfIfuonfs on moIocuIar roacfIvIfy
In a quaIIfafIvo fashIon. Hammoff, howovor, proposod a quanfIfafIvo roIafIonshIp bofwoon
sfrucfuro and roacfIvIfy.
BonzoIc acId IonIzos accordIng fo fho foIIowIng oquafIon:
whoro K roprosonfs fho IonIzafIon consfanf.
Tho nogafIvo IogarIfhm of K donofod by K
a
may bo fakon as a moasuro of fho acId
sfrongfh. Prosonco of poIar subsfIfuonfs on fho bonzono rIng wIII Incroaso or docroaso fho
acId sfrongfh. ThIs InfIuonco of subsfIfuonfs can bo roaIIzod from fho woII known Hammoff
oquafIon, formaIIzod In fho foIIowIng mannor:
Iog K1K
a
= H I
whoro K and K
a
aro fho IonIzafIon consfanfs of subsfIfufod and unsubsfIfufod bonzoIc acIds
I Is fho subsfIfuonf consfanf.
H Is fho roacfIon consfanf.
A pIof of Iog K1K
a
agaInsf I Is IInoar wIfh sIopo oquaI fo H. Tho roacfIon consfanf
moasuros fho suscopfIbIIIfy of a roacfIon fo fho poIar offocfs of fho subsfIfuonfs. Tho
magnIfudo of fho vaIuo of H IndIcafos fhaf fho roacfIon In sonsIfIvo fo fho poIar offocfs. If
provIdos InformafIon abouf fho nafuro of fho fransIfIon sfafo InvoIvod In fho roacfIon. A
nogafIvo vaIuo of H shows fhaf fho roacfIon In aIdod by oIocfron-donafIng groups and vIco
vorsa. To osfImafo H sovoraI subsfIfufod bonzoIc acIds aro fakon and pK
a
`s aro doformInod.
SInco K
a
=
and af haIf-oquIvaIonco [ ]
÷
ArCOO = [ ] ArCOOH
K
a
=
 
 
+
H
or pK
a
= - Iog H
+
= pH
Thoroforo, a pIof of fho Hammof oquafIon Is drawn bofwoon pK tsubsfIfufod), pK
a
tunsubsfIfufod) vorsus I. Tho I vaIuos for sovoraI subsfIfufonfs havo boon doformInod and
aro gIvon In TabIo ?.1.
ESTIMATION OF FUNCTIONAL GROUPS 165
Table 7.1: Substituent Constant (σ) Values
Group σ σσ σσ
m
σ σσ σσ
p
NH
2
– 0.161 – 0.660
CH
2
– 0.069 – 0.170
OH – 0.002 – 0.357
H – 0 – 0
NO
2
0.710 0.778
Cl 0.373 0.227
CN 0.678 0.628
Br 0.390 0.232
Chemicals
• Benzoic and substituted benzoic acids.
• Sodium hydroxide solution (0.01 N, 0.4 g/l).
Procedure: Weigh accurately about 0.2 g benzoic (Note I) in a 100 ml Erlenmeyer flask.
Dissolve it in one-half equiv. of standard 0.01 N sodium hydroxide solution in 50 ml of
ethanol (Note II). Let the solution equilibrate (it may take 30–45 min), then note the
temperature. Measure the pH of this solution on a pH meter and calculate the corresponding
pK
a
. Draw a plot between pK
a
and σ of the corresponding acids and obtain ρ.
Notes I: Each student is assigned an acid.
II: For 0.2 g (0.001 mole) of benzoic acid, 0.0005 equiv. of sodium hydroxide (half equiv.) is
needed. If sodium hydroxide is 0.01 N, then use 5 ml of this solution.
7.16 DETERMINATION OF CHEMICAL OXYGEN DEMAND (COD)
Presence of carbonaceous organic matter tends to deplete the concentration of oxygen in
waste waters which is so important for the life of aquatic animals. The COD determination
is a measure of the oxygen equivalent of that portion of organic material that is oxidized by
a strong oxidizing agent. The value is reported as mg/l of COD. It is an easily determined
parameter and is important in the control of waste in treatment plants.
Chemicals
• Potassium dichromate solution (0.25 N, 10.26 g/l).
• Ferrous ammonium sulfate solution (0.1 N, 39.2 g/l).
166 LABORATORY MANUAL OF ORGANIC CHEMISTRY
º MorcurIc suIfafo crysfaIs.
º SuIfurIc acId and sIIvor suIfafo tdIssoIvo 0.45 g of sIIvor suIfafo In 5 kg conc. suIfurIc
acId and Ioavo for fwo days).
º !orroIn IndIcafor.
Procedure: In a 250 mI round-boffomod fIask oquIppod wIfh a rofIux condonsor pIaco 0.4 g
of morcurIc suIfafo tNofo I), 20 mI of wasfo wafor sampIo tNofo II) and mIx. Add fo fhIs
mIxfuro 10 mI sfandard pofassIum dIchromafo soIufIon foIIowod by 30 mI suIfurIc acId
confaInIng sIIvor suIfafo tNofo III), wIfh consfanf shakIng. Add boIIIng chIps, ropIaco, fho
condonsor and rofIux for 2 hrs fo oxIdIzo fho carbonacoous maffor. CooI and wash fho
condonsor wIfh 20 mI of dIsfIIIod wafor. Transfor fho mIxfuro fo a 250 mI ÐrIonmoyor fIask.
RInso fho round-boffomod fIask fwIco wIfh dIsfIIIod wafor. TIfrafo agaInsf 0.1 N forrous
ammonIum suIfafo soIufIon usIng 2÷3 drops of forroIn IndIcafor. Tho ond-poInf Is IndIcafod
by a chango of coIor from bIuo-groon fo roddIsh brown. A bIank usIng 20 mI of dIsfIIIod
wafor shouId aIso bo run sImuIfanoousIy.
CuIcuIuIions
mg/I COÐ =
sampIo mI
8000 ) t
1
× − N V V
whoro V mI of forrous ammonIum suIfafo soIufIon usod for bIank.
V
1
mI of forrous ammonIum suIfafo soIufIon usod for fho sampIo.
N normaIIfy of forrous ammonIum suIfafo soIufIon.
Comparo fho rosuIf wIfh ofhor cIassmafos.
Notes ¡: If Is usod fo scavongo fho chIorIdo Ions.
¡¡: A sowago sampIo may bo obfaInod.
¡¡¡: If Is usod as a cafaIysf.
7.17 ESTIMATION OF KETO-ENOL EQUILIBRIUM OF A KETO ESTER
Equilibrium constant of ethyl acetoacetate
ÐfhyI acofoacofafo, oIfhor In soIufIon or In puro sfafo, consIsfs of an oquIIIbrIum mIxfuro of
fwo forms known as tuutomers. Tho fwo forms dIffor In fho posIfIon of a hydrogon afom.
ThIs phonomonon Is known as keto-enol tuutomerlsm. Tho oquIIIbrIum Is doformInod by
an IndIrocf mofhod by froafIng ofhyI acofoacofafo wIfh bromIno tIn fho prosonco of >-
naphfhoI) sInco fho onoIIc form roacfs af a much fasfor rafo fhan fho kofo form. Tho soIufIon
cannof bo fIfrafod dIrocfIy wIfh bromIno as HBr gonorafod cafaIyzos kofo-onoI
faufomorIzafIon.
ESTIMATION OF FUNCTIONAL GROUPS 167

Tho funcfIon of >-naphfhoI Is fo romovo oxcoss bromIno.

ChemicuIs
º BromIno 0.1 M In CH
3
OH t16 g/I).
º PofassIum IodIno soIufIon 0.1 M In H
2
O

t15.6 g/I).
º SodIum fhIosuIfafo soIufIon 0.1 M t24.8 g/I).
º >-NaphfhoI soIufIon 10% In CH
3
OH.
Procedure: WoIgh accurafoIy 6.5 g of ofhyI acofoacofafo In a 100 mI voIumofrIc fIask and
fIII If fo fho mark wIfh mofhanoI fo gIvo 0.5 M soIufIon. tNofo I) PIpoffo 10 mI of fhIs
soIufIon In a 250 mI ÐrIonmoyor fIask. Add 10 mI of 0.1 M bromIno soIufIon and shako.
ImmodIafoIy add 10 mI of 10% soIufIon of >-naphfhoI tNofo II). Shako fho fIask vIgorousIy
for 2 mIn. Add 25 mI of app. 0.1 M aquoous pofassIum IodIdo soIufIon and aIIow fo sfand for
15 mIn af room fomporafuro wIfh occasIonaI shakIng. Thon fIfrafo agaInsf sfandard sodIum
fhIosuIfafo soIufIon tno IndIcafor). Tho soIufIon passos from a wIno-rod fo a coIorIoss form
fo a IIghf yoIIow coIor tNofo III). Nofo fho voIumo of sodIum fhIosuIfafo soIufIon consumod.
168 LABORATORY MANUAL OF ORGANIC CHEMISTRY
CuIcuIuIions
Assumo voIumo of 0.1 M Na
2
S
2
O
3
soIufIon usod = V mI
V mI of 0.1 M Na
2
S
2
O
3
= V/2 mI of 0.1 M I
2
= V/20 mIIII oquIvaIonfs of 1 N |
2
= V/20 mIIII oquIvaIonfs of bromo osfor
= V/20 mIIII oquIvaIonfs of onoI form
= V/20 × 130 mg of onoI form
= 6.5 V mg of onoI form
AcofoacofIc osfor fakon = 10 mI of 0.5 M
= 10 × 0.5 mIIII oquIvaIonfs
= 10 × 0.5 × 130 mg
= 650 mg
Thoroforo, heIo from = 650 ÷ 6.5 V
K
cq
=
V
V
5 . 6 650
5 . 6

ThIs vaIuo Is around 0.0?.
Notes ¡: Tho conconfrafIon of fho osfor shouId bo known oxacfIy.
¡¡: !so a graduafod cyIIndor fo moasuro bromIno and >-naphfhoI soIufIons.
¡¡¡: Tho ond-poInf shouId porsIsf for af Ioasf 3 mIn.
Questions
?.9 Why doos fho onoIIc from roacf wIfh bromIno7
?.10 Why Is If nof nocossary fo know fho oxacf conconfrafIon of Br
2
and >-napfhoI7
7.18 DETERMINATION OF THE NUMBER OF METHOXY (–OCH
3
)
GROUPS
Tho mofhoxy group Is osfImafod accordIng fo fho procoduro of ZoIsoI. A known woIghf of
fho compound Is docomposod by rofIuxIng wIfh hydroIodIc acId whoroby If Is convorfod Info
voIafIIo mofhyI IodIdo. If Is washod froo of hydrogon IodIdo and IodIno and fhon absorbod In
a 4% aIcohoIIc sIIvor nIfrafo soIufIon. SIIvor IodIdo Is woIghod and osfImafod gravImofrIcaIIy
as AgI.
R ÷ OCH
3
+ HI R ÷ OH + CH
3
I
ESTIMATION OF FUNCTIONAL GROUPS 169
A rafhor moro convonIonf procoduro Is fo absorb fho IIborafod mofhyI IodIdo In acofIc acId
and sodIum acofafo soIufIon confaInIng bromIno and fhon osfImafod voIumofrIcaIIy. !Irsf
IodIno monobromIdo Is formod whIch Is furfhor oxIdIzod fo IodIc acId. Thon pofassIum IodIdo
soIufIon Is addod fo IIborafo IodIno whIch Is fIfrafod agaInsf sfandard sodIum fhIosuIfafo
soIufIon. Tho foIIowIng roacfIons fako pIaco:
CH
3
I + Br
2
CH
3
Br + IBr
IBr + 2 Br
2
+ 3 H
2
O HIO
3
+ 5 HBr
HIO
3
+ 5 HI 3 I
2
+ 3 H
2
O
3 I
2
+ 6 Na
2
S
2
O
3
NaI + Na
2
S
4
O
6
AppuruIus
Tho apparafus ompIoyod Is shown In !Ig. ?.3. If consIsfs of a pyrox gIass fwo nockod round-
boffomod fIask A. A LIobIg`s condonsor C and a frap Ð Is fIffod In ono joInf and an InIof
carbon dIoxIdo fubo B Is affachod fo fho socond joInf. Tho frap Ð Is connocfod fo fwo rocoIvors
Ð and !. Tho roacfIon fIask A Is Immorsod In an oII-bafh. Tho Ioff hand sIdo assombIy H Is
a dovIco by moans of whIch fho vapor of chIoroform boIIIng In fho fIask can bo passod
fhrough fho condonsor C.
ChemicuIs
AcofIc acId-sodIum acofafo-bromIno soIufIon. ÐIssoIvo 10 g anhydrous sodIum acofafo
In 100 mI gIacIaI acofIc acId. Add 0.3 mI of bromIno por 10 mI of soIufIon boforo uso.
º SodIum acofafo soIufIon t25%).
º SuIfurIc acId t10%, V1V).
º SodIum fhIosuIfafo soIufIon t0.05 N, 12.25 g/I).
º Sfarch IndIcafor.
Procedure: Pour anfImony sodIum farfarafo t8÷10% soIufIon In wafor) soIufIon In frap Ð
onough fo convor fho InfornaI fubo. ThIs soIufIon wIII rofaIn hydroIodIc acId and IodIno.
Chargo fho fubos Ð and ! wIfh oquaI quanfIfIos t10÷12 mI) of acofIc acId-sodIum acofafo-
bromIno soIufIon. WoIgh 20÷25 mg of fho sampIo accurafoIy In a fIn foII cup, foId If and drop
If Info fho fIask A fhrough fho InIof B. AIso add 0.5 g of phonoI, 1.0 mI of dIsfIIIod propIonIc
anhydrIdo and a fow chIps of carborundum tNofo I). ÐIssoIvo fho sampIo compIofoIy by
warmIng and Infroduco 10 mI of hydroIodIc acId tNofo II) fhrough B and ImmodIafoIy ropIaco
fho fubo and connocf fo fho carbon dIoxIdo sourco ÷ a KIpp`s apparafus. Now pass chIoroform
vapors fhrough fho condonsor C for 10 mIn and sfarf hoafIng fho oII-bafh. Adjusf fho passago
of fho carbon dIoxIdo fhrough fho InIof fubo so fhaf fho rafo of bubbIIng In fho rocoIvors Ð
and ! Is 1÷2 bubbIos/mIn. If fho rafo Is foo rapId somo hydroIodIc acId wIII oscapo absorpfIon.
170 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho oII-bafh shouId affaIn fomporafuro of 140°C In abouf ?5 mIn. ÐurIng fhIs porIod fho
roacfIon Is usuaIIy compIofo. In a 250 mI fIask fIffod wIfh a gIass sfoppor and confaInIng 10
mI of 25% sodIum acofafo soIufIon, fransfor fho confonfs of rocoIvors Ð and !. Tho sodIum
acofafo Is roquIrod fo buffor fho HBr formod. To dosfroy oxcoss of bromIno, formIc acId
t90%) Is addod dropwIso unIf fho smoII of bromIno Is no Iongor dofocfod tNofo III). RopIaco
fho sfoppor and shako fho fIask. ÐIIufo fho confonfs of fho fIask fo 100 mI wIfh wafor , 1 g
of pofassIum IodIdo and 10 mI of suIfurIc acId, sfoppor fho fIask ImmodIafoIy, swIrI gonfIy,
aIIow fo sfand undIsfurbod for 3-4 mIn. Tho soIufIon Is fhon fIfrafod agaInsf sfandard
fhIosuIfafo soIufIon, usIng sfarch IndIcafor. A bIank may bo run usIng phonoI and propIonIc
anhydrIdo.
Fig. 7.3 Assembly for the estimation of methoxy group.
CuIcuIuIions
AccordIng fo fho oquafIons abovo a convonIonf convorsIon facfor Is obfaInod as foIIows:
–OCH
3
CH
3
I HIO
3
3 I
2
6 Na
2
S
2
O
3
WoIghf of fho compound fakon = W

g
VoIumo of 0.05 Na
2
S
2
O
3
roquIrod = V
1
mI
6 × 1000 mI, 1 N Na
2
S
2
O
3
soIufIon = 31 g OCH
3
groups
6 × 20 × 1000 mI, 1 N Na
2
S
2
O
3
soIufIon = 31 g OCH
3
groups
V
1
mI of 0.05 N of Na
2
S
2
O
3
soIufIon =
000 , 120
31
1
V ×
g OCH
3
groups
ESTIMATION OF FUNCTIONAL GROUPS 171
Thoroforo, W g of fho unknown confaIns
3
1
OCH g
000 , 120
31 V ×
groups
Porconfago OCH
3
group =
X
W 120,000
100 V 31
1
=
×
× ×
If fho moIocuIar woIghf tM) of fho unknown Is gIvon fhon fho numbor of mofhoxy
groups Is gIvon by:
3
OCH
31 100
X M
×
×
groups tOno OCH
3
group = 31).
Notes ¡: Thoso roagonfs hoIp dIssoIvo as aIkoxy compound. ChIps of carborundum provonf bumpIng.
¡¡: Tho consfanf boIIIng acId tb.p. 120°C/?60 mm) confaInIng 5?% of hydroIodIc acId Is
safIsfacfory.
¡¡¡: To fosf dosfrucfIon of bromIno add a drop of mofhyI rod IndIcfor. ÐocoIorIzafIon IndIcafos
fho prosonco of bromIno. Add moro formIc acId.
7.19 DETERMINATION OF ASCORBIC ACID CONCENTRATION
VIf. C Is aIso known as ascorbIc acId. If Is found In a wIdo varIofy of fruIfs and vogofabIos.
Good sourcos IncIudo: broccoII, Iomon, orangos, kIwI fruIf, fomafoos, papaya, Ioafy groons,
brussoIs sproufs, ofc. VIf. C Is an anfIoxIdanf and hoIps provonf agoIng of skIn.
ConconfrafIon of ascorbIc acId tVIf. C) In fruIf juIco tIomon, orango) or VIf. C fabIofs
tCoIIn) can bo doformInod by fIfrafIng agaInsf a soIufIon of 2, 6-dIchIorophonoI IndophonoI
dyo. ThIs dyo gIvos pInk coIorafIon In acId soIufIon.
172 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ChemicuIs
Dye Solutlon: ÐIssoIvo sodIum saIf of fho dyo t0.125 g) In 240 mI of dIsfIIIod wafor In
a 250 mI voIumofrIc fIask. Mako up fo fho mark wIfh phosphafo buffor toquIvaIonf fo 0.0165
of K
2
HPO
4
and 0.0202 g of KH
2
PO
4
por 250 mI of fho soIufIon).
Stundurd Ascorblc Acld Solutlon: ÐIssoIvo tjusf boforo uso) puro 10 mg ascorbIc
acId In dIsfIIIod wafor In a 100 mI voIumofrIc fIask.
Source of Vitamin C
A vIfamIn C fabIof or fruIf juIco can bo usod fo osfImafo fho amounf of VIf. C.
Vitamin C Tablet
Tako a VIf. C fabIof confaInIng mInImum 100 mg of fho vIfamIn. WoIgh fho fabIof accurafoIy.
Crush If on a fIIfor papor and fransfor fho powdor fo a 100 mI ÐrIonmoyor fIask. Add 500 mI
of a coId 1% oxaIIc acId soIufIon In dIsfIIIod wafor. Loavo If for somo fImo. !IIfor fho mIxfuro
dIrocfIy Info a 1000 mI voIumofrIc fIask. Wash fho ÐrIonmoyor fIask and fho fIIfor papor
wIfh 200 mI, 1% oxaIIc acId soIufIon Info fho voIumofrIc fIask. !III fho fIask fo fho mark
wIfh addIfIonaI 1% oxaIIc acId soIufIon and mIx fhoroughIy. !or caIcuIafIng fho normaIIfy
of fho dyo agaInsf a sfandard ascobIc acId sampIo. Tho normaIIfy and fho amounf of VIf. C
can bo doformInod usIng 5 mI of VIf. C soIufIon.
Fruit Juice
!IIfor 10 mI of orango juIco oIfhor from fho fruIf torango) or from cannod juIco fo romovo
fho puIp. WIfh fho hoIp of a buroffo, fransfor 5 mI of fho juIco In a 50 mI voIumofrIc fIask.
ÐIIufo fho orango juIco wIfh 1% oxaIIc acId soIufIon up fo fho mark.
Procedure: In a cIoan 100 mI ÐrIonmoyor fIask, pIpoffo 5 mI of juIco tVIf. C fabIof or fruIf
juIco). TIfrafo If wIfh 2, 6-dIchIorophonoIIndophonoI dyo fakon In a buroffo wIfh consfanf
shakIng. Tho ond-poInf Is roachod whon a pInk coIor Is obfaInod. AIso carry ouf a bIank
wIfhouf fho sampIo usIng 5 mI of dIsfIIIod wafor onIy. ThIs Is an aIfornafIvo mofhod fo fho
ono doscrIbod undor VIf. C.
CuIcuIuIions
WoIghf of ascorbIc acId dIssoIvod In 100 mI = W g
dIsfIIIod wafor
VoIumo of dyo noodod for fruIf juIco = V mI
VoIumo of dyo noodod for ascorbIc acId = V
1
mI
VoIumo of dyo noodod for bIank = V
2
mI
ESTIMATION OF FUNCTIONAL GROUPS 173
TofaI amounf of VIf. C In fruIf juIco =

× ×

2
1
V V
W ÐIIufIon facfor
V V
Dllutlon Iuctor: In fho abovo caso 5 mI fruIf juIco Is dIIufod fo 50 mI fhoroforo, fho
dIIufIon facfor Is oquaI fo 10.
7.20 DETERMINATION OF MOLECULAR WEIGHT OF A SUBSTANCE
(RAST’S METHOD)
Tho moIfIng tor froozIng) poInf of a puro subsfanco Is doprossod whon an ImpurIfy Is addod.
ThIs IoworIng can bo oxprossod In quanfIfafIvo form as:
n K T
j j
=
whoro T
j
Is fho IoworIng In froozIng poInf of soIufo.
K
j
Is fho moIaI doprossIon consfanf.
In Rasf`s mofhod camphor Is usod as a soIvonf bocauso In fho moIfon sfafo If has a
hIgh soIvonf powor for organIc compounds. Moroovor, bocauso of Ifs Iargo moIocuIar
doprossIon consfanf If pormIfs fho obsorvafIon of doprossIon wIfh an ordInary fhormomofor.
ChemicuIs
º NaphfhaIono, camphor, acofanIIIdo.
ÐoformInafIon of moIocuIar woIghf of acofanIIIdo InvoIvos fho foIIowIng fwo sfops:
DeIerminuIion oj K
j
jor cumphor· WoIgh a cIoan, dry woIghIng boffIo and pIaco
abouf 0.2 g of naphfhaIono In If and doformIno Ifs accurafo woIghf. Add approxImafoIy 2 g
powdorod camphor and aIso doformIno fho accurafo woIghf of fho mIxfuro. Puf a gIass
sfoppor on fho woIghIng boffIo and gonfIy hoaf on a fIamo fo obfaIn a cIoar soIufIon. Shako
fho boffIo fo gof a homogonoous soIufIon. CooI and wIfhdraw a smaII porfIon of fho soIIdIfIod
mIxfuro and doformIno fho moIfIng poInf of fho mIxfuro In a capIIIary fubo. Ropoaf fo
obfaIn a safIsfacfory moIfIng poInf.
DeIerminuIion oj moIecuIur ueighI oj uceIuniIiJe· Ropoaf fho procoduro doscrIbod
In fho abovo sfop usIng approxImafoIy fho samo amounfs of chomIcaIs buf ropIaco acofanIIIdo
for naphfhaIono. ÐoformIno a safIsfacfory moIfIng poInf of fho mIxfuro.
CuIcuIuIions
WoIghf of naphfhaIono = W g
WoIghf of camphor = W
1
g
!roozIng poInf of fho mIxfuro = t°C tmoan of 2÷3 doformInafIons)
ÐoprossIon of froozIng poInf = t1?6 ÷ t)°C
174 LABORATORY MANUAL OF ORGANIC CHEMISTRY
whoro 1?6°C Is fho moIfIng poInf of camphor. W
1
g of naphfhaIono dIssoIvod In W g of
camphor causos a doprossIon of t1?6 ÷ t)°C.
128 g tmoI. woIghf of naphfhaIono) of naphfhaIono In 100 g of camphor wIII causo a
doprossIon of:
K
j
=
l000
l28 ) l?6 (
l
×
× −
9
9 J
ThIs Is fho vaIuo of K
j
WoIghf of acofanIIIdo = a g
WoIghf of camphor = W g
!roozIng poInf of fho mIxfuro = t°C
ÐoprossIon of froozIng poInf = t1?6 ÷ t
1
)°C
a g of acofanIIIdo dIssoIvod In W
1
g of camphor causos a doprossIon of t1?6 ÷ t
1
)°C.
MoIocuIar woIghf =
) 1?6 t
1000
1
t W
K a
j
− ×
× ×
.
ChupIer 8
ORGANIC PREPARATIONS
Tho sfudonf of organIc chomIsfry Is aIso concornod wIfh an Imporfanf cIass of Iaborafory
oxporImonfs, i.c., organIc proparafIons. If Is nocossary, fhoroforo, fo gIvo an adoquafo
fraInIng In fhIs aroa, such oxorcIsos wIII gIvo fho nocossary oxporIonco and confIdonco fo
work Iafor as a skIIIod rosoarch work. Tho synfhofIc oxporIonco gaInod af fho Iaborafory
sfago can bo adopfod on a Iargo scaIo. If Is Infondod fo doscrIbo a numbor of dIvorso
oxporImonfs whIch moof a numbor of crIforIa, i.c., bo roadIIy porformabIo wIfhIn fho
sfIpuIafod Iaborafory porIod, covor adoquafoIy somo concopf of organIc chomIsfry and fInaIIy
fho oxporImonf posos somo InforosfIng quosfIons In fho mInd of fho sfudonf. !urfhormoro,
fho soIocfIon of oxporImonfs Is aIso govornod by fho oaso of fho avaIIabIIIfy of chomIcaIs
and ossonfIaI apparafus. Laborafory procoduro and synfhofIc oxporImonfs of varIous
compounds of provon vaIuo wIII bo dIscussod. As far as possIbIo, oxporImonfs fhaf InvoIvo a
corfaIn anaIyfIcaI fochnIquo; concopf or roacfIon fypo havo boon groupod fogofhor. AII fho
oxporImonfs wIII ufIIIso fho fochnIquos dIscussod In Chapfor 2.
If Is Imporfanf fo nofo fhaf aII organIc compounds aro pofonfIaIIy dangorous and fIro
hazards aro Iargo, and many compounds aro poIsonous. Ono shouId, fhoroforo, bo awaro of
fho pofonfIaI dangors and for safo workIng, fho fumo hood shouId bo usod as much as possIbIo.
8.1 ELECTROPHILIC AROMATIC SUBSTITUTION REACTIONS
In an oIocfrophIIIc roacfIon, a hydrogon on fho bonzono rIng Is ropIacod by a sfrong
oIocfrophIIIc i.c., a posIfIvoIy chargod spocIos. SovoraI fypos of roagonfs yIoId subsfIfufIon
producfs. ThIs roacfIon Is IrrovorsIbIo.
whoro
176 LABORATORY MANUAL OF ORGANIC CHEMISTRY
An oIocfron dofIcIonf spocIos Is aIways fho affackIng roagonf. ÐIocfrophIIIc aramafIc
subsfIfufIon roacfIons aro fho mosf wIdoIy sfudIod roacfIons In organIc chomIsfry.
8.1.1 Preparation of Nitrobenzene (Nitration)
AromafIc compounds can bo nIfrafod by a varIofy of nIfrafIng agonfs. Though a mIxfuro of
conconfrafod nIfrIc acId and conconfrafod suIfurIc acId Is froquonfIy ompIoyod.
MochanIsfIcaIIy a nIfronIum Ion ( )
+
2
ÞO Is fIrsf producod form nIfrIc acId and suIfurIc
acId whIch affacks fho aromafIc rIng as oufIInod In fho foIIowIng sfops:
Procedure: Tako a 200 mI round-boffomod fIask fIffod wIfh a cork hoIdIng a fhormomofor
tfho buIb oxfonds fo fho boffom of fho fIask) and a gIass fubo taIr-condonsor) abouf 30
Inchos Iong. PIaco 16 mI of conc. nIfrIc acId tJ 1.42) and 17 mI of conc. suIfurIc acId tJ 1.84)
and cooI fho nIfrafIng mIxfuro In coId wafor. To fhIs mIxfuro add dropwIso wIfh consfanf
shakIng 15 mI t13 g) of bonzono. ÐurIng fho addIfIon fho fomporafuro shouId nof rIso abovo
60
o
C tNofo I). CooI fho fIask In a bafh of Ico-coId wafor If nocossary. Affor fho addIfIon Is
compIofo ropIaco fho condonsor and warm fho fIask on a wafor-bafh for 50 mIn maInfaInIng
a fomporafuro bofwoon 50÷60
o
C. Shako fho fIask occasIonaIIy. CooI and pour fho confonfs
In a boakor confaInIng 100 mI of wafor. Transfor fho mIxfuro fo a smaII soparafory funnoI,
ORGANIC PREPARATIONS 177
and shako. Savo fho Iowor organIc Iayor and dIscard fho uppor aquoous phaso. Wash fho
organIc Iayor fwIco wIfh 60 mI porfIons of wafor foIIowod by 15 mI of 1 M sodIum hydroxIdo
soIufIon and agaIn wIfh wafor fo romovo oxcoss nIfrIc acId. Tako fho organIc Iayor In an
ÐrIonmoyor fIask and shako wIfh anhydrous caIcIum chIorIdo fo dry nIfrobonzono and fIIfor
In a 50 mI dIsfIIIafIon fIask. ÐIsfII usIng an aIr-condonsor and coIIocf fho fracfIon boIIIng
bofwoon 206÷210
o
C tNofo II). NIfrobonzono Is obfaInod as a cIoar paIo yoIIow IIquId yIoId,
15-16 g.
Notes ¡: If fho fomporafuro Is aIIowod fo rIso abovo fhIs IImIf fhon dInIfrafIon of bonzono fakos
pIaco.
¡¡: Ðo nof dIsfII fo drynoss as fho brown mass consIsfIng of n-dInIfrobonzono and hIghor
nIfro compounds may docomposo and causo oxpIosIon.
Questions
8.1 Why shouId fho fomporafuro nof rIso abovo 60
o
C7
8.2 Whaf wIII happon If fho fomporafuro Is Ioworod fo 10
o
C7
8.3 How wIII fho absonco of suIfurIc acId InfIuonco fho rafo of nIfrafIon7
Calculation of percentage yield of a product
Ono way fo doformIno fho succoss of a synfhofIc procoss Is fo chock fho yIoId of fho producf
and purIfy. Tho yIoId Is gonoraIIy oxprossod as fho porconfago yIoId.
Percentage yield = 100
yIoId I ThoorofIcu
producf puro fho of yIoId AcfuuI
×
!suaIIy, aII buf ono of fho roacfanfs aro prosonf In oxcoss of fho sfoIchIomofrIc amounfs
In a proparafIon. Tho porconfago yIoId Is caIcuIafod horo by consIdorIng fho abovo nIfrafIon
oxporImonf. In fhIs caso nIfrIc acId and suIfurIc acId aro prosonf In oxcoss, fhoroforo,
caIcuIafIon Is mado on fho basIs of bonzono aIono. !rom fho oquafIon If Is ovIdonf fhaf
fhoorofIcaIIy 78 g bonzono wouId yIoId 123 g of nIfrobonzono. !sIng 13 g of bonzono, fho
fhoorofIcaI yIoId wouId bo
×
=
13 125
20.5 g.
78
.
Tho acfuaI yIoId obfaInod Is 16 g.
Thus fho porconfago yIoId Is oquaI fo
3 . 77 100
5 . 20
16
= ×
178 LABORATORY MANUAL OF ORGANIC CHEMISTRY
YIoIds aro obfaInod froquonfIy In fho rango of 55÷80% and aro consIdorod safIsfacfory.
In a proparafIon a yIoId of 100% In ImpossIbIo fo obfaIn bocauso Iosos occur durIng work-up.
Howovor, yIoIds of >99% aro roporfod as quanfIfafIvo.
8.1.2 Preparation of o- and p-Nitrophenols
Somo subsfancos, such as phonoI, may bo nIfrafod roadIIy ovon wIfh dIIufo nIfrIc acId In
aquoous soIufIon. In ofhor casos, acofIc acId, acofIc anhydrIdo or somo ofhor soIvonf Is
ompIoyod.
Tho nIfrafIon Is facIIIfafod undor mIId condIfIons bocauso phonoI confaIns a sfrong
acfIvafIng hydroxyI group and dIIufo nIfrIc acId Is suffIcIonf fo Infroduco fho nIfro group.
Tho fomporafuro shouId bo confroIIod ofhorwIso farry oxIdafIon producfs aro formod.
Procedure: In a 250 mI boIf-hoad fIask, mIx 18 mI of conc. suIfurIc acId wIfh 55 mI of wafor
tNofo I). ÐIssoIvo 20 g sodIum nIfrafo In fhIs soIufIon and cooI In a coId wafor-bafh. In a
droppIng funnoI mIx 12.5 g of moIfod phonoI wIfh 2.5 mI wafor fo form an omuIsIon. Add
fhIs omuIsIon fo fho abovo soIufIon wIfh consfanf sfIrrIng af such a rafo fhaf fho fomporafuro
doos nof rIso abovo 20
o
C. Affor fho addIfIon Is compIofo, Ioavo fho mIxfuro af room
fomporafuro for 1 hr shakIng occasIonaIIy. Thon add 50 mI of wafor, shako woII and aIIow
fo sfand. Ðocanf fho aquoous Iayor and dIscard If. Ropoaf fhIs procoss of washIng 2÷3 fImos
wIfh wafor fo onsuro fho romovaI of fho acId. Af fhIs sfago a crudo mIxfuro of o- and p-
nIfrophonoIs Is obfaInod.
Separation of the isomers
Tho fwo Isomors aro soparafod by sfoam dIsfIIIafIon. Tho ortho-Isomor Is moro voIafIIo and
Ioss soIubIo duo fo H-bondIng, whIIo fho para-Isomor Is Ioss voIafIIo and moro soIubIo.
To fho abovo rosIduo add 50 mI of wafor and sfoam dIsfII fho mIxfuro whoroby
o-nIfrophonoI passos ovor. Tho dIsfIIIafIon Is consIdorod compIofo whon fho soIIdIfIcafIon of
phonoI Is no Iongor obsorvod In fho condonsor. CooI fho dIsfIIIafo, o-nIfrophonoI soIIdIfIos
In fho rocoIvIng fIask. !IIfor fho soIId af fho pump on a Buchnor funnoI and dry In a
dosIccafor. Tho yIoId of o-nIfrophonoI Is 3.9 g, m.p. 46
o
C.
CooI fho rosIduo In fho dIsfIIIafIon fIask In an Ico-bafh for 20 mIn, and p-nIfrophonoI
soIIdIfIos. !IIfor fho soIId on a Buchnor funnoI and wash wIfh wafor. Transfor fho soIId fo a
boakor and boII wIfh 150 mI of 2% hydrochIorIc acId and 0.4 g of acfIvafod charcoaI. !IIfor
ORGANIC PREPARATIONS 179
fho hof soIufIon and aIIow fho fIIfrafo fo crysfaIIIzo. CoIorIoss crysfaIs of p-nIfrophonoI aro
obfaInod. Tho yIoId Is 2.6 g, m.p. 112
o
C.
Note ¡: AcId shouId bo addod fo wafor vory sIowIy. Insfoad 21 mI of conc. nIfrIc acId and 51 mI of
wafor may bo usod.
Questions
8.4 Why doos o-nIfrophonoI dIsfII ovor buf nof fho p-Isomor7
8.5 WhIch of fho fwo Isomors Is moro soIubIo In wafor and why7
8.1.3 Preparation of 2, 4, 6-Tribromoaniline (Bromination)
SImIIar fo fho hydroxy group, an amIno group Is a poworfuI acfIvafIng group of bonzono
rIng In an oIocfrophIIIc subsfIfufIon roacfIon. If Is froquonfIy dIffIcuIf fo provonf oxfonsIvo
subsfIfufIon In fho acfIvafod rIng. !or Insfanco, whon anIIIno Is froafod wIfh bromIno In
gIacIaI acofIc acId af room fomporafuro, fho onIy IsoIafod producf Is 2, 4, 6-frIbromoanIIIno
Procedure: In a 100 mI ÐrIonmoyor fIask dIssoIvo 2.5 g dIsfIIIod anIIIno In 10 g gIacIaI
acofIc acId. To fhIs add dropwIso a soIufIon of 13.5 g t4.2 mI) of bromIno dIssoIvod In 10 mI
gIacIaI acofIc acId tNofo I) wIfh consfanf shakIng In a rofafory mofIon. SInco fho roacfIon Is
oxofhormIc, cooI fho fIask In coId wafor durIng addIfIon. Affor fho addIfIon Is compIofo add
50 mI wafor fo fho fIask. !IIfor fho yoIIow soIId and dry fIrsf bofwoon fho foIds of fIIfor
papors and fhon In aIr. Tho yIoId Is 4.3 g, m.p. 120
o
C.
Note ¡: ThIs proparafIon shouId bo carrIod ouf In a good vonfIIafod hood bocauso bromIno Is an
oxfromoIy unpIoasanf chomIcaI.
Question
8.6 Why doos poIybromInafIon fako pIaco In anIIIno7 How can If bo confroIIod7
8.1.4 Preparation of Picric Acid (2, 4, 6-Trinitrophenol)
PIcrIc acId Is usod for fho proparafIon of moIocuIar compIoxos, i.c., pIcrafos. If can bo
proparod sfarfIng from phonoI by consocufIvo suIfonafIon and nIfrafIon procoduros.
180 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: PIaco 7.5 g of phonoI and 20 mI of conc. suIfurIc acId In a dry round-boffomod
fIask. Shako fho mIxfuro and hoaf on a wafor-bafh for 30 mIn. ÐurIng fhIs porIod a cIoar
soIufIon of o- and p-phonoIsuIfonIc acIds aro obfaInod. CooI fho fIask In an Ico-bafh. Now
add 22 mI of conc. nIfrIc acId dropwIso wIfh consfanf shakIng. An oxofhormIc roacfIon fakos
pIaco and copIous rod fumos toxIdos of nIfrogon) aro ovoIvod and fho IIquId bocomos doop
rod In coIor. Hoaf fho fIask In a wafor-bafh t80÷100
o
C) for 2 hrs wIfh occasIonaI shakIng.
CooI fho mIxfuro and pour If carofuIIy Info abouf 100 mI of coId wafor. !IIfor fho soIId on a
Buchnor funnoI and wash fhoroughIy wIfh coId wafor. RocrysfaIIIzo fho crudo pIcrIc acId
from hof aquoous aIcohoI, yIoId 11.5 g., m.p. 122°C.
8.1.5 Relative Rates of Electrophilic Aromatic Substitution
Tho subjocf of oIocfrophIIIc subsfIfufIon Is dIscussod In aII organIc chomIsfry foxfbooks.
Tho omphasIs Is IaId moro on fho orIonfafIon corrospondIng fo subsfIfuonf aIroady occupyIng
a posIfIon on fho aromafIc rIng. OnIy quaIIfafIvo sfafomonfs aro mado abouf fho roIafIvo
roacfIvIfy of varIous fypos of compounds. An osfImafIon of fho roIafIvo rafos wIII bo mado
horo by rafo comparIson aIso In a quaIIfafIvo mannor.
Procedure: Tho procoduro Is dosIgnod for a cIass of 10 sfudonfs. Tho Idoa Is fo sfudy fho
rafo of bromInafIon for a group of aromafIc compounds. Thoso compounds may bo dIvIdod
Info fwo groups. !Irsf proparo fho foIIowIng soIufIons:
ÐIssoIvo 2 g bromIno In 250 mI of 90% acofIc acId fo obfaIn a 0.05 M bromIno soIufIon
and uso fhIs as sfock soIufIon. ÐIssoIvo soparafoIy 1.56 g bonzono In 100 mI ofhyI acofafo
and In soparafo confaInors dIssoIvo phonoI t2 g), bonzoIc acId t1.2 g), mofhyI bonzoafo
t2.72 g), chIorobonzono t1.0 g), foIuono t1.0 g), p-xyIono t1.0 g), nIfrobonzono t1.2 g),
oach In abouf 50 mI of ofhyI acofafo fo gIvo a 0.2 M soIufIon. Now pIaco fIvo cIoan 2 × 15
mm fosf fubos on a fosf fubo sfand. Add 2 mI of oach soIufIon tgroup A) In oach fosf fubo
tNofo I) and 2 mI of bromIno soIufIon In oach fubo from a buroffo. Nofo fho fImo of addIfIon
In oach caso. Shako fho fubos for a fow soconds and fhon puf fhom on fho sfand tNofo II).
Rocord fho fImo for fho Ioss of bromIno coIor In oach fosf fubo tNofo III). ÐIscard fho
soIufIon In fho sInk tfumo hood), wash wIfh a smaII quanfIfy of acofono and dry. Ropoaf fho
oxporImonf wIfh fho socond group of compounds tgroup B) usIng fho samo voIumos of
roagonfs foIIowod by bromIno soIufIon. AgaIn nofo fho fImo for fho docoIorIzafIon of bromIno
coIor. Rocord fho rosuIfs In a fabuIar form.
ORGANIC PREPARATIONS 181
0.2 M compound 0.05 M bromlne Tlme Ior
solutlon used solutlon used decolorlzutlon
GroupA
C
6
H
6
2 mI 2 mI
C
6
H
5
OH 2 mI 2 mI
C
6
H
6
OCH
3
2 mI 2 mI
C
6
H
5
COOCH
3
2 mI 2 mI
C
6
H
5
COOH 2 mI 2 mI
Group B
C
6
H
6
2 mI 2 mI
C
6
H
5
CI 2 mI 2 mI
C
6
H
5
CH
3
2 mI 2 mI
2 mI 2 mI
C
6
H
5
NO
2
2 mI 2 mI
By a comparIson of fImo If wIII bo nofIcod fhaf fho coIor dIsppoars fasfor In caso of
compounds boarIng oIocfron-donafIng groups.
Notes ¡: !so a pIpoffo fIffod wIfh a rubbor sucfIon buIb.
¡¡: AvoId oxposuro of fubos fo sunIIghf.
¡¡¡: Tho roacfIon Is consIdorod fo bo compIofo whon fho soIufIon affaIns a vory paIo yoIIow
coIor.
¡V: Ðo nof spIII bromIno. If Is a hazardous chomIcaI.
Questions
8.7 Why Is chIorobonzono Ioss roacfIvo fhan bonzono In oIocfrophIIIc subsfIfufIon7
8.8 LIsf fIvo common oIocfrophIIIc subsfIfufIon roacfIons as appIIod fo aromafIc
compounds.
8.1.6 The Friedel-Crafts Reaction
Tho !rIodoI-Craffs roacfIon Is ono of fho mosf gonoraI aromafIc oIocfrophIIIc subsfIfufIon
roacfIons for fho proparafIon of aIkyI and acyI dorIvafIvos of bonzono. If Is carrIod ouf by
usIng a LowIs acId such as anhydrous aIumInum chIorIdo as a cafaIysf. An Inorf soIvonf
182 LABORATORY MANUAL OF ORGANIC CHEMISTRY
such as nIfrobonzono, carbon dIsuIfIdo, ofc. may bo ompIoyod If noodod. Howovor, If fho
aromafIc compound Is an InoxponsIvo IIquId hydrocarbon, for oxampIo, bonzono If Is usod
bofh as a roacfanf and a soIvonf.
8.1.6(a) Preparation of o-Benzoylbenzoic Acid (The Friedel-Crafts Reaction)
In fho foIIowIng proparafIon, bonzono and phfhaIIc anhydrIdo In fho prosonco of aIumInum
chIorIdo aro usod. Tho roacfIon procoods wIfh fho formafIon of a roacfIvo acyIIum Ion. Af
Ioasf fwo moIar oquIvaIonfs of anhydrous aIumInum chIorIdo bo usod bocauso fho cafaIysf
coordInafos bofh wIfh fho roacfanf and fho producf.
Procedure: In a 250 mI round-boffomod fIask fIffod wIfh a wafor condonsor and dryIng
fubo fo fho fop of fho condonsor pIaco 5 g phfhaIIc anhydrIdo and 25 mI fhIophono-froo
bonzono tNofo I). Thon add 10 g anhydrous aIumInum chIorIdo tNofo II) and shako
vIgorousIy. An oxofhormIc roacfIon usuaIIy commoncos af fhIs sfago wIfh fho ovoIufIon of
hydrochIorIc acId gas. A gas frap Is affachod fo fho fop of fho dryIng fubo. Affor fho InIfIaI
roacfIon has subsIdod, hoaf fho fIask undor rofIux In a boIIIng wafor-bafh carofuIIy for
20 mIn wIfh froquonf shakIng. CooI fho fIask In an Ico-bafh af fho ond of hoafIng and add 40
g of crushod Ico In smaII Iofs wIfh consfanf shakIng. Now add 50 mI of wafor and 7 mI conc.
hydrochIorIc acId fo hydroIyso fho addIfIon compIox tNofo III). Romovo oxcoss bonzono by
sfoam dIsfIIIafIon. Transfor fho romaInIng soIId fo a boakor and aIIow If fo cooI In Ico-bafh.
!IIfor fho acId on a Buchnor funnoI af fho pump and wash wIfh coId wafor. ÐIssoIvo fho
soIId In 40 mI of 10% aquoous sodIum carbonafo soIufIon and fIIfor agaIn fo romovo InsoIubIo
aIumInum hydroxIdo. AcIdIfy fho fIIfrafo wIfh conc. hydrochIorIc acId sfIrrIng wIfh a gIass
rod. Tho acId soparafos ouf as a soIId. !IIfor and dry In aIr.
Tho acId obfaInod abovo usuaIIy has a Iow moIfIng poInf tapprox. 94
o
C). Tho puro
anhydrous acId can bo proparod by dIssoIvIng If In 40 mI of bonzono In a round-boffomod
fIask and hoafIng for 15 mIn. Transfor fo a soparafory funnoI and romovo fho wafor Iayor.
Conconfrafo fho bonzono soIufIon fo haIf Ifs voIumo and procIpIfafo fho acId by addIng
pofroIoum ofhor, sImuIfanoousIy cooIIng If In an Ico-bafh. !IIfor fho soIId and dry In a
vacuum dosIccafor. Tho yIoId of fho puro acId Is 6.51 g, m.p. 128
o
C.
Notes ¡: ThIophono-froo bonzono can bo proparod by shakIng commorcIaI bonzono wIfh conc. suIfurIc
acId sovoraI fImos In a soparafory funnoI, subsoquonfIy washIng wIfh wafor and dIsfIIIIng
affor dryIng ovor anhyd. caIcIum chIorIdo.
ORGANIC PREPARATIONS 183
¡¡: WoIgh anhyd. aIumInum chIorIdo In a sfopporod boffIo as roadIIy as possIbIo.
¡¡¡: Koop fho confonfs of fho fIask af room fomporafuro.
Question
8.9 Whaf Is fho prIncIpIo InvoIvod In fho proparafIon of fhIophono-froo bonzono by washIng
wIfh conc. suIfurIc acId7
8.1.6(b) Preparation of Diphenylmethane (The Friedel-Crafts Reaction)
In fho prosonco of LowIs acId cafaIysf such as aIumInum chIorIdo, aIkyI haIIdos aIkyIafo
bonzono fo gIvo aIkyIbonzono. Tho foIIowIng oxporImonf Is an oxampIo of bonzyIafIon of
bonzono by fho !rIodoI-Craffs roacfIon.
Tho mochanIsm of fho roacfIon procoods In fho foIIowIng sfops:
Procedure: In a 250 mI round-boffomod fIask, pIaco 19.3 g dIsfIIIod bonzyI chIorIdo and
75 mI sodIum-dry bonzono. !If fho fIask wIfh a wafor condonsor, and a gas frap for coIIocfIng
hydrochIorIc acId gas ovoIvod In fho roacfIon Is connocfod fo fho fop of fho condonsor wIfh
fho hoIp of a rubbor fubIng. In a sfopporod boffIo woIgh 6 g of anhyd. aIumInum chIorIdo
tNofo I). Immorso fho fIask In an Ico-bafh. Add abouf 1 g of aIumInum chIorIdo fhrough fho
condonsor and shako. An oxofhormIc roacfIon commoncos wIfh fho ovoIufIon of hydrochIorIc
acId gas. Whon fho roacfIon has subsIdod add anofhor 1 g porfIon of aIumInum chIorIdo.
Ropoaf fho addIfIon and shako. Koop fho fIask woII cooIod. Affor fho addIfIon Is compIofo,
184 LABORATORY MANUAL OF ORGANIC CHEMISTRY
rofIux fho confonfs of fho fIask for 20 mIn on a boIIIng wafor-bafh. AIIow fo cooI, add 50 g of
crushod Ico and 50 mI wafor fo fho fIask and shako. Transfor fho mIxfuro fo a soparafory
funnoI. ÐIscard fho Iowor aquoous Iayor. Wash fho bonzono Iayor wIfh 10% hydrochIorIc
acId foIIowod by wafor. Ðry fho bonzono soIufIon ovor anhydrous caIcIum chIorIdo. Tho
drIod IIquId Is fIIforod Info a dIsfIIIIng fIask and dIsfIIIod fo romovo bonzono. ÐIsfII fho
rosIduo usIng an aIr condonsor and coIIocf dIphonyImofhano bofwoon 250÷275
o
C tb.p. of
puro dIphonyImofhano Is 262
o
C). Tho yIoId Is 14.0 g.
Note ¡: !suaIIy an oxcoss of anhydrous aIumInum chIorIdo In usod.
Question
8.10 Whaf aro fho IImIfafIons of fho !rIodoI-Craffs aIkyIafIon7
8.1.6(c) Preparation of >-Benzoylpropionic Acid (The Friedel-Crafts Reaction)
SuccInIc anhydrIdo Is ompIoyod wIfh a Iargo oxcoss of bonzono undor fho !rIodoI-Craffs
condIfIons.
Procedure: !If a 250 mI dry round-boffomod fIask wIfh a rofIux condonsor and a dryIng
fubo af fho fop of If. Chargo fho fIask wIfh 4.2 g of succInIc anhydrIdo and 25 mI dry bonzono.
Supporf fho fIask ovor a wafor-bafh In fho fumo cupboard tNofo I) and add accurafoIy
woIghod tNofo II) 12.5 g powdorod anhyd. aIumInum chIorIdo In ono porfIon. !Irsf cooI fho
mIxfuro. Affor fho oxofhormIc roacfIon coasos ropIaco fho condonsor ImmodIafoIy and hoaf
fho fIask for 30 mIn. Shako froquonfIy durIng fhIs porIod. If an unconfroIIabIo roacfIon
occurs durIng hoafIng, cooI fho fIask In a bafh of coId wafor agaIn. Pour fho coId mIxfuro In
a 250 mI boakor and Immorso If In Ico. To fhIs add sIowIy wIfh consfanf sfIrrIng 20 mI of
50% hydrochIorIc acId. !IIfor fho soIId on a Buchnor funnoI af fho pump wash fho soIId wIfh
10 mI coId dII. hydrochIorIc acId foIIowod by coId wafor. ÐIssoIvo fho crudo producf so
obfaInod In sodIum carbonafo soIufIon t5 g of sodIum carbonafo dIssoIvod In 30 mI of wafor)
by boIIIng. Broak fho Iumps wIfh a gIass rod. !IIfor fho soIufIon and cooI. AcIdIfy fho coId
fIIfrafo wIfh 13 mI of conc. hydrochIorIc acId. !IIfor fho soIId, wash wIfh coId wafor and dry.
Tho yIoId Is 7.0 g, m.p. 115
o
C.
Notes ¡: Bocauso hydrochIorIc acId gas Is ovoIvod.
¡¡: WoIgh anhyd. aIumInum chIorIdo In a dry woIghIng boffIo.
ORGANIC PREPARATIONS 185
8.1.6(d) Preparation of p-Xylene-2-Sulfonic Acid
p-XyIono Is roadIIy suIfonafod fo yIoId suIfonIc acId. SInco aII fho four ortho posIfIons aro
IdonfIcaI onIy a sIngIo suIfonafod producf Is obfaInod.
Procedure: PIaco 5 g t6 mI) of xyIono In a 100 mI round-boffomod fIask. WIfh gonfIo
sfIrrIng add carofuIIy 10 mI of conc. suIfurIc acId. Hoaf fho mIxfuro for 10÷15 mIn on a
wafor-bafh. Romovo fho fIask and shako fIII fho Iayor of p-xyIono on fho surfaco has
dIsappoarod. CooI fho fIask af room fomporafuro and fo If add 50 mI of wafor and fhon
Immorso fho fIask In Ico fIII a soIId appoars. !IIfor fho crysfaIIIno acId on a Buchnor funnoI.
RocrysfaIIIzo from a smaII quanfIfy of boIIIng wafor and dry. Tho yIoId Is 8.2 g, m.p. 82
o
C.
8.2 THE DIELS-ALDER REACTION
If Is an Imporfanf roacfIon for fho proparafIon of cycIIc compounds. In fhIs roacfIon a
conjugafod dIono unIfos wIfh an unsafurafod compound tcaIIod fho dIonophIIo).
Tho ÐIoIs-AIdor roacfIon In an oxampIo of cycIoaddIfIon roacfIon, i.c., a roacfIon whIch
Ioads fo fho formafIon of a rIng. Tho roacfIon In froquonfIy carrIod ouf fhormaIIy buf In
somo casos can bo achIovod In fho prosonco of a LowIs acId.
8.2.1 Preparation of 9, 10-Dihydroanthracene-9 10-=, >-Succinic Anhydride
(The Diels-Alder Reaction)
Anfhracono and maIoIc anhydrIdo roacf on hoafIng fo form fho fIfIo compound.
Procedure: PIaco 3 g of puro anfhracono, 30 mI of dry xyIono tNofo I) and 1.5 g of maIoIc
anhydrIdo In a 100 mI dry round-boffomod fIask. Affach a wafor condonsor and rofIux fho
186 LABORATORY MANUAL OF ORGANIC CHEMISTRY
confonfs on a wafor-bafh for 25 mIn wIfh froquonf shakIng. CooI fho mIxfuro and coIIocf
fho soIId on a Buchnor funnoI. RocrysfaIIIzo fho adducf from ofhyI acofafo. Tho yIoId Is 3.3
g, m.p. 262÷263
o
C.
Note ¡ : Ðry bonzono may bo usod buf fho rofIuxIng fImo shouId bo Incroasod. Tho yIoId In fhIs
soIvonf may aIso bo Iow.
Question
8.11 WrIfo fho sfrucfuro of fho ÐIoIs-AIdor producf bofwoon cycIoponfadIono and
bonzoquInono.
8.3 THE BECKMANN REARRANGEMENT
Tho roarrangomonf of a kofoxImo fo an amIdo undor fho cafaIyfIc acfIon of a sfrong acId or
fhIonyI chIorIdo Is known as fho Beckmunn reurrungement.
Tho roacfIon procoods accordIng fo fho foIIowIng mochanIsm:
8.3.1 Preparation of Benzanilide
ThIs proparafIon Is accompIIshod In fho foIIowIng fwo sfops:
Step A: PrepuruIion oj benzophenone oxime
Tho kofo oxImo Is fIrsf proparod by a roacfIon bofwoon bonzophonono and
hydroxyIamIno hydrochIorIdo.
ORGANIC PREPARATIONS 187
Procedure: ÐIssoIvo 3.6 g bonzophonono and 4 g of hydroxyIamIno hydrochIorIdo
tNH
2
OH.HCI) In a 100 mI round-boffomod fIask In 50 mI ofhanoI. Add 35 mI wafor and
shako fho mIxfuro. To fhIs soIufIon add 4 g sodIum hydroxIdo poIIofs In smaII porfIons wIfh
consfanf swIrIIng tNofo I). Affor fho addIfIon Is compIofo affach a rofIux condonsor fo fho
fIask and rofIux fho mIxfuro gonfIy for 40 mIn. CooI and pour fho confonfs In a boakor
confaInIng 200 mI of coId wafor. !IIfor fo romovo any unchangod bonzophonono. AcIdIfy fho
fIIfrafo wIfh dII. suIfurIc acId fo procIpIfafo fho oxImo. !IIfor fho soIId on a Buchnor funnoI
and wash sovoraI fImos wIfh coId wafor and dry fho soIId In fho ovon af 70÷80
o
C.
RocrysfaIIIzo from ofhanoI. Tho yIoId Is 3.7 g, m.p. 142
o
C.
Step B: PrepuruIion oj benzuniIiJe
Procedure: In an ÐrIonmoyor fIask, dIssoIvo 3 g of bonzophonono oxImo In 30 mI dry ofhor
Nofo tII). To fhIs add 4 mI of fhIonyI chIorIdo or a fow drops of conc. suIfurIc acId or 4 g of
phosphorus ponfachIorIdo. Shako fho mIxfuro for 15 mIn. Romovo ofhor on a wafor-bafh
NofotIII). CooI fho rosIduo and add 35 mI wafor. BoII for 10÷5 mIn. Ðocanf fho supornafanf
IIquId and rocrysfaIIIzo fho romaInIng soIId from hof ofhanoI. Tho yIoId Is 2.4 g, m.p. 162
o
C.
Notes ¡ : If fho roacfIon bocomos foo vIgorous cooI fho fIask undor fho fap.
¡¡ : BoII off ofhor on a wafor-bafh In a fumo hood.
¡¡¡ : OnIy sodIum dry ofhor shouId bo usod.
8.4 THE PERKIN REACTION
Tho PorkIn roacfIon Is usod for fho proparafIon of unsafurafod compounds, parfIcuIarIy
unsafurafod carboxyIIc acIds. In fhIs roacfIon an aromafIc aIdohydo Is condonsod wIfh acId
anhydrIdo In fho prosonco of sodIum or pofassIum saIf whIch funcfIons as a cafaIysf.
8.4.1 Preparation of Cinnamic Acid
BonzaIdohydo Is condonsod wIfh acofIc anhydrIdo In fho prosonco of pofassIum acofafo,
foIIowod by hydroIysIs. ThIs roacfIon Is usofuI for fho proparafIon of unsafurafod carboxyIIc
acIds.
Procedure: PIaco 10.5 g t10 mI) of bonzaIdohydo, 14 mI of acofIc anhydrIdo and 6 g of
froshIy fusod sodIum acofafo tNofo I) In a 200 mI round-boffomod fIask. RofIux fho mIxfuro
188 LABORATORY MANUAL OF ORGANIC CHEMISTRY
In an oII-bafh af 170÷180
o
C for 90 mIn. !oamIng occurs InIfIaIIy bocauso of fho ovoIufIon of
carbon dIoxIdo. CooI fho fIask and add 75 mI of wafor foIIowod by fho addIfIon of 10% sodIum
hydroxIdo soIufIon fIII aIkaIIno. Ðxfracf fho cIoar soIufIon wIfh fwo 35 mI porfIons of ofhor
fo romovo any unchangod bonzaIdohydo. AcIdIfy fho aquoous Iayor wIfh conc. hydrochIorIc
acId unfII no moro carbon dIoxIdo ovoIvos. !IIfor off fho procIpIfafod soIId on a Buchnor
funnoI af fho pump, wash wIfh wafor and rocrysfaIIIzo from hof wafor. Tho yIoId Is 8.5 g,
m.p. 133
o
C.
Note ¡: Ðo nof uso sodIum hydroxIdo a sfrong baso, ofhorwIso fho CannIzzaro roacfIon wIII fako
pIaco.
8.5 THE CANNIZZARO REACTION
Tho PorkIn roacfIon Is a baso-cafaIyzod oxIdafIon-roducfIon roacfIon. In fhIs roacfIon an
aIdohydo havIng no =-hydrogon Is froafod wIfh acofIc anhydrIdo In fho prosonco of pofassIum
hydroxIdo whIch acfs as a cafaIysf. If fwo moIos of bonzaIdohydo aro fakon, ono moIo Is
oxIdIzod fo acId and fho ofhor Is roducod fo an aIcohoI. If Is a roacfIon offon usod for fho
proparafIon of bonzyI aIcohoI. BonzoIc acId prosonf as Ifs sodIum saIf Is soIubIo In wafor.
BonzyI aIcohoI Is InsoIubIo In wafor and fhus can bo oasIIy soparafod from fho mIxfuro.
8.5.1 Base-Catalyzed Oxidation-Reduction of Benzaldehyde
AromafIc aIdohydos aro fho mosf common fypo of compounds whIch undorgo fho CannIzzaro
roacfIon. BonzaIdohydo In fho prosonco of a sfrong baso forms bonzyI aIcohoI and bonzoIc
acId.
Proceduce: In a 200 mI round-boffomod fIask dIssoIvo 12.5 g of pofassIum hydroxIdo poIIofs
In 65 mI wafor. To fho soIufIon add 21.1 g t20 mI) of dIsfIIIod bonzaIdohydo. Affach a
condonsor and rofIux fho mIxfuro for 1 hr. CooI fho fIask and add jusf suffIcIonf wafor fo
dIssoIvo any procIpIfafod sodIum bonzoafo. Transfor fho mIxfuro fo a soparafory funnoI and
oxfracf fhrIco wIfh 25 mI porfIons of ofhor. Savo fho Iowor aquoous Iayor. Wash fho combInod
ofhor oxfracfs wIfh aquoous sodIum bIsuIfIfo t20%) soIufIon fo romovo unchangod
bonzaIdohydo. Now wash wIfh wafor and dry fho ofhoroaI soIufIon tMgSO
4
). Romovo ofhor
In fho hood on a hof pIafo and dIsfII fho rosIduo and coIIocf bonzyI aIcohoI af 204÷207°C.
Tho yIoId Is 5.9 g.
Tako 30 mI conc. hydrochIorIc acId, 30 mI wafor and abouf 60 g crushod Ico In a 400 mI
boakor. Pour fho abovo aquoous soIufIon sIowIy Info fho acId, sfIrrIng If consfanfIy. Tho
acId procIpIfafos. !IIfor off fho soIId bonzoIc acId on a Buchnor funnoI af fho pump and
wash wIfh coId wafor. RocrysfaIIIzo from boIIIng wafor. Tho yIoId Is 8.8 g, m.p. 121°C.
ORGANIC PREPARATIONS 189
Questions
8.12 By whaf mochanIsm wouId sodIum bIsuIfIfo romovo unchangod bonzaIdohydo from fho
roacfIon mIxfuro7
8.13 WrIfo an oquafIon for fho roacfIon of a mIxfuro of bonzaIdohydo and formaIdohydo
wIfh conc. sodIum hydroxIdo soIufIon.
8.6 THE FRIES REARRANGEMENT
Tho roarrangomonf of phonoIIc osfors In fho prosonco of anhydrous aIumInum chIorIdo on
hoafIng Info IsomorIc hydroxy kofonos Is caIIod fho Frles reurrungement. PhonyI croafafo
undor fhoso condIfIons Is convorfod Info 2- and 4- hydroxyacofophononos. Tho mIxfuro can
bo soparafod by sfoam dIsfIIIafIon.
8.6.1 Preparation of 2, 5-Dihydroxyacetophenone
ThIs proparafIon wIII bo carrIod ouf In fwo sfops:
Step A: PrepuruIion oj hyJroguinone JiuceIuIe
Procedure: PIaco 5.5 g of hydroquInono and 10 g of froshIy dIsfIIIod acofIc anhydrIdo In a
100 mI dry ÐrIonmoyor fIask. Add 2 drops of conc. suIfurIc acId. Shako fho fIask for 10 mIn.
190 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Pour fho mIxfuro onfo 40 g of Ico, fakon In a boakor. CoIIocf fho soIId on a Buchnor funnoI.
RocrysfaIIIzo from hof aquoous ofhanoI. Tho yIoId Is 9 g, m.p. 122
o
C.
Step B: PrepuruIion oj 2, 5-JihyJroxyuceIophenone
Procedure: In a 100 mI round-boffomod fIask, pIaco 4 g powdorod hydroquInono dIacofafo
woIgh 8.5 g anhyd. aIumInum chIorIdo. GrInd In a posfIo and morfar and ImmodIafoIy add
fo fho fIask. Affach an aIr condonsor fIIIod wIfh a dryIng fubo and hoaf fho fIask bofwoon
115÷120
o
C In an oII-bafh In fho fumo hood for 30 mIn. Affor fhIs durafIon, raIso fho
fomporafuro fo 150
o
C. Whon fho ovoIufIon of hydrochIorIc acId gas commoncos hoaf af fhIs
fomporafuro for 1 hr. CooI fho fIask, add 50 g of crushod Ico and 4 mI conc. hydrochIorIc
acId and swIrI. CoIIocf fho soIId on a Buchnor funnoI and wash If wIfh coId wafor. RocrysfaIIIzo
from aquoous boIIIng ofhanoI. Tho yIoId Is 1.8 g, m.p. 202÷203
o
C.
Question
8.14 ÐIscuss fho mochanIsm of fho !rIos roarrangomonf.
8.7 THE SCHÖTTEN-BAUMANN REACTION
ThIs roacfIon Is usod for fho bonzoyIafIon of aromafIc amInos usIng bonzoyI chIorIdo and
aquoous sodIum hydroxIdo soIufIon. SInco an amIno Is moro soIubIo In acId chIorIdo fhan In
sodIum hydroxIdo, roacfIon occurs proforonfIaIIy bofwoon bonzoyI chIorIdo and fho amIno.
PhonoIs can sImIIarIy bo bonzoyIafod. In fhIs roacfIon fho funcfIon of fho baso Is nof cIoar.
If sooms nof onIy fo noufraIIzo fho hydrochIorId acId fhaf wouId ofhorwIso bo IIborafod, buf
aIso fo cafaIyso fho roacfIon. ThIs roacfIon shouId bo carrIod ouf In fho fumo hood.
8.7.1 Preparation of Benzanilide
!or bonzanIIIdo proparafIon anIIIno Is froafod wIfh bonzoyI chIorIdo In fho prosonco of
sodIum hydroxIdo soIufIon.
Procedure: In a 100 mI ÐrIonmoyor fIask pIaco 2.6 g t2.5 mI) of anIIIno and 25 mI of 10%
aquoous sodIum hydroxIdo soIufIon. To fhIs add 4.3 g t3.5 mI) of bonzoyI chIorIdo In smaII
porfIons wIfh vIgorous shakIng for 1 mIn affor ovory addIfIon. Cork fho fIask and shako
vIgorousIy for 10 mIn. Tho roacfIon Is oxofhormIc and fho fIask bocomos hof. BonzoyI
dorIvafIvo may soparafo ouf as a whIfo powdor whon fho roacfIon Is compIofo tNofos I and
ORGANIC PREPARATIONS 191
II). !IIfor fho soIId on a Buchnor funnoI af fho pump. Wash sovoraI fImos wIfh wafor and
draIn. RocrysfaIIIzo from boIIIng aIcohoI. Tho yIoId Is 4.4 g, m.p. 162
o
C.
Notes ¡: ThIs can bo osfabIIshod whon fho roacfIon mIxfuro no Iongor smoIIs of bonzoyI chIorIdo.
¡¡: Af fhIs poInf mako suro fhaf fho roacfIon mIxfuro Is aIkaIIno.
Question
8.15 Why Is an aromafIc acId chIorIdo Ioss roacfIvo fhan fho aIIphafIc acId chIorIdo In fho
Schöffon-Baumann roacfIon7
8.8 BENZILIC ACID REARRANGEMENT
BonzoIn, an =-hydroxy kofono obfaInod from bonzaIdohydo by fho bonzoIn condonsafIon Is
oxIdIzod by nIfrIc acId fo bonzII, an =, >-dIkofono. ThIs In fho prosonco of pafassIum hydroxIdo
Is convorfod fo bonzIIIc acId and fho roacfIon Is caIIod benzlllc ucld reurrungement. ThIs
roacfIon can bo carrIod ouf by fakIng bonzII.
8.8.1 Preparation of Benzilic Acid
MochanIsfIcaIIy bonzII, proparod from bonzoIn, on rofIuxIng wIfh aquoous aIc. pofassIum
hydroxIdo undorgoos a skoIofaI roarrangomonf fo yIoId bonzIIIc acId accordIng fo fho
foIIowIng soquonco:
Tho CN
÷
Ion Is a spocIfIc cafaIysf for condonsafIon. Tho spocIfIcIfy Is affrIbufod fo
many facfors. Through for many yoars If was boIIovod fhaf onIy cyanIdo Ion can cafaIyzo
fho bonzoIn condonsafIon, howovor, roconfIy fhIamIno hydrochIorIdo tVIfamIn B
1
) has boon
found fo bo an offocfIvo cafaIysf as woII.
192 LABORATORY MANUAL OF ORGANIC CHEMISTRY
ThIs proparafIon InvoIvos fho foIIowIng fhroo sfops. Howovor, fho roacfIon Is froquonfIy
accompIIshod by fakIng bonzIn.
Step A: PrepuruIion oj benzoin
Procedure: In a 200 mI round-boffomod fIask, pIaco 12.5 g bonzaIdohydo, 25 g pofassIum
cyanIdo tNofo I) and add 25 mI ofhyI aIcohoI. RofIux fho mIxfuro for 30 mIn In fho hood.
CooI fho fIask and fIIfor fho crudo bonzoIn on a Buchnor funnoI af fho pump. Wash fhoroughIy
wIfh coId wafor and dry. Tho yIoId of bonzoIn Is 10.5 g, m.p. 137
o
C.
Step B: PrepuruIion oj benziI
Procedure: PIaco 5.0 g bonzoIn and 25 mI conc. nIfrIc acId In a 100 mI round-boffomod
fIask. ÐquIp fho fIask wIfh an aIr condonsor and hoaf on a wafor-bafh for 1 hr or fIII fho
ovoIufIon of fho oxIdos of nIfrogon coasos. Pour fho confonfs of fho fIask In 100 mI of coId
wafor fakon In a boakor. A crysfaIIIno yoIIow mass soparafos ouf. CoIIocf fho soIId on a
Buchnor funnoI and wash fhoroughIy wIfh coId wafor. RocrysfaIIIzo from aIcohoI. Tho yIoId
Is 4.8 g, m.p. 94÷96
o
C.
Step C: PrepuruIion oj benziIic uciJ
Procedure: PIaco 3 g of bonzII In a 100 mI round-boffomod fIask and fo fhIs add a soIufIon
of 3 g of pofassIum hydroxIdo In 10 mI of wafor. AIso add 7 mI of ofhanoI and shako fo obfaIn
a bIuIsh-bIack soIufIon. RopIaco fho wafor condonsor and rofIux fho mIxfuro on a wafor-
bafh for 15 mIn. Transfor fho confonfs fo a ChIna dIsh and cooI If In an Ico-bafh for 30 mIn.
Tho pofassIum saIf of bonzIIIc acId soparafos ouf. !IIfor fho soIId and wash fhoroughIy wIfh
coId wafor. ÐIssoIvo fho saIf In 30 mI wafor and acIdIfy fho soIufIon wIfh conc. hydrochIorIc
acId wIfh consfanf sfIrrIng. A rod-brown procIpIfafo of fho acId Is formod. !IIfor and wash
wIfh coId wafor. RocrysfaIIIzo from boIIIng wafor usIng somo acfIvafod charcoaI. Tho yIoId
Is 3 g, m.p. 150
o
C.
Note ¡: KCN Is a fafaI poIson, If shouId bo handIod carofuIIy and wIsoIy. ThIs roacfIon shouId bo
porformod undor fho sfrIcf suporvIsIon of fho foachor. ThIs proparafIon shouId, profocfIy
bo carrIod ouf by fakIng bonzII.
Question
8.16 WouId aIphafIc aIdohydos undorgo sfop A7
ORGANIC PREPARATIONS 193
8.9 THE REIMER-TIEMANN REACTION
In fhIs roacfIon phonoI Is convorfod fo o- and p-hydroxybonzaIdohydos In fho prosonco of
chIoroform and sodIum hydroxIdo.
8.9.1 Preparation of Salicylaldehyde
An IsomorIc mIxfuro, In whIch saIIcyIaIdohydo Is fho major producf Is obfaInod from phonoI,
chIoroform and sodIum hydroxIdo.
A dIchIorocarbono Is gonorafod InIfIaIIy from chIoroform by fho acfIon of baso whIch
affacks fho bonzono rIng.
Procedure: In a 250 mI round-boffomod fIask fIffod wIfh a wafor condonsor and a
fhormomofor, pIaco 20 g sodIum hydroxIdo and dIssoIvo In 20 mI wafor. To fhIs add a
soIufIon of 6.2 g of froshIy dIsfIIIod phonoI In 7 mI wafor. MIx fho confonfs. Hoaf fho fIask
on a wafor-bafh so fhaf fho fomporafuro romaIns boIow 60÷65
o
C tNofo I). Add 15 g
t10.2 mI) of chIoroform In smaII porfIons ovor a porIod of 10 mIn from a droppIng funnoI
wIfh offIcIonf sfIrrIng. MaInfaIn fho fomporafuro boIow 60÷65
o
C by hoafIng or cooIIng fho
bafh as nocossary. !so a fhormomofor. Hoaf fho mIxfuro on a wafor-bafh for 30 mIn.
Sfoam dIsfII fho mIxfuro fo romovo unroacfod chIoroform. AIIow fho fIask fo cooI and an
194 LABORATORY MANUAL OF ORGANIC CHEMISTRY
orango-rod IIquId romaIns In fho fIask. AcIdIfy If wIfh dII. suIfurIc acId carofuIIy and sfoam
dIsfII fho mIxfuro agaIn unfII no moro oIIy drops of saIIcyIaIdohydo pass ovor. Tho rosIduo
In fho fIask confaIns p-hydroxybonzaIdohydo. Ðxfracf fho dIsfIIIafo wIfh ofhor fwIco fo obfaIn
saIIcyIaIdohydo as woII as somo unroacfod phonoI. Romovo ofhor on a hof wafor-bafh In a
hood and fransfor fho romaInIng IIquId fo a soparafory funnoI and add fwIco fho amounf of
a safurafod soIufIon of sodIum bIsuIfIfo and shako vIgorousIy for 30 mIn. Thon cIamp fho
soparafory funnoI on an Iron-sfand and aIIow If fo sfand for 1 hr. !IIfor fho bIsuIfIfo adducf
on a Buchnor funnoI. Wash If wIfh a IIffIo aIcohoI and fhon wIfh ofhor fo romovo any
phonoI. Tako fho bIsuIfIfo compound In a boakor, add dII. suIfurIc acId and warm on a
wafor-bafh. CooI and oxfracf saIIcyIaIdohydo wIfh ofhor and dIsfII. Tho producf dIsfIIs bofwoon
195÷97
o
C. Tho yIoId Is 2.4 g.
To obfaIn p-hydroxybonzaIdohydo tby-producf) fIIfor fho rosIduo whIIo hof fhrough a
fIIfor papor and cooI. Ðxfracf wIfh ofhor and romovo fho soIvonf on a hof wafor-bafh.
RocrysfaIIIzo fho crudo soIId so obfaInod from boIIIng wafor. Tho yIoId Is 0.55 g, m.p. 116
o
C.
Note ¡: Tho fomporafuro of fho bafh may bo adjusfod by cooIIng or hoafIng as Is doomod ossonfIaI.
8.10 OXIDATION AND REDUCTION
SovoraI fypos of oxIdIzIng and roducIng agonfs aro ompIoyod In organIc synfhosos. ThoIr
uso wIII bo IIIusfrafod In fho proparafIon of somo compounds.
8.10.1 Preparation of Cyclohexanone (Oxidation)
OxIdafIon of sodIum dIchromafo Is a common mofhod for fho oxIdafIon of a socondary aIcohoI
fo kofono. In fhIs proparafIon, cycIohoxanono Is obfaInod by fho oxIdafIon of cycIohoxanoI.
Nasconf oxygon Is fho acfIvo oxIdIzIng opocIos and Is avaIIabIo accordIng fo fho foIIowIng
roacfIons:
Procedure: In a 250 mI ÐrIonmoyor fIask, pIaco 20.5 g Na
2
Cr
2
O
7
.2H
2
O, 100 mI wafor and
add carofuIIy 9.5 mI conc. suIfurIc acId. Shako and cooI fho rosuIfIng orango-rod soIufIon of
chromIc acId fo 15
o
C. In a socond ÐrIonmoyor fIask, fako 10 g of cycIohoxanoI and cooI fhIs
ORGANIC PREPARATIONS 195
aIso fo 15
o
C. !so a fhormomofor. Pour fho dIchromafo soIufIon In ono Iof fo fho fIask
confaInIng cycIohoxanoI. Shako fho fIask vIgorousIy. SInco fho roacfIon Is oxofhormIc and
If fho fomporafuro rIsos abovo 60
o
C, cooI If In an Ico-bafh tNofo I). Whon fho fomporafuro
sfops rIsIng aIIow fho fIask fo sfand for 30 mIn af room fomporafuro. Transfor fho roacfIon
mIxfuro fo a 250 mI round-boffomod fIask, add 100 mI of wafor, a fow pIocos of boIIIng
sfonos and dIsfII wIfhouf usIng a fhormomofor. ÐIsfII fho mIxfuro unfII 70 mI of fho dIsfIIIafo
has coIIocfod. PIaco fho dIsfIIIafo In a soparafory funnoI and shako wIfh a safurafod soIufIon
of sodIum chIorIdo. CoIIocf fho uppor organIc Iayor. Wash fho aquoous Iayor wIfh 20 mI of
ofhor. CombIno fho oxfracf wIfh fho organIc Iayor and dry tNa
2
SO
4
). !IIfor and romovo
ofhor on a wafor-bafh In a hood. ÐIsfIII fho rosIduo and coIIocf fho fracfIon bofwoon
154÷156
o
C. Tho yIoId Is 6.6 g.
Note ¡: Tho fomporafuro shouId nof faII boIow 55
o
C or rIso abovo 60
o
C.
8.10.2 Preparation of p-Nitrobenzoic Acid (Oxidation)
Tho oxIdafIon of foIuono fo bonzoIc acId Is oxfromoIy sIow and cannof bo compIofod In fho
IImIfod Iaborafory porIod. If a nIfro group Is Infroducod af fho para posIfIon, fho oxIdafIon
of fho mofhyI group Is achIovod roadIIy.
Procedure: Chargo a 250 mI round-boffomod fIask wIfh 6.2 g of p-nIfrofoIuono, 17 g of
sodIum dIchromafo tNa
2
Cr
2
O
7
.
2 H
2
O) and 40 mI of wafor. Add 21 mI of conc. suIfurIc acId
dropwIso fo fho fIask shakIng whIIo addIng. An oxofhormIc roacfIon commoncos, cooI fho
fIask undor fho fap from fImo fo fImo. Whon fho addIfIon of fho acId Is compIofo, rofIux fho
mIxfuro gonfIy for 15 mIn on a wIro gauzo. AIIow fho fIask fo cooI fhon pour fho confonfs In
a boakor confaInIng 40 mI of wafor. CoIIocf fho crudo acId on a Buchnor funnoI and wash
fwIco wIfh wafor. Transfor fho soIId from fho funnoI fo a 400 mI boakor and add 20 mI of 5%
suIfurIc acId. ÐIgosf fho confonfs of fho boakor on a wafor-bafh for 20 mIn wIfh froquonf
sfIrrIng wIfh a gIass rod for fho romovaI of chromIum saIf. AIIow fho boakor fo cooI and
fIIfor agaIn. ÐIssoIvo fho acId In 50 mI of 5% sodIum hydroxIdo soIufIon and fIIfor fo romovo
any chromIum hydroxIdo and unchangod p-nIfrofoIuono. Wash fho fIIfrafo on a Buchnor
funnoI fhoroughIy wIfh coId wafor. RocrysfaIIIzo from hof bonzono. Tho yIoId Is 5.2 g, m.p.
237
o
C.
196 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
8.17 WouId If bo possIbIo fo affompf proparafIon of bonzaIdohydo by pormanganafo
oxIdafIon of foIuono7
8.10.3 Preparation of Anthraquinone (Oxidation)
Though bonzono Is vory much rosIsfanf fo oxIdafIon, anfhracono can bo oasIIy oxIdIzod fo
9, 10-anfhraquInono usIng a mIxfuro of sodIum dIchromafo and conc. suIfurIc acId.
Procedure: PIaco 5 g of crysfaIIIzod anfhracono and 50 mI of gIacIaI acofIc acId In a 500 mI
round-boffomod fIask fIffod wIfh a rofIux condonsor. BoII fho soIufIon on a Bunson burnor
and sIowIy add a soIufIon of 13 g sodIum dIchromafo proparod In a mIxfuro of 15 mI wafor
and 5 mI conc. suIfurIc acId. PIaco a droppIng funnoI af fho fop of fho rofIux condonsor
confaInIng 35 mI of gIacIaI acofIc acId, add If dropwIo fo fho fIask ovor a porIod of 15 mIn.
Koop fho fomporafuro of fho roacfIon mIxfuro af fho boIIIng poInf. Affor fho addIfIon Is
compIofo, boII for an addIfIonaI porIod of 20 mIn. CooI fho fIask fo aIIow fho soparafIon of
soIId anfhraquInono. !IIfor and wash fho soIId wIfh 20 mI of 70% soIufIon of acofIc acId and
fhon wIfh coId wafor. RocrysfaIIIzo from dII. acofIc acId. Tho yIoId of anfhraquInono Is 5.2 g,
m.p. 285÷286
o
C.
8.10.4 Preparation of Adipic Acid (Oxidation)
AdIpIc acId Is obfaInod by fho dIrocf oxIdafIon of cycIohoxanoI wIfh conc. nIfrIc acId usod as
an oxIdIzIng agonf. In fhIs roacfIon cycIohoxanoI Is oxIdIzod fo cycIohoxanono InIfIaIIy whIch
Is ImmodIafoIy convorfod fo adIpIc acId.
Procedure: !If a 500 mI fhroo-nockod fIask oquIppod wIfh a smaII droppIng funnoI, a
fhormomofor and an oxIf fubo noodod fo oxIf fho ovoIvod oxIdos of nIfrogon ovor fho surfaco
ORGANIC PREPARATIONS 197
of a 50 mI 10% sodIum hydroxIdo confaInod In a Iargo boffIo. PIaco 20 mI of conc. nIfrIc acId
tJ 1.42) In fho fIask and dIIufo If wIfh 10 mI of wafor. Tako 4 mI of cycIohoxanoI In fho
droppIng funnoI. Hoaf fho dIIufod acId fo abouf 85
o
C and add ono drop of cycIohoxanoI af a
fImo from fho droppIng funnoI. A hIghIy oxofhormIc roacfIon commoncos ImmodIafoIy,
whon fho fomporafuro has faIIon fo 80
o
C, add anofhor drop of cycIohoxanoI tNofo I). Tho
addIfIon of cycIohoxanoI Is usuaIIy compIofo In 15÷20 mIn. !InaIIy warm fho confonfs of fho
fIask fo 99÷100
o
C for 5 mIn and fhon cooI In an Ico-bafh, adIpIc acId crysfaIIIzos ouf. !IIfor
fho adIpIc acId undor sucfIon and wash wIfh coId wafor. RocrysfaIIIzo fho acId from a mInImum
amounf of hof wafor. !IIfor agaIn and wash wIfh coId wafor. Tho yIoId Is 3.1 g, m.p. 152
o
C.
Note ¡: Ðo nof affompf fo add frosh drop of cychIohoxanoI unfII fho provIous ono has roacfod.
Moroovor, do nof aIIow any cycIohoxanoI fo accumuIafo In fho fIask ofhorwIso an aImosf
vIoIonf oxpIosIon may fako pIaco.
8.10.5 Preparation of Benzoic Acid (Oxidation)
Acofophonono cannof bo oxIdIzod fo bonzoIc acId by fho usuaI oxIdIzIng agonfs. !or kofonos
In whIch ono group Is mofhyI, can Insfoad bo oxIdIzod by fho haIoform roacfIon. Acofophonono
In froafod wIfh bromIno and sodIum hydroxIdo soIufIon whoroby bonzoIc acId and bromoform
a IIquId aro formod In fho roacfIon.
Procedure: BromIno soIufIon Is fIrsf proparod. In a 250 mI round-boffomod fIask, dIssoIvo
1 g of sodIum hydroxIdo In 50 mI of wafor. To fhIs soIufIon add 40 g of crushod Ico. Tako fho
fIask fo fho fumo hood tNofo I) and add 2 mI of bromIno and shako fho fIask unfII bromIno
dIssoIvos. Add 2 mI of acofophonono dropwIso and shako fho fIask for 10 mIn. Transfor fho
confonfs of fho fIask fo a soparafory funnoI and wIfhdraw fho Iowor Iayor of
bromoform.Transfor fho IIquId Info a boakor, add abouf 0.5 g of acfIvafod carbon, sfIr and
fIIfor. To fho fIIfrafo, add somo crushod Ico and acIdIfy wIfh dIIufo suIfurIc acId. Tho soIufIon
offon has a yoIIowIsh orango coIor af fhIs sfago duo fo fho prosonco of oxcoss bromIno. ThIs
coIor can bo romovod by addIng dropwIso a soIufIon of sodIum bIsuIfIfo. !IIfor agaIn and
rocrysfaIIIzo bonzoIc acId from boIIIng wafor. YIoId 6.2 g, m.p. 122
o
C.
Note ¡: WIfh bromIno aIways work In fho fumo hood.
198 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
8.18 Whaf fypo of kofonos aro oxIdIzod by sodIum hypobromIfo7
8.10.6 Preparation of Trimethylacetic Acid (Oxidation)
PInacoIono on oxIdafIon wIfh sodIum hypobromIfo forms frImofhyIacofIc acId, aIso known
as pIvaIIc acId.
ThIs acId aIfornafIvoIy can aIso bo obfaInod from GrIgnard roacfIon by carbonafIon of
t-bufyI chIorIdo foIIowod by profonafIon of fho InformodIafo compIox.
Procedure: ÐIssoIvo 40 g sodIum hydroxIdo In 75 mI wafor In a 500 mI ÐrIonmoyor fIask
and cooI In Ico. AIso add 75 g crushod Ico. Tako fho fIask fo fho hood and add 48 g t16.0 mI)
of bromIno In porfIons of abouf 1.0 mI af a fImo and shako fho fIask affor oach addIfIon and
waIf fIII aII fho bromIno has dIssoIvod boforo addIng fho noxf Iof. Romovo fho fIask from fho
Ico-bafh and add 10 g t12.5 mI) pInacoIono ovor a porIod of 5 mIn. Shako fho fIask and fhon
pour fho mIxfuro Info a fhroo-nockod fIask fIffod wIfh fwo droppIng funnoIs. Hoaf fho fIask
on a burnor fIII fho soIufIon sfarfs boIIIng and bromoform tCHBr
3
) soparafos ouf. As soon
as fho oxofhormIc roacfIon coasos, dIsfII off fho bromoform Info a rocoIvor cooIod In Ico.
CoIIocf abouf 40 mI of fho dIsfIIIafo and soparafo bromoform In a soparafory funnoI. Tho
yIoId Is 5 mI, b.p. 150
o
C.
ORGANIC PREPARATIONS 199
PIaco 35 mI coId conc. suIfurIc acId In 50 mI of wafor Info fho Iargor droppIng funnoI.
In fho socond funnoI pIaco 10% sodIum fhIosuIfafo soIufIon. CooI fho confonfs of fho fIask
fo around 70
o
C fhon add suIfurIc acId sIowIy. Bocauso of fho prosonco of oxcoss hypobromIfo
soIufIon, ovoIufIon of bromIno fakos pIaco as fho mIxfuro In fho fIask Is acIdIfIod. Whon fho
rod coIor of bromIno appoars, sfop addIng acId and run In somo sodIum fhIosuIfafo soIufIon.
ConfInuo fho procoss of aIfornafo addIfIon of acId and fhIosuIfafo soIufIons. Affor fho addIfIon
Is ovor fho soIufIon shouId bo acIdIc fo IIfmus. Af fhIs sfago fho soIufIon Is coIorIoss and
frImofhyIacofIc acId soparafos ouf as an oII. ÐIsfII fho mIxfuro and coIIocf fho acId whIch
dIsfIIs ovor wIfh wafor. CoIIocf abouf 75 mI of fho dIsfIIIafo, soparafo fho acId In a soparafory
funnoI. Tho yIoId Is 56 mI, b.p. 164
o
C/760 mm.
8.10.7 Preparation of Ethylbenzene (The Wolff-Kishner Reduction)
ÐIrocf roducfIon of a carbonyI group fo a mofhyIono group roquIros fho uso of corfaIn
spocIaI roagonfs. Such a roducfIon has boon accompIIshod by fho CIommonson roducfIon or
by fho RaNI roducfIon of fhIokofaI. Thoso roacfIons suffor from corfaIn drawbacks. Tho
CIommonson roducfIon, for Insfanco, Is subjocf fo sforIc hIndranco by fho prosonco of
noIghbourIng subsfIfuonfs. An IndIrocf mofhod of roducfIon of carbonyI fo mofhyIono Is
known as fho WoIff-KIshnor roducfIon.
OrIgInaIIy fho mofhod InvoIvod fwo sfops, fIrsf formIng a hydrazono of fho carbonyI
compound and socond hoafIng fho porformod hydrazono wIfh sodIum ofhoxIdo In a fubo.
Nowadays, fho Huang-MInIon modIfIcafIon Is found moro convonIonf. AccordIng fo fhIs a
mIxfuro of carbonyI compound, hydrazIno hydrafo and pofassIum hydroxIdo aro hoafod In a
hIgh boIIIng soIvonf such as dIofhyIono gIycoI`. Thon fho fwo sfops aro carrIod ouf In a
sIngIo sfop. ThIs modIfIcafIon Is usod In fho prosonf proparafIon.
Tho roacfIon has fho foIIowIng mochanIsm:
`AIfornafIvoIy, frIofhyIono gIycoI tb.p. 278°C) tHOCH
2
CH
2
O CH
2
CH
2
O CH
2
CH
2
OH) may bo usod.
200 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a 200 mI round-boffomod fIask, pIaco 9 g of puro acofophonono, 60 mI
dIofhyIono gIycoI tb.p. 245
o
C) 10 g pofassIum hydroxIdo and 8 mI of 90%
hydrazIno hydrafo. Add 2÷3 boIIIng chIps. Hoaf fho mIxfuro on a wafor-bafh fIII mosf of fho
pofassIum hydroxIdo has dIssoIvod. Affach a wafor condonsor fo fho fIask and rofIux on fho
fIamo for 1 hr. Affor fhIs porIod romovo fho condonsor and dIsfII off mosf of fho wafor and
hydrazIno unfII fho fomporafuro of fho IIquId rIsos fo 200
o
C tNofo I) and coIIocf fho dIsfIIIafo.
Soparafo fho organIc Iayor In a soparafory funnoI. Ðxfracf fho aquoous Iayor fwIco wIfh
ofhor. CombIno fho organIc Iayor and fho oxfracfs, dry ovor anhydrous sodIum suIfafo.
Romovo ofhor and dIsfII fho rosIduo and coIIocf fho fracfIon bofwoon 134÷137
o
C. Tho yIoId
Is 5.8 g.
Note ¡: !so a fhormomofor.
8.10.8 Preparation of Benzhydrol (Reduction)
RoducfIon of bonzophonono wIfh zInc dusf and aIc. sodIum hydroxIdo soIufIon, a mIId roducIng
agonf, rosuIfs In fho formafIon of a socondary aIcohoI, I.o., bonzhydroI.
Procedure: PIaco 6.3 g bonzophonono, 65 mI ofhanoI, 6.3 g sodIum hydroxIdo and 6.3 g of
zInc powdor In a 200 mI boIf-hoad fIask. ÐquIp fho fIask wIfh a rofIux condonsor. MIx fho
confonfs and fhon warm gonfIy on a wafor-bafh for 1.5 hr. AIIow fho fIask fo cooI fo 60
o
C
and fhon fIIfor fho roacfIon mIxfuro by sucfIon. Wash fho rosIduo on fho fIIfor papor fwIco
wIfh 5 mI porfIons of ofhanoI. Pour fho cIoar fIIfrafo In 250 mI coId wafor and acIdIfy wIfh
25 mI of conc. hydrochIorIc acId. A vIscous oII soparafos ouf whIch soIIdIfIos on cooIIng or
koopIng ovornIghf. !IIfor fho soIId undor sucfIon and rocrysfaIIIzo from 10 mI of hof ofhyI
aIcohoI. Tho yIoId Is 3.9 g, m.pf. 58
o
C.
8.10.9 Preparation and Stereochemistry of Azobenzene (Reduction)
Azobonzono Is proparod by roducIng nIfrobonzono In fho prosonco of a mIId roducIng agonf,
I.o., magnosIum mofaI and mofhyI aIcohoI.
ORGANIC PREPARATIONS 201
Procedure: In a 250 mI round-boffomod fIask oquIppod wIfh a rofIux condonsor, pIaco
6.2 g of nIfrobonzono and 110 mI of absoIufo mofhanoI. Add 3 g of a magnosIum furnIngs
and a fow crysfaIs of IodIno. If no roacfIon fakos pIaco, warm fho fIask. Onco fho roacfIon
has sfarfod no addIfIonaI hoaf Is nocossary. Affor mosf of fho magnosIum has roacfod add
anofhor 3 g of If and aIIow If fo roacf compIofoIy. RofIux fho roacfIon mIxfuro for 30 mIn,
cooI fho fIask and pour fho confonfs Info 200 mI of Ico wafor. NoufraIIzo fho aIkaIIno soIufIon
wIfh gIacIaI acofIc acId tchock wIfh a IIfmus papor) and cooI agaIn. !IIfor fho orango-yoIIow
azobonzono on a Buchnor funnoI. RocrysfaIIIzo If from ofhanoI. Tho yIoId Is 3.1 g, m.p.
68
o
C.
SepuruIion oj ¡somers
Azobonzono dIspIays goomofrIc IsomorIsm and oxIsfs In fho foIIowIng syn-and anti-
forms.
Thoso fwo forms can bo soparafod by coIumn chromafography and fhoIr IdonfIfy Is
osfabIIshod by uIfravIoIof spocfroscopy.
Procedure: Proparo a chromafographIc coIumn tNofo I) from 10 g of acfIvafod aIumIna
and pofroIoum ofhor. ÐIssoIvo 1 g azobonzono tNofo II) In a mInImum amounf of ofhor and
appIy fo fho coIumn.
ÐIufo fho coIumn wIfh 150 mI of pofroIoum ofhor tboIIIng rango 30÷60
o
C). As fho
soIvonf runs fhrough fho coIumn, a broad orango band of anti-Isomor shouId bo obsorvod fo
movo sIowIy down fho coIumn. A yoIIow narrow band of syn-Isomor shouId romaIn vory
noar fho fop of fho coIumn. CoIIocf onIy ono fracfIon In an ÐrIomoyor fIask wrappod In
aIumInum foII tNofo III). Now oIufo fho coIumn wIfh a soIvonf mIxfuro of pofroIoum ofhor
and 1% mofhanoI, and coIIocf fho fracfIon. Ðvaporafo fho soIvonf from bofh fho fracfIons on
a sfoam-bafh and fako fho u.v. spocfrum In ofhanoI. Tho fIrsf fracfIon shows
max
= 321
corrosponds fo fho anti-Isomor whIIo fho socond fracfIon as a
max
= 280 and Is fho syn-
Isomor.
Notes ¡: Puf a gIass wooI pIug af fho boffom of a 25 mI buroffo. Now pour 20 mI of pof ofhor In fho
buroffo and add 10 g of aIumIna from fho fop In a confInuous sfroam. Tho buroffo shouId
bo maInfaInod In a vorfIcaI posIfIon and cIampod on an Iron-sfand. Thon add a Iayor of
sand and draIn off fho soIvonf fIII Ifs IavoI Is abouf 2 cm abovo fho IovoI of packIng.
¡¡: Ðo nof uso an oId sampIo of azobonzono.
¡¡¡: AIfornafIvoIy carbon papor can bo wrappod.
202 LABORATORY MANUAL OF ORGANIC CHEMISTRY
8.10.10 Preparation of m-Nitroaniline from m-Dinitrobenzene (Reduction)
n-ÐInIfrobonzono Is soIocfIvoIy roducod by sodIum bIsuIfIfo fo obfaIn n-nIfroanIIIno.
Tho proparafIon Is carrIod ouf In fwo sfops:
Step A: PrepuruIion oj m-JiniIrobenzene
Proceduce: In a 100 mI round-boffomod fIask, pIaco 11.3 g t7.5 mI) of fumIng nIfrIc acId, fo
fhIs sIowIy add 18.4 g t10.5 mI) of conc. suIfurIc acId. !If fho fIask wIfh a rofIux condonsor
and fhrough If, add 7.5 g t6.3 mI) of nIfrobonzono In four smaII porfIons wIfh fhorough
shakIng. Affor fho addIfIon Is compIofo rofIux fho mIxfuro on a wafor-bafh In a fumo hood
for 15 mIn. WIfh froquonf shakIng, cooI and pour fho confonfs Info 200 mI of coId wafor
fakon In a 600 mI boakor. Tho producf soparafos ouf as a paIo yoIIow soIId. !IIfor on a
Buchnor funnoI and wash fhoroughIy wIfh coId wafor fo romovo fho acId. To purIfy n-
dInIfrobonzono, fako fho crudo producf In a 100 mI round-boffomod fIask wIfh 40 mI of
ofhanoI and rofIux on a wafor-bafh fIII aII fho soIId has dIssoIvod. !IIfor fho hof soIufIon
and aIIow fho fIIfrafo fo cooI. Soparafo fho soIId by sucfIon and dry. Tho yIoId Is 7.2 g, m.p.
89÷90
o
C.
Step B: PrepuruIion oj m-niIrouniIine
Procedure: In a 250 mI ÐrIonmoyor fIask dIssoIvo 15.0 g of sodIum bIsuIfIfo tNa
2
S. 9H
2
O)
In 30 mI of wafor and fo fho soIufIon add 5.0 g of powdorod sodIum bIcarbonafo In smaII
porfIons wIfh consfanf sfIrrIng. Thon add 40 mI of mofhanoI and cooI fho mIxfuro fo 20
o
C.
!IIfor fo romovo fho procIpIfafod sodIum carbonafo and wash fho soIId wIfh a IIffIo mofhanoI.
Tho fIIfrafo confaIns sodIum bIsuIfIfo tNaHS) soIufIon noodod for roducfIon.
Transfor 5 g of n-dInIfrobonzono In a 250 mI round-boffomod fIask, add 45 mI of
mofhanoI and warm. To fhIs add sodIum bIsuIfIfo soIufIon proparod abovo. !Ix a rofIux
condonsor fo fho fIask and rofIux for 20 mIn tNofo I). AIIow fho fIask fo cooI and dIsfII mosf
of mofhanoI from a wafor-bafh. Pour fho rosIduo from fho dIsfIIIIng fIask Info a boakor and
koop sfIrrIng. CoIIocf fho yoIIow n-nIfroanIIIno on a Buchnor funnoI and wash wIfh wafor.
RocrysfaIIIzo from 75% mofhanoI. Tho yIoId Is 3.1 g, m.p. 114
o
C.
Note ¡: Somo sodIum carbonafo may aIso procIpIfafo af fhIs sfago, Ignoro If.
8.10.11 Reduction of p-Nitroacetophenone (Selective Reduction)
SodIum borohydrIdo Is a mIId roducIng agonf whIIo IIfhIum aIumInum hydrIdo Is a poworfuI
roducIng agonf. LIfhIum aIumInum hydrIdo roducos mosf funcfIonaI groups. If Is usod In
dry soIvonfs as If roacfs vIoIonfIy wIfh wafor. SodIum borohydrIdo, on fho ofhor hand, Is a
ORGANIC PREPARATIONS 203
mIId roducIng agonf and oxhIbIfs consIdorabIo soIocfIvIfy. If roducos aIdohydos and kofonos
rapIdIy. Ofhor funcfIonaI groups such as , ofc. aro oIfhor sIowIy
roducod or aro Inorf. ThIs roagonf Is usod In ofhanoI or mofhanoI. In fho foIIowIng oxporImonf
p-nIfroacofophonono In roducod Is p-nIfro-1-phonyI-1-ofhanoI usIng sodIum borohydrIdo.
RoducfIon of bonzophonono fo bonzhydroI of oxporImonf t8.10.8) can aIso bo carrIod
ouf usIng sodIum borohydrIdo.
Procedure: ÐIssoIvo 2.2 g p-nIfroacofophonono In 28 mI ofhanoI by warmIng In an
ÐrIonmoyor fIask. CooI fho soIufIon In Ico fo produco a fIno susponsIon of soIId. In a
fosf fubo dIssoIvo 0.69 sodIum borohydrIdo In 1 mI of wafor and add fo fho roacfIon mIxfuro
dropwIso compIofIng In 30 mIn. ÐurIng fhIs fImo a sIIghf docoIorIzafIon fakos pIaco. Pour
fho mIxfuro In a boakor confaInIng 20 mI wafor and 1 mI of conconfrafod hydrochIorIc acId.
Affor a fow mInufos fransfor fho confonfs fo a soparafory funnoI and oxfracf fwIco wIfh
30 mI porfIons of ofhor. Ðry fho combInod oxfracfs ovor anhyd. sodIum suIfafo. Romovo
ofhor on a hof pIafo fo obfaIn a IIghf brown oII. Tho p-nIfrophonyImofhyIcarbInoI Is dIsfIIIod
undor roducod prossuro, b.p. 161÷3
o
C/4 mm.
Questions
8.19 WrIfo fho producfs obfaInod by fho roducfIon of n-nIfroacofophonono wIfh Sn/HCI
and NaBH
4
rospocfIvoIy.
8.20 Whaf ofhor roagonfs bosIdos NaBH
4
wIII roduco acofophonono fo 1-phonyI-1-ofhanoI7
8.11 ORGANOMETALLIC CHEMISTRY
OrganomofaIIIc compounds probabIy roprosonf ono of fho sIngIo mosf usofuI synfhofIc fooIs
for fho proparafIon of organIc compounds. In an organomofaIIIc compound, a mofaI afom Is
IInkod dIrocfIy fo an organIc group tR ÷ M). Tho bond formod has a hIgh dogroo of IonIc
characfor.
8.11.1 Preparation of Benzoic Acid (The Grignard Reaction)
A GrIgnard roagonf has fho gonoraI formuIa RMgX. Such roagonfs aro hIghIy roacfIvo and
havo provon fo bo of groaf synfhofIc ufIIIfy.
204 LABORATORY MANUAL OF ORGANIC CHEMISTRY
BonzoIc acId can bo proparod by froafIng phonyI magnosIum bromIdo tfho GrIgnard
roagonf) wIfh carbon dIoxIdo and subsoquonf hydroIysIs of fho compIox.
Procedure: In a 250 mI round-boffomod fIask fIffod wIfh a rofIux condonsor, pIaco 2.4 g of
dry magnosIum furnIngs In 30 mI of sodIum dry ofhor. To fhIs add sIowIy 15.7 g t10 mI) of
dry bromobonzono tNofo I) and a crysfaI of IodIno. Thoro Is an ImmodIafo commoncomonf
of roacfIon wIfh ofhor appoarIng mIIky whIfo. If, howovor, fho roacfIon doos nof sfarf,
warm fho fIask on a wafor-bafh and romovo If affor fho mIxfuro sfarfs rofIuxIng. ThIs wIII
usuaIIy promofo fho roacfIon. Tho roacfIon subsoquonfIy wIII sfarf IfsoIf, boII for 35÷40
mIn. Affor fhIs hoaf fho fIask In a boakor of warm wafor for an addIfIonaI porIod of 10 mIn.
PIaco approxImafoIy 15 g of crushod dry lce In a 250 mI boakor and pour Info If sIowIy fho
GrIgnard roagonf proparod abovo, wIfh consfanf sfIrrIng. A vIgorous roacfIon onsuos and
fho confonfs In fho fIask furn Info a pasfy mass. SfIr If fIII aII fho carbon dIoxIdo has
ovaporafod. Add 50 mI of warm wafor and fhon acIdIfy fho confonfs wIfh dII. hydrochIorIc
acId In ordor fo gonorafo bonzoIc acId as woII as dIssoIvo fho magnosIum saIf. CooI fho
boakor In Ico and fIIfor. RocrysfaIIIzo from hof wafor, yIoId 6.0 g, m.p. 122
o
C.
Note ¡ : Bromobonzono may bo drIod ovor anhydrous caIcIum chIorIdo.
Question
8.21 Suggosf fhroo addIfIonaI mofhods for fho proparafIon of bonzoIc acId.
8.11.2 Preparation of Triphenylmethanol (The Grignard Reaction)
ÐxfromoIy dry condIfIons aro nocossary for Ifs proparafIon. Tho roacfIon may proforabIy bo
porformod undor an afmosphoro of nIfrogon.
ORGANIC PREPARATIONS 205
Procedure: In a 250 mI fhroo-nockod fIask oquIppod wIfh a mochanIcaI sfIrror, a wafor
condonsor, a dryIng fubo and a droppIng funnoI, pIaco 2.7 g of magnosIum furnIngs In 20 mI
sodIum dry ofhor. AIso add a crysfaI of IodIno. !rom fho droppIng funnoI add sIowIy a
soIufIon of 18 g of bromobonzono In 50 mI of dry ofhor wIfh consfanf sfIrrIng. An oxofhormIc
roacfIon onsuos tNofo I). Whon fho addIfIon of bromobonzono Is compIofo rofIux fho mIxfuro
for 5 mIn fo compIofo fho formafIon of GrIgnard roagonf. CooI fho fIask In coId wafor, and
add fo If a soIufIon of 7.5 g bonzophonono In 25 mI of ofhor fakon In fho droppIng funnoI.
RofIux for 10÷15 mIn on a wafor-bafh. CooI fho fIask agaIn and pour fho confonfs In a
boakor confaInIng 200 g of Ico and 60 mI of 20% suIfurIc acId. SfIr fho mIxfuro wIfh a gIass
rod fo docomposo fho magnosIum compound. Transfor fo a soparafory funnoI, dIscard fho
aquoous Iayor. Wash fho organIc Iayor wIfh 25 mI of 10% suIfurIc acId and fhon wIfh wafor.
Sfoam dIsfII fho mIxfuro fIII no moro oII passos ovor. CooI fho dIsfIIIafIon fIask and
rocrysfaIIIzo fho rosIduo from mofhanoI or bonzono. Tho yIoId Is 8.4 g, m.pf. 160÷162
o
C.
Note: If fho roacfIon doos nof commonco, warm fho fIask sIIghfIy. Appoaranco of furbIdIfy
IndIcafos fho occurronco of fho roacfIon.
Question
8.22 Why aro absoIufoIy dry condIfIons nocossary for fhIs roacfIon7
8.11.3 Preparation of p-Toluic Acid from p-Bromotoluene
OrganoIIfhIum compounds anaIogous fo fho GrIgnard roagonfs yIoId carboxyIIc acIds on
carbonafIon. An organoIIfhIum compound can bo proparod by fho ropIacomonf of fho haIo
afom of an organIc haIIdo by IIfhIum In dry ofhor undor an afmosphoro of nIfrogon. Tho
rosuIfIng organoIIfhIum Is carbonafod wIfh dry lce and subsoquonfIy hydroIyzod fo yIoId
fho acId. ThIs procoss Is domonsfrafod for fho proparafIon of p-foIuIc acId from
p-bromofoIuono.
Procedure: In a 250 mI fhroo-nockod fIffod wIfh a rofIux condonsor, morcury soaI, sfIrror
and a smaII droppIng funnoI combInod wIfh a gIass InIof, pIaco 20 mI of anhydrous ofhor and
fIush fho fIask wIfh dry nIfrogon gas. Add 0.95 g of IIfhIum mofaI tNofo I) In fho form of
shavIngs and sfIr. Tako a soIufIon of 10.8 g of p-bromofoIuono In 20 mI of dry ofhor In fho
droppIng funnoI. Add abouf 1 mI of fhIs soIufIon Info fho fIask. An oxofhormIc roacfIon
commoncos ImmodIafoIy bocauso IIfhIum roacfs moro rapIdIy wIfh organIc haIIdo fhan
magnosIum doos. Add fho romaInIng soIufIon sIowIy wIfhIn a porIod of 15 mIn wIfh consfanf
206 LABORATORY MANUAL OF ORGANIC CHEMISTRY
sfIrrIng and sImuIfanoous passago of nIfrogon gas. RofIux fho rosuIfanf soIufIon on a wafor-
bafh for 25÷30 mIn fo compIofo fho roacfIon. CooI fho fIask In an Ico-bafh, dIIufo wIfh 25 mI
of ofhor and cooI agaIn fo ÷50°C wIfh fho acId of acofono dry Ico mIxfuro. In a 500 mI boakor
fako 200 g of crushod dry Ico and 50 mI ofhor and sfIr. To fhIs add sIowIy fho soIufIon of
IIfhIum dorIvafIvo of p-bromofoIuono. RInso fho fIask wIfh a smaII quanfIfy of ofhor and
pour Info fho boakor. AIIow fho mIxfuro fo sfand af room fomporafuro for 2÷3 hrs for
compIofo ovaporafIon of dry Ico. Affor fhIs porIod add 100 mI of wafor. Af fhIs poInf a soIId
may appoar whIch dIssoIvos on sfandIng. To fhIs add 20 mI of ofhor and fransfor fho confonfs
fo a soparafory funnoI, shako and wIfhdraw fho aquoous Iayor. Wash fho aquoous Iayor
fwIco wIfh ofhor. Savo fho oxfracf In a boakor. Shako fho romaInIng aquoous Iayor wIfh 25
mI of 10% sodIum hydroxIdo soIufIon fo obfaIn fho acId as Ifs sodIum saIf. Hoaf on a wafor-
bafh fo drIvo off fho dIssoIvod ofhor and fhon coId fho soIufIon fo 5
o
C, and sfrongIy acIdIfy
wIfh conc. hydrochIorIc acId fo soparafo p-foIuIc acId. CoIIocf fho soIId on a Buchnor funnoI,
wash wIfh coId wafor and dry. RocrysfaIIIzo fho acId from hof ofhanoI. Tho yIoId Is 5.1 g,
m.pf. 176÷177
o
C.
A by-producf, namoIy, dI-p-foIyIkofono Is aIso obfaInod whIch can bo oasIIy soparafod
from fho maIn producf. Ðry fho combInod ofhor oxfracf ovor anhydrous mognosIum suIfafo
and romovo ofhor ovor a wafor-bafh. RocrysfaIIIzo fho rosIduo from hof aIcohoI, yIoId 1.8 g,
m.pf. 95
o
C.
8.12 DEHYDRATION
AIcohoIs, acIds, oxImos, ofc. can bo mado fo Ioso a moIocuIo of wafor undor fho acfIon of
dIfforonf fypos of cafaIysfs. Tho rosuIf Is fho formafIon of an unsafurafod producf.
8.12.1 Preparation of Cyclohexene
ÐohydrafIon of aIcohoIs roquIros an acIdIc cafaIysf fo profonafo fho hydroxyI group of fho
aIcohoI and convorf If Info a good IoavIng group. A ÷OH group by IfsoIf Is a poor IoavIng
group. An oquIIIbrIum Is osfabIIshod bofwoon fho roacfanfs and fho producfs:
Thoroforo, In ordor fo drIvo fhIs oquIIIbrIum fo fho rIghf, If Is nocossary fo romovo
ono or moro of fho producfs as fhoy aro formod. ThIs can bo accompIIshod oIfhor by dIsfIIIIng
fho producfs or by addIng a dohydrafIng agonf fo romovo wafor. In pracfIco, howovor, a
combInafIon of dIsfIIIafIon and dohydrafIon Is offon ompIoyod. CycIohoxanoI may bo
dohydrafod usIng oIfhor 9 M suIfurIc acId or 85% phosphorIc acId.
ORGANIC PREPARATIONS 207
AIcohoI dohydrafIon fakos pIaco fhrough Ð
1
mochanIsm.
Procedure: Infroduco 10 mI of 9 M suIfurIc acId Info a CIaIson fIask. Add a fow boIIIng
chIps. In ono oponIng fIf a 50 mI droppIng funnoI ta soparafory funnoI may bo usod) and
pIaco 20 g cycIohoxanoI. !If fho ofhor oponIng wIfh a fracfIonafIng coIumn and a fhormomofor
and affach a LIobIg`s condonsor. Mako suro fhaf aII fho gIass sfoppors fIf fIghfIy fo provonf
Iossos duo fo ovaporafIon. Hoaf fho fIask In an oII-bafh af 160÷170
o
C. !rom fho droppIng
funnoI add cycIohoxanoI dropwIso ovor a porIod of 45 mIn. Affor fho addIfIon Is compIofo,
raIso fho fomporafuro fo 190÷200
o
C tNofo I) and dIsfII. Tho fomporafuro af fho fop of fho
coIumn shouId romaIn boIow 90°C. Transfor fho dIsfIIIafo fo a soparafory funnoI and shako
wIfh safurafod sodIum chIorIdo soIufIon. ÐIscard fho Iowor Iayor. Tako fho uppor Iayor and
dry tMgSO
4
). ÐIsfII fho crudo cycIohoxono from a 10 mI dIsfIIIIng fIask and coIIocf fho
fracfIon passIng ovor af 81÷83
o
C. Tho yIoId Is 13 g. Tho rosIduo romaInIng In fho dIsfIIIafIon
fIask Is IargoIy unroacfod cycIohoxanoI.
Notes ¡: 85% phosphorIc acId Is Ioss offIcIonf and gIvos Ioss yIoId.
¡¡: !so a fhormomofor.
Questions
8.23 Whaf ofhor sIdo-producfs may bo formod In fho abovo roacfIon7
8.24 WrIfo fho dohydrohaIogonafIon producf.
208 LABORATORY MANUAL OF ORGANIC CHEMISTRY
8.12.2 Preparation of Succinic Anhydride
SuccInIc acId dohydrafos on hoafIng wIfh acofIc anhydrIdo fo yIoId succInIc anhydrIdo.
Procedure: PIaco 7.5 g of succInIc acId In a dry 100 mI round-boffomod fIask fIffod wIfh a
rofIux condonsor and a dryIng fubo. To fhIs carofuIIy add 12.5 mI of acofIc anhydrIdo and
hoaf fho mIxfuro on a sfoam-bafh wIfh occasIonaI shakIng unfII a cIoar soIufIon Is obfaInod.
Hoaf for an addIfIonaI porIod of 30 mIn. Thon cooI fho fIask In an Ico-bafh. CoIIocf fho
crysfaIs on a Buchnor funnoI af fho pump and wash wIfh ofhor tNofo I). Tho yIoId Is
5.2 g, m.p. 119÷120
o
C.
Note ¡: Tosf fho producf wIfh coId sodIum bIcarbonafo soIufIon for fho prosonco of unchangod
succInIc acId.
8.12.3 Dehydration of Camphor Oxime (Molecular Rearrangement)
ÐohydrafIon of camphor oxImo undor fho Bockmann condIfIons offors an InforosfIng oxampIo
of a skoIofaI roarrangomonf. Tho oxImo doos nof produco fho usuaI N-subsfIfufod amIdo,
buf a nIfrIIo.
MochanIsfIcaIIy Ifs formafIon can bo shown as boIow:
ThIs roacfIon Is carrIod ouf In fwo sfops:
ORGANIC PREPARATIONS 209
Step A: PrepuruIion oj cumphor oxime
Procedure : In a 250 mI ÐrIonmoyor fIask pIaco a mIxfuo of 3 g of camphor, 3 g hydrazIno
hydrochIorIdo, 3.5 mI of pyrIdIno and 25 mI of ofhanoI. Shako and warm fho fIask on a
sfoam-bafh for 1 hr. Thon dIsfII ofhanoI undor vacuum of an aspIrafor. Add 25 mI of wafor
fo fho rosIduo, swIrI and fIIfor fho soIId on a Buchnor funnoI. Wash fho producf wIfh 10 mI
of coId wafor. Tho oxImo Is obfaInod In a yIoId of 2.5 g, m.p. 118÷119
o
C.
Step B: DehyJruIion oj cumphor oxime
Procedure: Tako 2 g of dry camphor oxImo In an ÐrIonmoyor fIask and cooI If In an Ico-
bafh. Thon add 1.4 g of froshIy dIsfIIIod acofyI chIorIdo In smaII Iofs, shakIng fho roacfIon
mIxfuro consfanfIy. Affor fho addIfIon Is compIofo, aIIow If fo cooI fo room fomporafuro.
Pour fho confonfs Info 50 mI of Ico wafor. Transfor fo a soparafory funnoI and oxfracf fho
rosuIfIng nIfrIIo wIfh a mIxfuro of 10 mI of bonzono and 10 mI of sodIum bIcarbonafo soIufIon.
WIfhdraw fho organIc Iayor. Wash wIfh wafor and dry ovor sodIum suIfafo. !IIIor and dIsfII
off bonzono from a hof wafor-bafh. Transfor fho vIscous oII fo a dIsfIIIafIon fIask and dIsfII
af roducod prossuro. Tho nIfrIIo Is obfaInod as a coIorIoss IIquId. Tho yIoId Is 1.3 g, b.p. 130÷
132
o
C/37 mm.
8.13 OPTICAL ACTIVITY
Compounds confaInIng an asymmofrIc carbon afom aro opfIcaIIy acfIvo, I.o., fhoy rofafo
fho pIano of poIarIzod IIghf. Tho opfIcaI rofafIon of fho compound Is oxprossod as a physIcaI
consfanf. If Is common fo roporf fho spocIfIc roacfIon t α ) gIvon by fho foIIowIng oxprossIon:
[ ] α
t
D
=
c I ×
θ
whoro [ ]
f
Ð
α Is fho spocIfIc rofafIon af t
o
C, θ Is fho numbor of dogroos fhrough whIch fho
IncIdonf boam has boon rofafod, I tdocImofor) Is fho Iongfh of fho sampIo fubo and C Is fho
conconfrafIon of soIufIon In g/mI of fho soIufIon. Tho spocIfIc rofafIon Is oxprossod as a
dImonsIonIoss fIguro. If fho spocIfIc rofafIon of an onanfIomor of say monfhoI Is quofod as
[ ]
20
Ð
α = + 49.2, fho t+) sIgn boforo fho vaIuo IndIcafos fhaf fho pIano of IncIdonf hIghf has
boon rofafod In a cIockwIso dIrocfIon, fhoroforo, If Is doxfrorofafory. Tho angIo of rofafIon
Is moasurod In an Insfrumonf caIIod a polurlmeter.
Tho Insfrumonf consIsfs of a Iong cyIIndrIcaI fubo confaInIng varIous parfs. A boam of
IIghf tsodIum Iamp), omorgos pIano poIarIzod affor passIng fhrough fho poIarIzor ta nIcoI
prIsm). Tho IIghf sfIII vIbrafos In ono pIano buf fho pIano Is fIIfod duo fo rofafIon of fho
pIano of poIarIzafIon so fhaf If IIos af dIfforonf angIo fhan If dId orIgInaIIy. If Is fhon aIIowod
fo pass fhrough an anaIyzor ta socond nIcoI prIsm).
Affor fho IIghf passos fhrough fho sampIo If Is no moro aIIgnod In a vorfIcaI pIano and
fho IIghf Is bIockod by fho anaIyzor fo a corfaIn oxfonf.
210 LABORATORY MANUAL OF ORGANIC CHEMISTRY
In ordor fo aIIow fho poIarIzod IIghf fo pass frooIy, fho anaIyzor musf fhus bo rofafod
so fhaf If Is fIIfod af fho samo angIo as fho omorgod poIarIzod IIghf from fho sampIo. !or
fhIs purposo fho anaIyzor Is mounfod on a cIrcuIar dIaI markod In dogroos. Tho angIo of
rofafIon for maxImum IIghf fo pass fhrough fho sampIo Is rocordod.
Fig. 8.1 Set up of a polarimeter.
Tho oxfonf of rofafIon In forms of spocIfIc rofafIon Is caIcuIafod wIfh fho hoIp of fho
abovo oxprossIon.
8.13.1 Resolution of Racemic =-Phenylethylamine
=-PhonyIofhyIamIno may bo proparod from acofophonono and ammonIum formafo. Tho
onanfIomors aro formod In oquaI amounfs, i.c., a racomIc modIfIcafIon Is formod. Tho fwo
opfIcaIIy acfIvo forms can bo soparafod by proparIng fhoIr dIasforooIsomors and fhon
soparafIng fhom by sfandard oxporImonfaI procoduro and fInaIIy rogonorafIng fho
onanfIomors.
Procedure: WoIgh accurafoIy abouf 5 g of racomIc =-phonyIofhyIamIno and dIssoIvo In
35 mI of mofhanoI. ÐoformIno Ifs spocIfIc rofafIon.
ÐIssoIvo 0.028 moIo of t+) farfarIc acId In 415 mI of mofhanoI In a 1 IIfro ÐrIonmoyor
fIask by boIIIng. To fho hof soIufIon add fho amIno soIufIon caufIousIy tNofo I). Add addIfIonaI
=-phonyIofhyIamIno fo mako a fofaI of 0.206 moIo of fho amIno. AIIow fho soIufIon fo sfand
af room fomporafuro for 24 hrs tNofo II). !IIfor fho crysfaIs on a Buchnor funnoI and wash
fhom wIfh a smaII quanfIfy of mofhanoI tNofo III). ÐIssoIvo fho crysfaIs In abouf four
fImos fhoIr woIghf of wafor and sIowIy add wIfh consfanf sfIrrIng a soIufIon of 8.2 g of
sodIum hydroxIdo dIssoIvod In 15 mI wafor. Ðxfracf fho rosuIfIng mIxfuro four fImos wIfh
75 mI porfIons of ofhor. CombIno fho ofhor oxfracfs and wash wIfh 50 mI of safurafod
sodIum chIorIdo soIufIon. Ðry fho ofhor soIufIon ovor magnosIum suIfafo. Romovo ofhor on
a hof pIafo and dIsfII fho rosIduo, t=-phonyIofhyIamIno) undor aspIrafor vacuum usIng a
burnor bocauso fho amIno has a b.p. of 94÷95
o
C/28 mm. Tho yIoId Is 5.5 g.
WoIgh fho amIno accurafoIy and dIssoIvo In 35 mI of mofhanoI and moasuro Ifs spocIfIc
rofafIon. Tho roporfod spocIfIc rofafIon of fho compound Is [ ]
20
Ð
α = +40.1
ORGANIC PREPARATIONS 211
Notes ¡: Add fho amIno soIufIon sIowIy and caufIousIy fo avoId foamIng.
¡¡: May bo kopf fIII fho noxf Iaborafory porIod.
¡¡¡: Tho fIIfrafo confaIns ono Isomor.
8.14 HETEROCYCLIC COMPOUNDS
HoforocycIIc compounds aro cycIIc compounds In whIch, In addIfIon fo carbon, hoforo afoms
such as N, S, O, ofc. aro aIso prosonf In fho rIng. Tho hoforocyIIc rIngs form a parf of many
fypos of nafuraI producfs. Synfhosos of a fow hoforocycIIc compounds wIII bo gIvon horo.
8.14.1 Preparation of Quinoline (The Skraup Synthesis)
QuInoIIno Is proparod by fho Skraup synfhosIs from anIIIno, gIycoroI, suIfurIc acId and an
oxIdIzIng agonf. NIfrobonzono Is usod as fho oxIdIzIng agonf In fhIs proparafIon.
GIycoroI Is fIrsf convorfod Info acroIoIn by conc. suIfurIc acId whIch subsoquonfIy roacfs
wIfh anIIIno, foIIowod by oxIdafIon by nIfrobonzono fo form quInoIIno.
Procedure: !If a fhroo-nockod 250 mI fIask wIfh a mochanIcaI sfIrror, a rofIux condonsor
and a fhormomofor. In fho fIask pIaco 10 g t9.8 mI) of anIIIno, 15 g gIycoroI and 400 mg
IodIno. SfIr fho mIxfuro and pour 30 g t16.4 mI) of conc. suIfurIc acId sIowIy down fho
condonsor. An oxofhormIc roacfIon bogIns and fho fomporafuro rIsos fo 100÷105
o
C. Hoaf
fho fIask gonfIy on an oII-bafh af 140
o
C. Affor 15 mIn raIso fho fomporafuro fo 170
o
C and
hoaf for 1 hr. CooI fho fIask and add 90 mI of 6 N sodIum hydroxIdo soIufIon sIowIy wIfh
AcroIoIn
212 LABORATORY MANUAL OF ORGANIC CHEMISTRY
consfanf shakIng. Sfoam dIsfII fho mIxfuro. ÐIsfII fIII no oIIy drops pass ovor. Ðxfracf fho
dIsfIIIafo wIfh fwo 25 mI porfIons of ofhor, dry and romovo ofhor on a wafor-bafh. ÐIssoIvo
fho crudo producf, confaInIng somo anIIIno, In 100 mI of 2.5 N hydrochIorIc acId In a 250 mI
boakor, warm and add 13 g of zInc chIorIdo soIufIon In 22 mI of 2.5 N hydrochIorIc acId wIfh
consfanf sfIrrIng. CooI fho boakor In Ico and fIIfor fho soIId quInoIIno chIorozIncafo tNofo I)
on a Buchnor funnoI and wash wIfh dII. hydrochIorIc acId. Transfor fho saIf fo a 250 mI
boakor, add 6 mI of wafor foIIowod by 10% sodIum hydroxIdo soIufIon unfII fho InIfIaI
procIpIfafo of zInc chIorIdo dIssoIvos compIofoIy. Pour fho mIxfuro In a soparafory funnoI
and oxfracf quInoIIno wIfh fwo 25 mI porfIons of ofhor. Ðry fho combInod oxfracfs ovor
anhyd. magnosIum suIfafo and ovaporafo ofhor on a hof wafor-bafh. ÐIsfII fho rosIduo and
coIIocf fho fracfIon dIsfIIIIng bofwoon 236÷238
o
C. Tho yIoId Is 6.8 g.
Note ¡: SInco quInoIIno Is confamInafod wIfh a smaII amounf of anIIIno, fho Iaffor Is romovod
by makIng Ifs chIorozIncafo saIf whIch Is soIubIo In wafor buf fhaf of quInoIIno
¦tC
9
H
7
N)
2
ZnCI
4
¦H
2
Is InsoIubIo.
8.14.2 Preparation of 2-Phenylindole (The Fischer-Indole Synthesis)
ThIs compound Is proparod accordIng fo fho !Ischor IndoIo synfhosIs sfarfIng from
phonyIhydrazIno and acofophonono.
Tho proparafIon Is carrIod ouf In fho foIIowIng fwo sfops:
ORGANIC PREPARATIONS 213
Step A: PrepuruIion oj uceIophenonephenyIhyJruzone
Procedure : In a 100 mI boakor pIaco 6 g of froshIy dIsfIIIod acofophonono and a soIufIon of
5.4 g of phonyIhydrazIno tNofo I) In 20 mI ofhanoI. To fho mIxfuro add 2÷3 drops of gIacIaI
acofIc acId and hoaf af 100
o
C for 15 mIn. CooI and fIIfor fho soIId acofophonono
phonyIhydrazono. Wash wIfh dII. hydrochIorIc acId and ofhanoI, rospocfIvoIy. RocrysfaIIIzo
fho producf form hof ofhanoI, m.p. 106
o
C.
Step B: PrepuruIion oj 2-phenyIinJoIe
Procedure: MIx 3 g of fho compound proparod In sfop A wIfh 20 g of poIyphosphorIc acId
tNofo II) In a boakor and hoaf fo boIIIng for 12 mIn. SfIr wIfh a fhormomofor maInfaInIng
a fomporafuro In fho rango of 100÷120°C tNofo III). To fhIs add 50 mI of coId wafor and sfIr
agaIn fo dIssoIvo unroacfod poIyphosphorIc acId. CoIIocf fho soIId on a Buchnor funnoI,
wash wIfh coId wafor and fInaIIy wIfh 5 mI of ofhanoI. Tho yIoId Is 2.2 g, m.p. 187
o
C.
Notes ¡: PhonyIhydrazIno Is vory poIsonous, If If comos In confacf wIfh fho skIn wash woII wIfh
wafor.
¡¡: CommorcIaI poIyphosphorIc acId Is dIffIcuIf fo handIo bocauso of Ifs hIgh vIscosIfy. If may
bo proparod frosh by mIxIng 26 g of phosphorus ponfoxIdo and 14 g of commorcIaI
orfhophosphorIc acId tdonsIfy = 1.7).
¡¡¡: !so a fhormomofor.
8.14.3 Preparation of 1-Phenyl-3-Methyl-5-Pyrazolone
ThIs compound Is formod by hoafIng fogofhor ofhyI acofoacofafo wIfh phonyIhydrazIno.
PhonyImofhyIpyrozoIono Is an InformodIafo In fho synfhosIs of anfIpyrIno.
Procedure: PIaco 6.4 g of froshIy dIsfIIIod ofhyI acofoacofafo and 5.4 g of phonyIhydrazIno
In a Iargo fosf fubo or a 100 mI round-boffomod fIask. Hoaf fho mIxfuro on a wafor-bafh In
a hood wIfh occasIonaI sfIrrIng. Tho cIoar soIufIon soon bocomos furbId duo fo fho formafIon
214 LABORATORY MANUAL OF ORGANIC CHEMISTRY
of dropIofs of wafor. !If an aIr condonsor and confInuo hoafIng t135÷145
o
C) for 1 hr. and
durIng fhIs porIod a hoavy roddIsh syrup soparafos ouf. Pour fhIs Info a boakor and cooI.
SfIr If wIfh 40 mI of ofhor. As soon as fho crysfaIs soparafo, cooI fho boakor In Ico and
coIIocf fho soIId on a Buchnor funnoI. Wash wIfh ofhor and rocrysfaIIIzo from hof wafor or
aIcohoI. Tho yIoId Is 6.5 g., m.p. 127
o
C.
8.14.4 Preparation of 5-Hydroxy-1, 3-Benzoxazol-2-One
p-BonzoquInono and fhIouroa roacf In an acIdIc modIum In an addIfIon-cycIIzafIon roacfIon
fo form fho fIfIo compound.
Tho proparafIon Is carrIod ouf In fwo sfops:
Step A: PrepuruIion oj p-benzoguinone.
Procedure: PIaco 10 g of hydroquInono, 5 g pofassIum bromafo, 5 mI of 1 N suIfurIc acId
and 100 mI wafor In a 250 mI boIf-hoad fIask. !If fho fIask wIfh a rofIux condonsor and a
fhormomofor. Hoaf fho mIxfuro sIowIy fo 60
o
C on a wafor-bafh. A roddIsh-brown coIor
sfarfs appoarIng af 50
o
C. A cIoar soIufIon Is obfaInod af 60
o
C. Affor 5 mIn, hoaf fho roacfIon
mIxfuro fo 80°C and maInfaIn fhIs fomporafuro for 10 mIn wIfh froquonf sfIrrIng. ÐurIng
fhIs porIod fho roacfIon mIxfuro furns brownIsh-yoIIow. CooI fho fIask In an Ico-bafh. !IIfor
fho yoIIow crysfaIs of p-bonzoquInono on a Buchnor funnoI, wash wIfh Ico coId wafor and
dry In aIr. Tho yIoId Is 7.2 g, m.p. 115.5
o
C.
Step B: PrepuruIion oj Ihe jinuI proJucI
Procedure: ÐIssoIvo 5.7 g fhIouroa In 35 mI of 2 N hydrochIorIc acId In a 200 mI
round-boffomod fIask. To fhIs add 5.4 g p-bonzoquInono dIssoIvod In 40 mI gIacIaI acofIc
acId wIfh consfanf sfIrrIng. Affor fho addIfIon, sfIr fho mIxfuro af room fomporafuro for
30 mIn durIng whIch fImo a soIId soparafos ouf. Hoaf fho mIxfuro furfhor on a sfoam-bafh
for 1 hr, durIng whIch porIod a cIoar soIufIon Is obfaInod. CooI fho fIask In Ico-bafh fIII a
soIId soparafos. !IIfor fho soIId on a Buchnor funnoI, wash wIfh wafor and dry. RocrysfaIIIzo
from hof aquoous ofhanoI. Tho yIoId Is 9.0 g, m.p. 174÷175
o
C.
ORGANIC PREPARATIONS 215
8.14.5 Preparation of 1, 2-Diphenyl-5-Nitrobenzimidazole
ThIs compound Is proparod by condonsIng 2-amIno-4-nIfrophonyIamIno wIfh bonzII tproparod
In SocfIon 8.8.1) In an acIdIc modIum.
Tho proparafIon Is carrIod ouf In fwo sfops:
Step A: PrepuruIion oj 2-umino-4-niIroJiphenyIumine
Procedure: In a 250 mI ÐrIonmoyor fIask, suspond 6 g 2, 4-dInIfrodIphonyIamIno In 50 mI
of propanoI and conc. ammonIum hydroxIdo soIufIon. Warm fho mIxfuro on a sfoam-bafh In
a hood and fo fho susponsIon add 18 g sodIum suIfIdo tNa
2
S.9H
2
O) In smaII porfIons, sfIrrIng
If confInuousIy. Hoaf fho mIxfuro for an addIfIonaI porIod of 30 mIn and fhon pour If In
160 mI coId wafor In a boakor. Immorso fho fIask In an Ico-bafh and crysfaIs soparafo ouf.
CoIIocf fho crysfaIs on a Buchnor funnoI. Ðry In aIr, rocrysfaIIIzo from hof wafor. Tho yIoId
Is 3.8 g, m.p. 131÷133
o
C.
Step B: PrepuruIion oj 1, 2-JiphenyI-5-niIrobenzimiJuzoIe
Procedure: In a 250 mI ÐrIonmoyor fIask pIaco 2 g of 2-amIno-4-nIfrodIphonyIamIno, 2 g of
bonzII In 40 mI of absoIufo ofhanoI and 2 mI conc. hydrochIorIc acId. RofIux fho mIxfuro on
a sfoam-bafh for 15 mIn. CooI and fIIfor fho producf undor sucfIon on a Buchnor funnoI and
wash wIfh coId ofhanoI. Tako 2 g of fhIs InformodIafo producf In a 100 mI round-boffomod
fIask oquIppod wIfh a rofIux condonsor. To fhIs add 12 mI of absoIufo propanoI and 4 mI of
conc. hydrochIorIc acId. RofIux fho mIxfuro for 2 hrs. CooI and fIIfor fho dark soIId on a
Buchnor funnoI. RocrysfaIIIzo for hof 95% ofhanoI, uso acfIvafod charcoaI. Tho yIoId Is
1.5 g, m.p. 181
o
C.
8.15 DIAZOTISATION
Tho procoss of formIng a dIazonIum compound from an approprIafo prImary aromafIc amIno
In fho prosonco of nIfrous acId Is caIIIod JiuzoIisuIion. Tho dIazonIum compounds aro
oxfromoIy usofuI In organIc synfhosos. ThIs Is duo fo fho facf fhaf fho dIazonIum group can
bo ropIacod by groups such as hydroxy, cyano, haIo and hydrogon wIfh groaf oaso. Many
compounds fhaf couId nof bo obfaInod by ofhor moans, aro oasIIy avaIIabIo fhrough
ropIacomonf of fho dIazonIum group. Tho roacfIon sfarfs by fho dIazofIsafIon of an amIno
group of an anIIIno usIng sodIum nIfrIfo and a mInoraI acId.
216 LABORATORY MANUAL OF ORGANIC CHEMISTRY
8.15.1 Preparation of p-Iodonitrobenzene
In fhIs proparafIon, p-nIfroanIIIno Is dIazofIsod and fhon froafod wIfh KI.
Procedure: In a 250 mI boakor pIaco a mIxfuro of 2.5 g p-nIfroanIIIno, 2 mI conc. suIfurIc
acId, 15 mI wafor and sfIr wIfh a gIass rod. Immorso a fhormomofor In fho fIask and koop
fho fIask In crushod Ico unfII fho fomporafuro IIos bofwoon 0 and 5
o
C. In anofhor boakor
dIssoIvo 1.3 g of sodIum nIfrIfo In 5 mI wafor and add fhIs soIufIon fo fho abovo anIIIno saIf
soIufIon sIowIy wIfh consfanf sfIrrIng and maInfaInIng fho fomporafuro boIow 5
o
C tNofo I).
!IIfor fho coId soIufIon and add fho fIIfrafo fo a soIufIon of 5 g pofassIum IodIdo In 15 mI of
wafor fakon In an ÐrIonmoyor fIask. !IIfor fho soIId fhus obfaInod and rocrysfaIIzo from
hof ofhanoI. Tho yIoId Is 3.6 g, m.p. 170
o
C.
Note ¡: Add a fow pIocos of crushod Ico fo fho roacfIon mIxfuro If nocossary fo maInfaIn fho
dosIrod fomporafuro.
Question
8.25 Why shouId fho fomporafuro bo maInfaInod boIow 5
o
C In fhIs proparafIon7
8.15.2 Preparation of p-Chlorotoluene (The Sandmeyer Reaction)
ThIs proparafIon consIsfs of fhroo sfops:
Step A: PrepuruIion oj cuprous chIoriJe
Cuprous chIorIdo Is fIrsf proparod by roducIng coppor suIfafo usIng sodIum suIfIfo In
fho prosonco of sodIum chIorIdo.
+

+ + +
2
2
3 2
2Cu 2CI SO H O

− +
+ +
2
1
2 CuCI SO 2H
ORGANIC PREPARATIONS 217
Procedure: ÐIssoIvo 30 g of cuprIc suIfafo tCuSO
4
. 5H
2
O) In 100 mI of wafor In a 500 mI
round-boffomod fIask by hoafIng. Add 10 g sodIum chIorIdo tNofo I). In anofhor ÐrIonmoyor
fIask dIssoIvo 7 g of sodIum bIsuIfIfo In 75 mI of wafor. Add fhIs soIufIon troducIng soIufIon)
fo fho hof coppor suIfafo soIufIon durIng 5 mIn. Shako woII and cooI fho fIask In Ico.
Step B: DiuzoIisuIion
Procedure: PIaco 11 g of p-foIuIdIno, 15 mI of wafor and 25 mI of conc. hydrochIorIc acId In
a 250 mI ÐrIonmoyor fIask and shako. Koop fho fIask In an Ico-bafh. Tho saIf p-foIuIdIno
hydrochIorIdo soparafos ouf. ÐIssoIvo 7 g sodIum nIfrIfo In 20 mI of wafor and add fhIs
soIufIon dropwIso fo fho amIno saIf koopIng fho fomporafuro bofwoon 0÷5
o
C. OccasIonaIIy
add Ico Info fho fIask. Affor fho addIfIon Is ovor, a cIoar soIufIon of fho soIubIo dIazonIum
saIf Is obfaInod tNofo II).Koop fho fIask In Ico.
Step C: The SunJmeyer reucIion
Procedure: Ðocanf fho supornafanf IIquId from fho coIorIoss soIId cuprous chIorIdo proparod
In tSfop A). Wash fho whIfo soIId wIfh coId wafor and fhon dIssoIvo In 45 mI conc.
hydrochIorIc acId. Pour fho coId dIazonIum saIf soIufIon sIowIy In fho Ico-coId cuprous
chIorIdo soIufIon wIfh consfanf shakIng. Tho mIxfuro InIfIaIIy bocomos vory fhIck tNofo
III). AIIow fho mIxfuro fo como fo room fomporafuro wIfh occasIonaI swIrIIng. Whon fho
fomporafuro roachos abouf 15
o
C, fho compIox sfarfs docomposIng wIfh fho ovoIufIon of
nIfrogon and an oII soparafos ouf. Warm fho confonfs fo 60
o
C on a wafor-bafh fo compIofo
fho docomposIfIon. Sfoam dIsfII fho mIxfuro unfII no moro oII passos ovor. Transfor fho
dIsfIIIafo fo a soparafory funnoI and romovo fho Iowor Iayor of p-chIorofoIuono. Wash If
wIfh 10% sodIum hydroxIdo soIufIon tNofo IV) and subsoquonfIy wIfh wafor. Ðry ovor
anhyd. magnosIum suIfafo, fIIfor and ovaporafo ofhor. ÐIsfII fho rosIduo and coIIocf
p-chIorofoIuono passIng ovor bofwoon 156÷160
o
C. Tho yIoId Is 10.6 g.
Notes ¡: On addIng sodIum chIorIdo a smaII procIpIfafo of basIc coppor chIorIdo may bo formod.
¡¡: Af fhIs sfago a smaII oxcoss of nIfrous acId shouId bo prosonf. A bIuo coIor shouId bo
obfaInod wIfh a sfarch IodIdo papor whon fouchod wIfh a drop of fho soIufIon.
¡¡¡: Ðuo fo fho prosonco of a doubIo saIf of p-CH
3
C
6
H
4
N
2
+
CI
÷
. CuCI.
¡V: To romovo any p-crosoI prosonf.
8.15.3 Preparation of o-Chlorobenzoic Acid (The Sandmeyer Reaction)
Tho acId Is obfaInod from anfhranIIIc acId by fho Sandmoyor roacfIon.
218 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: In a 250 mI ÐrIonmoyor fIask dIssoIvo 5 g anfhranIIIc acId In a mIxfuro of 7 mI
of conc. hydrochIorIc acId and 35 mI wafor. CooI fho soIufIon fo 5
o
C. In anofhor ÐrIonmoyor
fIask proparo a soIufIon of 2.5 g of sodIum nIfrIfo In 10 mI wafor and cooI fo 5
o
C. Add fhIs
soIufIon fo fho saIf of anfhranIIIc acId sIowIy and wIfh sfIrrIng koopIng fho fomporafuro af
5
o
C. Affor fho addIfIon Is compIofo aIIow fho dIazofIsod soIufIon fo cooI af 5
o
C.
ÐIssoIvo 9.3 g of coppor suIfafo and 8.6 g of sodIum chIorIdo In 20 mI of wafor In a 500
round-boffomod fIask. Hoaf fho mIxfuro fo boIIIng, fhon add 30 mI conc. hydrochIorIc acId
and 5 g of coppor furnIngs and confInuo hoafIng undor rofIux fIII fho soIufIon bocomos
coIorIoss. CooI fho cuprous chIorIdo soIufIon In Ico and add fho coId dIazofIsod soIufIon
sIowIy wIfh shakIng. AIIow fho soIufIon fo sfand In Ico wIfh froquonf shakIng for 1 hr. !IIfor
fho soIId and wash wIfh coId wafor. RocrysfaIIIzo from hof wafor. Tho yIoId Is 4.9 g, m.p.
139÷140
o
C.
8.16 PREPARATION OF DYES
An Imporfanf uso of dIazofIsafIon Is In fho proparafIon of dyos. Tho dIazonIum compound Is
coupIod wIfh anofhor aromafIc nucIous confaInIng an ortho or para dIrocfIng group. Ðyos
fInd appIIcafIons In Indusfry and as IndIcafors In fho Iaborafory.
8.16.1 Preparation of Methyl Orange
ThIs azo dyo Is proparod by coupIIng dIazofIsod suIfanIIIc acId wIfh N, N-dImofhyIanIIIno In
a woakIy acIdIc soIufIon. AnIIInos usuaIIy roquIro acIdIc modIum.
Procedure: ÐIssoIvo 4.8 g of suIfanIIIc acId In 50 mI of 2.5% sodIum carbonafo soIufIon In
an ÐrIonmoyor fIask by boIIIng. CooI fho soIufIon fo 15
o
C and fo fhIs add 1.9 g sodIum
nIfrIfo and sfIr. Pour If In a boakor confaInIng 25 g of crushod Ico and 5.0 mI conc.
hydrochIorIc acId. Soon a whIfo procIpIfafo of fho dIazonIum saIf soparafos ouf. In a socond
ÐrIonmoyor fIask mIx 3.2 mI of dImofhyIanIIIno and 2 mI gaIcIcaI acofIc acId fo dIssoIvo
amIno as Ifs saIf. Add fhIs soIufIon fo fho coId susponsIon of dIazofIsod suIfanIIIc acId wIfh
ORGANIC PREPARATIONS 219
confInuous sfIrrIng. Somo coupIIng fakos pIaco In fho acId modIum and fho dyo Imparfs rod
coIor fo fho soIufIon. Now add 35 mI of 10% sodIum hydroxIdo soIufIon fo produco an orango
coIorod sodIum saIf. SfIr woII wIfh a gIass rod and add 25 g sodIum chIorIdo. Hoaf fho
mIxfuro fo boIIIng, fhon cooI In an Ico-bafh for somo fImo. Tho dyo soparafos ouf as orango
crysfaIs. !IIfor, wash wIfh a IIffIo ofhanoI and dry. Tho yIoId Is 5÷6 g.
Question
8.26 In fho proparafIon of mofhyI orango, why Is suIfanIIIc acId convorfod Info Ifs sodIum
saIf7
8.16.2 Preparation of Phenolphthalein
PhonoIphfhaIoIn Is usod as IndIcafor In acId-baso fIfrafIons. If Is proparod by condonsIng
phfhaIIc anhydrIdo wIfh fwo moIocuIos of phonoI. If gIvos pInk coIor In aIkaIIno soIufIon.
Procedure: Tako 19 of phonoI In a Iargo fubo fo fhIs add 0.79 of phfhaIIc anhydrIdo and
mIx woII wIfh a gIass rod. Add abouf 10÷12 drops of conc. suIfurIc acId and sfIr woII wIfh a
fhormomofor. Hoaf fho vIscous mass for 4÷5 mIn af approxImafoIy 160
o
C. Pour fho hof
moIf Info 100 mI of wafor In a boakor. !IIfor fho soIId and wash wIfh coId wafor. WoIgh fho
dry sampIo.
220 LABORATORY MANUAL OF ORGANIC CHEMISTRY
8.16.3 Preparation of Fluorescein
ThIs dyo Is a condonsafIon producf of phfhaIIc anhydrIdo and fwo moIocuIos of rosorcInoI In
fho prosonco of anhydrous zInc chIorIdo cafaIysf.
Procedure: GrInd 5 g phfhaIIc anhydrIdo and 7.4 g rosorcInoI In a morfar. Transfor fho
mIxfuro fo a 250 mI ÐrIonmoyor fIask, Immorso a fhormomofor and hoaf fho fIask sIowIy fo
180
o
C on a sand-bafh. In fho moanfImo woIgh 2.3 g of anhyd. zInc chIorIdo tNofo I) In a
smaII sfopporod boffIo and add If fo fho roacfIon mIxfuro In smaII Iofs by sfIrrIng wIfh fho
fhormomofor affor oach addIfIon. ConfInuo hoafIng fho mIxfuro fIII If bocomos dark rod
and hIghIy vIscous tNofo II). CooI fho fIask fo abouf 90
o
C and fo fhIs add 70 mI wafor and
3.5 mI conc. hydrochIorIc acId. Hoaf agaIn fIII zInc saIfs havo dIssoIvod. !IIfor fho coIorod
saIf on a Buchnor funnoI, wash wIfh wafor, draIn woII and dry In an ovon af 100
o
C. Tho
yIoId Is 8.6 g.
Notes ¡: If ZnCI
2
appoars moIsf, dry by fusIng If In a procoIaIn dIsh In an ovon.
¡¡: ThIs may fako abouf 40÷50 mIn.
Question
8.27 Why Is anhydrous zInc chIorIdo noodod In fho proparafIon of fIuoroscoIn dyo7
ORGANIC PREPARATIONS 221
8.16.4 Preparation of Eosin
ÐosIn Is a fofrabromo dorIvafIvo of fIuoroscoIn. Ifs bromInafIon In fho prosonco of oxcoss
bromIno Ioads fo oosIn.
Procedure: Tako 5 g of fho drIod fIuoroscoIn In a 250 mI ÐrIonmoyor fIask and add 25 mI of
ofhanoI and shako. WoIgh 10.8 g of bromIno tNofo I) and fransfor fo a droppIng funnoI. Add
bromIno sIowIy fo fIuoroscoIn soIufIon wIfh consfanf sfIrrIng. Whon abouf haIf of fho bromIno
has boon addod a soIId appoars tNofo II). Moro fofrabromofIuoroscoIn procIpIfafos ouf as
fho addIfIon Is confInuod. AIIow fho mIxfuro fo sfand for 1 hr af room fomporafuro. !IIfor
fho soIId on a Buchnor funnoI, wash fwIco wIfh ofhanoI and dry In an ovon af 100
o
C. Tho
yIoId of fho orango dyo Is 7.2 g.
Notes ¡: Work wIfh bromIno Is fho fumo hood.
¡¡: ThIs Is so bocauso dIbromofIuoroscoIn Is soIubIo In ofhanoI.
Questions
8.28 Why do you nof obsorvo fho ovoIufIon of HBr gas durIng bromInafIon7
8.29 Why do fhoso four pIacos In fIuoroscoIn gof bromInafod7
8.16.5 Preparation of Methyl Red
ThIs dyo Is obfaInod by coupIIng N, N-dImofhyIanIIIno wIfh dIazofIsod anfhranIIIc acId. ThIs
dyo Is usod as an IndIcafor.
222 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: ÐIssoIvo 6.5 g of crysfaIIIzod anfhranIIIc acId In a mIxfuro of 5 mI of conc.
hydrochIorIc acId and 15 mI of wafor. !IIfor fho soIufIon fo romovo any suspondod parfIcIos.
Pour fho soIufIon In a 250 mI boakor Immorsod In an Ico-bafh. To fho boakor add 20 g of
crushod Ico and 8 mI of conc. hydrochIorIc acId and sfIr confInuousIy wIfh a gIass rod. Whon
fho fomporafuro of fho soIufIon roachos 2÷3
o
C, add a coId soIufIon of 3.5 g of sodIum nIfrIfo
proparod soparafoIy In 10 mI wafor. tNofo I). If Is ossonfIaI fhaf durIng fhIs addIfIon fho
fomporafuro romaIns boIow 5
o
C tNofo II). To fho rosuIfIng soIufIon of fho dIazonIum saIf
of anfhranIIIc acId add 8.5 g t8.9 mI) of dImofhyIanIIIno sIowIy wIfh vIgorous sfIrrIng. Affor
fho addIfIon Is compIofo, confInuo sfIrrIng for an addIfIonaI porIod of 15 mIn maInfaInIng
fho fomporafuro boIow 5
o
C tNofo III). Koop fho roacfIon mIxfuro asIdo.
ÐIssoIvo 6.8 of sodIum acofafo In 12 mI wafor and add 6 mI of fhIs soIufIon fo fho abovo
roacfIon mIxfuro wIfh confInuous cooIIng and sfIrrIng. AIIow fhIs mIxfuro fo sfand ovornIghf
In an Ico-box af a fomporafuro of nof abovo 7
o
C. Thon add fho romaInIng of fho sodIum
acofafo soIufIon wIfh sfIrrIng fo fho cooIod mIxfuro. SfIr for ono hour and agaIn aIIow fo
sfand for 24 hrs and durIng fhIs porIod aIIow fho fomporafuro fo rIso abovo 25
o
C. To fhIs
roacfIon mIxfuro add 2.5 mI of a 40% sodIum hydroxIdo soIufIon wIfh sfIrrIng. !IIfor off fho
soIId af fho pump. Wash If wIfh wafor foIIowod by 10% acofIc acId and fInaIIy wIfh wafor.
Ðry fho dyo and fhon suspond If In 40 mI of mofhanoI In a round-boffomod fIask. SfIr fho
mIxfuro and rofIux for 1 hr. CooI fho fIask In Ico whoroby mofhyI rod dyo procIpIfafos ouf.
!IIfor fho soIId and dry, yIoId Is 7.5 g, m.p. 181÷182
o
C.
Notes ¡: Chock wIfh a sfarch papor.
¡¡: OfhorwIso farry producfs aro formod.
¡¡¡: Add Ico If nocossary.
8.17 THE PINACOL-PINACOLONE REARRANGEMENT
PInacoI t2, 3-dImofhyI -2, 3-bufanoI) whon froafod wIfh conc. suIfurIc acId roarrangos fo
pInacoIono t3, 3-dImofhyI-2-bufanono). Such a roarrangomonf Is known as fho Beckmunn
reurrungement and procoods accordIng fo fho foIIowIng mochanIsm:
ORGANIC PREPARATIONS 223
Tho kofono has boon usod for fho proparafIon of pIvaIIc acId by oxIdafIon wIfh sodIum
hypobromIfo.
Tho proparafIon Is carrIod ouf In fwo sfops:
Step A: PrepuruIion oj pinucoI
Procedure: RoducfIon of acofono wIfh mosf roducIng agonfs yIoIds IsopropyI aIcohoI and a
smaII quanfIfy of pInacoI as by-producf. Howovor, roducfIon In fho prosonco of amaIgamafod
magnosIum yIoIds a consIdorabIo amounf of fho bImoIocuIar roducfIon producf, pInacoI.
PInacoI Is IsoIafod as Ifs haxahydrafo.
Procedure: !If a 500 mI dry fwo-nockod fIask tNofo I) wIfh a rofIux condonsor, a droppIng
funnoI and pIaco 8 g of magnosIum furnIngs and 100 mI dry bonzono. Tako a soIufIon of 9 g
of morcurIc chIorIdo In 75 mI dry acofono In fho droppIng funnoI. Add abouf 20 mI soIufIon
fo fho fIask. If fho roacfIon doos nof sfarf ImmodIafoIy warm fho fIask on a sfoam-bafh.
CooI fho fIask In an Ico-bafh In caso fho roacfIon bocomos foo vIgorous. Add fho romaInIng
soIufIon from fho droppIng funnoI sIowIy. Affor fho addIfIon Is compIofo, hoaf fho fIask on
a sfoam-bafh for 1 hr wIfh occasIonaI shakIng. If fho formafIon of soIId magnosIum pInacoIafo
makos sfIrrIng dIffIcuIf, broak fho Iumps wIfh a gIass rod. Af fho ond of 1 hr pour 20 mI of
wafor fhrough fho condonsor and boII fho mIxfuro for 30 mIn wIfh froquonf sfIrrIng. ThIs
brIngs abouf hydroIysIs of magnosIum pInacoIafo fo magnossIum hydroxIdo and pInacoI
dIssoIvos In bonzono-acofono mIxfuro. !IIfor fho hof soIufIon and rofurn fho procIpIfafo of
magnossIum hydroxIdo fo fho fIask and rofIux agaIn for 15÷20 mIn affor addIng 50 mI of
ordInary bonzono. !IIfor fho soIufIon agaIn. Tho combInod bonzono soIufIon Is ovaporafod
In a boakor on a sfoam-bafh fo 1/3 of Ifs voIumo. Thon add 15 mI wafor and cooI woII In an
Ico-bafh. PInacoI hydrafo soparafos as an oII whIch ImmodIafoIy soIIdIfIos. !IIfor on a Buchnor
funnoI, wash wIfh coId bonzono and draIn. RocrysfaIIIzo fho soIId from hof wafor tNofo II).
Tho yIoId Is 18÷20 g, m.p. 46÷47
o
C.
Notes ¡: A fhroo-nockod fIask may Insfoad bo usod.
¡¡: PInacoI hydrafo Is hIghIy soIubIo In hof wafor. If fho soIufIon Is foo dIIufo fo pormIf
crysfaIIIzafIon, ovaporafo somo wafor.
Step B: PrepuruIion oj pinucoIone
PInacoI roarrangos fo pInacoIono t3, 3-dImofhyI-2-bufanono) In fho prosonco of an
acId as cafaIysf.
224 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: ÐIssoIvo 15 g of pInacoI hydrafo In a soIufIon of 60 mI wafor and 15 mI conc.
suIfurIc acId In a 200 mI round-boffomod fIask oquIppod wIfh a rofIux condonsor. Add a fow
boIIIng chIps ropIaco fho condonsor and rofIux gonfIy for 15 mIn. An oIIy uppor Iayor of
pInacoI bogIns fo form as boIIIng progrossos. CooI fho fIask and add 25 mI wafor and sof up
for dIsfIIIafIon. ÐIsfII pInacoIono whIch passos ovor aIong wIfh somo wafor. Transfor fho
dIsfIIIafo fo a soparafory funnoI and soparafo pInacoIono from wafor. Ðry ovor anhyd. caIcIum
chIorIdo. PurIfy fho producf by dIsfIIIafIon, usIng a fracfIonafIng coIumn. Tho yIoId Is 15.0 g,
b.p. 106
o
C.
Somo 2, 3-dImofhyI-1,3-bufadIono tb.p. 70
o
C) aIso dIsfIIs ovor. To romovo If, hoaf fho
fIask sIowIy In fho bogInnIng and dIscard 1÷2 mI of fho fororun.
Questions
8.30 ÐxpIaIn fho mochanIsm for fho fromafIon of 2-3-dImofhyI-1, 3-bufadIono In fho
proparafIon of pInacoIono.
8.31 !rom whIch gIycoI can fho foIIowIng compound bo synfhosIzod by a pInacoI-pInacoIono
roarrangomonf7 WrIfo fho mochanIsm.
8.18 CHROMATOGRAPHIC METHODS
A wIdoIy usod fochnIquo for fho soparafIon of a dosIrod compound from Ifs ImpurIfIos or a
mIxfuro of compounds Info Ifs compononfs Is chromafography. Tho namo fo fhIs fochnIquo
was gIvon by fho RussIan chomIsf, Tswoff af fho furn of fho confury. Ho usod If for fho
soparafIon of coIorod compounds tchromu, coIor). AnaIogous fo oxfracfIon, chromafography
aIso doponds on fho prIncIpIo of phaso dIsfrIbufIon. In fhIs fochnIquo fho compononfs of a
mIxfuro aro soIocfIvoIy adsorbod on a sfafIonary phaso and aro fhon dIsIodgod from If by a
mobIIo phaso.
VarIous fypos of chromafographIc mofhods aro cIassIfIod accordIng fo fho physIcaI
sfafos of fho dIfforonf phasos InvoIvod, i.c., sfafIonary and mobIIo. Tho mobIIo phaso can bo
gas or IIquId, whIIo fho sfafIonary phaso can bo soIId or IIquId. Whon fho soparafIon InvoIvos
parfIfIonIng bofwoon fwo IIquId phasos tono of fhom absorbod on fho soIId phaso) fhon If Is
roforrod fo as purtltlon chromutogruphy or llquld-llquld chromutogruphy. Thoso In
whIch soIId-IIquId InforacfIon fakos pIaco aro cIassIfIod as coIumn Chromutogruphy, hlgh
ORGANIC PREPARATIONS 225
pressure llquld chromutogruphy and lon exchunge. In gus llquld chromutogruphy
tgIc), on fho ofhor hand, fho mobIIo phaso Is a gas whIIo fho sfafIonary phaso Is a IIquId
coafod on a soIId.
Gel chromutogruphy or gel Illtrutlon Is a caso of an oxcIusIon chromafography In
whIch fho soIId phaso Is a goI and soparafIon fakos pIaco on fho basIs of moIocuIar sIzo.
8.18.1 Column Chromatography
In fhIs fypo of chromafography fho soparafIon Is affocfod by adsorpfIon on a soIId sfafIonary
phaso. SovoraI fypos of forcos fhaf causo InforacfIons of fho subsfanco wIfh fho soIId aro
hydrogon-bondIng, van dor WaaIs forcos, oIocfrosfafIc InforacfIons. A cyIIndrIcaI gIass coIumn
of fho fypo shown boIow Is ompIoyod fo soparafo a mIxfuro by coIumn chromafography. To
pack a coIumn, fIrsf cIoan If fhoroughIy and dry. Now posIfIon If vorfIcaIIy on an Iron-sfand
wIfh fho hoIp of a cIamp. CIoso fho sfopcock and fIII fho coIumn wIfh an approprIafo soIvonf.
Insorf a smaII pIug of gIass wooI fo fho boffom of fho coIumn. Pour somo dry sand so fhaf If
forms a 1 cm Iayor on fho fop of fho gIass wooI. Add sIowIy fho adsorbonf i.c., aIumIna or a
sIurry tIf If Is sIIIca) on fho fop of fho coIumn wIfh consfanf fappIng fho sIdos of fho coIumn.
An udsorbent Is a porous soIId fhaf can rofaIn bofh soIufo and soIvonfs. Opon fho sfopcock
and aIIow fho soIvonf fo draIn ouf sImuIfanoousIy af a rafo of 1÷2 drops por soc. Whon aII
fho adsorbonf has boon addod, Infroduco moro sand fo form a 1 cm Iayor af fho fop of fho
packIng. Tho coIumn Is now roady for uso. Tho adsorbonfs of common choIco aro aIumIna,
sIIIca goI, coIIuIoso, charcoaI, ofc. SovoraI consIdorafIons govorn fho choIco of an adsorbonf.
If shouId bo InsoIubIo In fho soIvonf and musf nof roacf wIfh fho subsfanco fo bo soparafod.
Tho mIxfuro fo bo soparafod Is fhon fakon In a mInImum amounf of soIvonf and Infroducod
from fho fop of fho coIumn. Thon a suIfabIo soIvonf tmobIIo phaso) Is aIIowod fo porcoIafo
fhrough fho coIumn. Tho procoss Is known as elutlon.
If Is cusfomary fo uso a roIafIvoIy non-poIar soIvonf In fho bogInnIng. Tho adsorpfIon
doponds on bofh fho nafuro of fho soIvonf and fho adsorbonf. !or offocfIvo soparafIon fho
oIufIng soIvonf musf bo sIgnIfIcanfIy Ioss poIar fhan fho compononfs of fho mIxfuro. In caso
fho soIvonf Is moro poIar and sfrongIy adsorbod fhan fho compononfs of fho mIxfuro wIII
romaIn In fho mobIIo phaso and IIffIo If any, soparafIon wIII fako pIaco. If Is aIso ossonfIaI
fhaf fho mIxfuro Is soIubIo In fho soIvonf, ofhorwIso If wIII romaIn pormanonfIy adsorbod
on fho adsorbonf. PoIar soIvonfs aro usod for oIufIng sfrongIy adsorbod compononfs whIIo
non-poIar soIvonfs aro usod for woakIy adsorbod compononfs of a mIxfuro. An approxImafo
ordor of IncroasIng poIarIfy of somo common soIvonfs Is as foIIows: pofroIoum ofhor, hoxano,
carbon fofrachIorIdo, foIuono, chIoroform, and wafor. A mIxfuro of fwo soIvonfs may bo
moro usofuI for soparafIon In many Insfancos.
226 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Fig. 8.2 A packed adsorption column.
(a) Separation of anthracene from anthracene picrate
Anfhracono pIcrafo Is proparod from anfhracono and pIcrIc acId. If Is a IoosoIy bound
compound of fho fwo roagonfs. Tho forcos hoIIdng fhom fogofhor aro woak. Whon soIufIon
of fho compIox Is addod on fho coIumn pIcrIc acId Is sfrongIy adsorbod whIfo anfhracono Is
adsorbod onIy woakIy. ThIs as a rosuIf, passos rapIdIy fhrough fho coIumn. TochnIcaI grado
anfhracono Is offon coIorod and fhIs sorvos a mofhod for Ifs purIfIcafIon.
Procedure: !Ix an approprIafo cIoanod gIass coIumn on an Iron-sfand vorfIcaIIy. Pack fho
coIumn wIfh 50 g of aIumIna In fho mannor doscrIbod oarIIor usIng bonzono as soIvonf.
Soparafo anfhracono pIcrafo and dry If. AppIy 1 g of fhIs sampIo dIssoIvod In mInImum
quanfIfy of bonzono fo fho coIumn wIfh fho hoIp of a pIpoffo. Opon fho sfopcock fo pormIf
fho soIvonf fo fIow ouf. Tho soIufo wIII bo adsorbod on fho adsorbonf. Wash fho sIdo of fho
coIumn wIfh abouf 2 mI of bonzono, and aIso aIIow If fo run down tNofo I). Add 100÷150 mI
of bonzono and oIufo anfhracono tNofo II). Whon aII fho anfhracono has boon washod
down, wash fho coIumn wIfh 50÷100 mI of ofhanoI fo oIufo pIcrIc acId and coIIocf fho oIufanf
In a soparafo fIask. Ðvaporafo fIrsf fracfIon undor roducod prossuro fo obfaIn anfhracono as
coIorIoss, hIghIy fIuorosconf pIafos of m.p. 216
o
C. Rocord fho woIghf of anfhracano and
doformIno fho fofaI rocovory.
ORGANIC PREPARATIONS 227
Notes ¡: Ðo nof aIIow fho coIumn fo gof dry, If wIII dovoIop cracks.
¡¡: Tho compIofIon of oIufIon can bo porIodIcaIIy chockod by oxposIng fho coIumn fo u.v. IIghf.
Anfhracono shows a sfrong fIuoroscono.
8.18.2 Thin Layer Chromatography (TLC)
ThIn Iayor chromafography InvoIvos fho samo prIncIpIo as coIumn chromafography. If Is a
form of soIId-IIquId adsorpfIon chromafography In whIch fho sfafIonary phaso Is sproad on
a gIass pIafo. IzmaIIov and ShraIbor In 1938 dovoIopod fhIs fochnIquo. Howovor, If was duo
fo fho offorfs of SfahI t1958) fhaf fhIs fochnIquo was uIfImafoIy accopfod as a now modorn
fochnIquo of anaIyfIcaI chomIsfry. ThIs mofhod Is sImpIo, rapId In soparafIon and vory
offIcIonf. Somo sopcIaI grados of adsorbonfs aro usod In TLC. Thoro aro dIfforonf ways of
coafIng fho gIass pIafos wIfh an adsorbonf such as pourIng, dIppIng, sprayIng. Tho soIId
adsorbonf Is sproad In a fhIn Iayor t0.25 mm fhIcknoss) on a gIass pIafo wIfh fho hoIp of a
sproador. Tho samo soIId adsorbonfs usod In coIumn chromafography can bo usod horo,
howovor, sIIIca and aIumIna aro mosf common. If Is aIso moro fIno and Is mIxod wIfh a
smaII amounf of "blnder", for Insfanco, pIasfor of parIs or caIcIum suIfafo, so fhaf fho
adsorbonf doos nof fIako off on dryIng fho pIafo. Tho sampIo Is appIIod as a soIufIon In a
non-poIar soIvonf af ono ond of fho pIafo In fho form of a symmofrIcaI spof tuso a syrIngo or
a capIIIary fubo) and fho spofs drIod. If Is offon nocossary fo ropoaf fhIs procoss fo gof
sovoraI mIIIIgrams of fho sampIo on fho pIafo. Thoroforo uso 2÷3 succossIvo appIIcafIons
for oach spof. Tho pIafo Is fhon drIod and pIacod In a chambor safurafod wIfh fho soIvonf.
SoIvonf for dovoIopmonf Is soIocfod on fho basIs of fho nafuro of fho compononfs. Ðo
nof movo or dIsfurb fho chambor durIng dovoIopmonf. Tho varIous compononfs aro fhon
soparafod dopondIng on fho proforonfIaI adsorpfIon on fho pIafo. Affor fho soIvonf has
movod a dIsfanco of approxImafoIy 10 cm on fho pIafo, fho pIafo Is fakon ouf and drIod. Tho
dofocfIon of spofs on fho chromafogram can bo vIsuaIIzod by a numbor of roagonfs. !or
Insfanco, suIfurIc acId, pofassIum pormanganafo soIufIon, p-anIsaIdohydo ofc. can bo sprayod
on fho pIafo and fho spofs aro rovoaIod as coIorod compounds. IodIno Is anofhor roagonf
whIch Is wIdoIy usod. In fhIs fho drIod pIafo Is pIacod In a cIosod confaInor confaInIng somo
IodIno crysfaIs. Tho IodIno vapors aro adsorbod Info fho aroas of fho pIafo confaInIng organIc
compounds and brown sporfs appoar duo fo fho formafIon of IodIno chargo-fransfor compIoxos.
SomofImo oxposuro of fho pIafo fo u.r. IIghf pormIfs IocafIon of fho spofs for compounds
fhaf fIuorosco.
!ndor a gIvon sof of condIfIons tadsorbonf, soIvonf, pIafo fhIcknoss, ofc.) TLC fochnIquo
can bo usod for IdonfIfIcafIon purposo aIso. !or fhIs purposo R
!
vaIuo whIch Is fho rafIo of
fho dIsfanco fravoIIod by fho subsfanco from fho orIgIn fo fho dIsfanco fravoIIod by fho
soIvonf from fho orIgIn Is moasurod.
R
F
=
fronf soIvonf fho by fravoIIod ÐIsfanco
fronf subsfanco fho by fravoIIod ÐIsfanco
Tho appIIcafIon of fhIs fochnIquo Is domonsfrafod by fho foIIowIng fwo oxporImonfs:
228 LABORATORY MANUAL OF ORGANIC CHEMISTRY
(a) Separation of green leaf pigments
Groon Ioavos offon confaIn chIorophyIIs, carofonoIds and xanfhophyIIs. On soparafIon fhoy
appoar as coIorod spofs.
Procedure: In a morfar pIaco 15 mI of a mIxfuro of pofroIoum ofhor and ofhanoI t2 : 1) and
a fow groon Ioavos tNofo I). Crush fho Ioavos wIfh a posfIo. Transfor fho oxfracf wIfh a
pIpoffo fo a soparafory funnoI. SwIrI tNofo II) fho oxfracf wIfh an oquaI voIumo of wafor.
ÐIscard fho Iowor aquoous Iayor. Ropoaf fho washIng fwIco wIfh 5 mI porfIons of wafor.
WashIng wIfh wafor sorvos fo romovo ofhanoI and ofhor wafor soIubIo maforIaI. Transfor
fho oxfracf fo a smaII ÐrIonmoyor fIask and dry ovor 2 g of anhyd. sodIum suIfafo. !IIfor
and conconfrafo fho soIufIon If nocossary by a sfroam of dry nIfrogon. PIaco a smaII spof
wIfh fho hoIp of a capIIIary fubo on a 10 cm TLC pIafo. Tho spofs musf bo abovo fho IovoI of
fho soIvonf. AIIow fho spof fo dry and dovoIop fho chromafogram usIng chIoroform as a
dovoIopIng soIvonf. A wIdo-moufhod boffIo t!Ig. 8.3) can bo usod In pIaco of a chambor. A
foIdod pIoco of fIIfor papor may bo pIacod Info fho boffIo fo maInfaIn a safurafod afmosphoro
In fho boffIo.
Fig. 8.3 Arrangement for developing a TLC plate.
Ðry fho pIafo agaIn, and If wIII bo possIbIo fo obsorvo as many as oIghf coIorod spofs.
ÐoformIno fho R
!
vaIuos. In fho ordor of docroasIng R
!
vaIuos, fho spofs may bo IdonfIfIod
as carofonos t2 spof, orango), chIorophyII a t1 spof, bIuo and groon), chIorophyII b t1 spof,
groon) and xanfhophyIIs t4 spofs, yoIIow).
Notes ¡: Groon Ioavos or spInach may bo usod.
¡¡: ShakIng may Ioad fo omuIsIon formafIon.
(b) Separation of 2, 4-dinitrophenylhydrazones
Tho 2, 4-dInIfrophonyIhydrazono dorIvafIvo of aIdohydos and kofonos aro coIorod and can
bo soparafod and oasIIy vIsuaIIzod on TLC pIafos.
Procedure: Proparo 2, 4-dInIfrophonyIhydrazonos of acofono, bonzaIdohydo and
acofophonono accordIng fo fho procoduro gIvon oarIIor. Coaf a 10 cm pIafo usIng sIIIca goI.
ORGANIC PREPARATIONS 229
Proparo a soIufIon In chIoroform or dIoxano by mIxIng 10 mg of oach hydrazono. Spof fho
TLC pIafo wIfh fhIs mIxfuro soIufIon as woII as appIy ono spof oach of fho IndIvIduaI puro
hydrazono for comparIson. AIIow fho spofs fo dry and fhon pIaco fho pIafo In a dovoIopIng
chambor confaInIng bonzono: PofroIoum ofhor t3 : 1) soIvonf. ÐovoIop fho chromafogram.
Romovo fho pIafo from fho chambor, mark fho posIfIon of fho soIvonf fronf and fho coIorod
spofs. AIIow fho pIafo fo dry. ÐsfImafo fho R
!
vaIuos and IdonfIfy fho soparafIon of fho
mIxfuro wIfh fho hoIp of fho sfandard spofs.
8.18.3 Paper Chromatography
Papor chromafography Is sImIIar fo fhIn Iayor chromafography. In fhIs fochnIquo a smaII
spof of fho sampIo Is pIacod noar ono ond of a sfrIp of fIIfor papor. Tho papor sfrIp Is
suspondod In a jar In such a way fhaf fho ond of fho papor sfrIp Is Immorsod In fho dovoIopIng
soIvonf. Tho sampIo Is soparafod Info IndIvIduaI spofs as fho soIvonf asconds fho papor. In
fhIs caso a dIsfrIbufIon fakos pIaco bofwoon wafor tadsorbod by fho fIIfor papor fo an oxfonf
of 20%) and fho mobIIo soIvonf. If Is for fhIs roason If Is aIso roforrod fo as IIquId-IIquId
parfIfIon chromafography. Tho dIfforonf compounds may bo IdonfIfIod by caIcuIafIng fho R
!
vaIuos. Papor chromafography Is usofuI for poIar moIocuIos IIko amIno acIds. Tho IndIvIduaI
spofs of amIno acIds aro vIsuaIIzod by sprayIng wIfh nInhydrIn soIufIon t0.1% soIufIon In
95% ofhanoI) and a bIuo-vIoIof coIor Is producod. Tho coIor formIng roacfIon fakos pIaco as
foIIows:
230 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Mosf of fho amIno acIds gIvo bIuo coIor toxcopf proIIno whIch gIvos a yoIIow coIor) If
IndIcafos fhaf fho coIorod producf formod Is fho samo In fhIs roacfIon.
(a) Separation of a mixture of =-amino acids
Papor chromafography Is a vaIuabIo fooI for fho soparafIon of =-amIno acIds as fhoy mIgrafo
af dIfforonf rafos.
Procedure: !rom Whafmann No 1 fIIfor papor, cuf a sfrIp moasurIng 30 × 10 cm. Ðraw a
IIno wIfh a poncII abouf 3 cm from ono odgo. Proparo amIno acId soIufIons by dIssoIvIng
120 mg oach of gIycIno, proIIno, phonyIaIanIno, IoucIno and asparfIc acId In 20 mI of wafor.
Spof fho papor wIfh fho mIxfuro of fho abovo amIno acIds and aIso puf ono spof oach of fho
IndIvIduaI acId abouf 1.5 cm aparf. Tho spof shouId bo 2÷3 mm In dIamofor. If If Is foo Iargo
If may Ioad fo poor rosoIufIon durIng dovoIopmonf. AIIow fho spofs fo dry. !asfon fho papor
wIfh cIIps and Insorf If Info a gIass cyIIndor confaInIng fho dovoIopIng soIvonf tn-bufanoI :
gIacIaI acofIc acId : wafor rospocfIvoIy In a rafIo of 4 : 1 : 5). Mako suro fho papor doos nof
fouch fho sIdos of fho cyIIndor and fho sampIos spofs aro abovo fho IovoI of fho soIvonf. Tho
soIvonf wIII rIso by capIIIary acfIon. Whon fho soIvonf fronf has mIgrafod fwo fhIrds fho
Iongfh of fho papor, romovo fho papor and mark fho posIfIon of fho soIvonf fronf. Ðry fho
chromafogram. Now spray If IIghfIy buf ovonIy wIfh nInhydrIn soIufIon and dry If agaIn.
Hoaf fho chromafogram In an ovon af 105
o
C for 15 mIn, whoroby fho coIors aro vIsIbIo.
Mark fho posIfIons of fho spofs wIfh a poncII and osfImafo fho R
!
vaIuos.
Questions
8.32 Whaf facfors govorn fho choIco of a soIvonf In coIumn chromafography7
8.33 Why do IodIno vapors yIoId coIorod spofs on TLC7
8.34 Why shouId fho InIfIaI spofs of amIno acIds musf nof bo foo Iargo7
8.19 POLYMERIZATION
A poIymor may bo doscrIbod as a Iargo moIocuIo formod by IInkIng fogofhor a numbor of
smaIIor moIocuIos. Thoso smaIIor moIocuIos havo Iow moIocuIar woIghfs and aro joInod by
covaIonf bonds. Tho smaIIor unIf Is caIIod a monomer.
Monomor tMonomor)
n
tA polymer)
Thoso poIymors In whIch fho fwo monomors aro bondod ond-fo-ond In a IInoar mannor
usuaIIy dIssoIvo, bocomo soff whon hoafod and can bo mouIdod aro roforrod fo as
thermoplustlc. On fho ofhor hand, If fho poIymor chaIns aro IInkod fogofhor af sovoraI
poInfs, fho poIymor Is ono Iargo fhroo-dImonsIonaI nof-work, InsoIubIo and InfusIbIo, and
ORGANIC PREPARATIONS 231
cannof bo mouIdod, such poIymors aro caIIod thermosettlng. Thoso poIymors aro crosod-
IInkod poIymors. Tho procoss of makIng hIgh moIocuIar woIghf compounds Is saId fo bo
polymerlzutlon. Such a procoss can bo InIfIafod by an IonIc or radIcaI roacfIon. Two fypos
of poIymors aro rocognIzod: ta) addIfIon tb) condonsafIon poIymors.
PoIymors, nowadays, aro nof dIffIcuIf fo proparo bocauso of fho oasy avaIIabIIIfy of fho
raw maforIaI. Tho synfhofIc poIymors aro mado from smaIIor moIocuIos by chomIcaI moans.
Thoy aro aIso roforrod fo as mun-mude polymers.
8.19.1 Preparation of Phenol-Formaldehyde Resin
Tho poIymors usod In Indusfry aro aIso somofImo roforrod fo as reslns.
!ormaIdohydo condonsos roadIIy wIfh phonoI In fho prosonco of a cafaIysf af fho
o- and p-posIfIons. Tho rosIn so obfaInod Is caIIod 'Novoluc` havIng a moIocuIar woIghf
bofwoon 1200 and 1500.
Procedure: In a 250 mI round-boffomod fIask fIffod wIfh a rofIux condonsor pIaco 65 g of
phonoI, 46 g of 37% aq. formaIdohydo soIufIon tformaIIn) and 0.5 g oxaIIc acId. RofIux for an
addIfIonaI porIod of 1 hr. Tho mIxfuro bocomos vIscous. Add 150 mI of wafor and cooI fho
fIask In Ico. AIIow fho mIxfuro fo sfand for somo fImo fhon docanf off fho supornafanf
IIquId. Tho rosIn Is obfaInod as a pasfy mass. Tho yIoId Is 65 g. Wafor can bo romovod from
fho rosIn af fho pump fIII If bocomos a brIffIo soIId.
8.19.2 Preparation of Thiokol Rubber
A group of synfhofIc rubbors aro known whIch do nof oxacfIy approxImafo nafuraI rubbor.
Thoso subsfancos aro caIIod thlokols. Thoso rubbors aro proparod from a dIhaIo organIc
compound and sodIum poIysuIfIdo tusuaIIy Na
2
S
4
).
Procedure: In a 100 mI boakor dIssoIvo 2 g sodIum hydroxIdo In 50÷60 mI of warm wafor.
BoII fho soIufIon and fo fhIs add In smaII Iofs wIfh consfanf sfIrrIng 4 g of powdorod suIfur
tNofo I). ÐurIng addIfIon and sfIrrIng fho yoIIow soIufIon furns dark brown. Affor 5 mInufos,
aIIow fho soIufIon fo cooI and docanf fho dark brown IIquId from fho undIssoIvod suIfur.
Add 10 mI of 1, 2-dIchIoroofhano tofhyIono chIorIdo) wIfh sfIrrIng. Warm fho mIxfuro fo
60÷70
o
C and sfIr for an addIfIonaI porIod of 20 mIn whIIo rubbor poIymor soparafos ouf as a
232 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Iump af fho boffom. Pour ouf fho IIquId from fho boakor In fho sInk and coIIocf fho fhIokoI
rubbor. Wash If fhoroughIy wIfh wafor undor fho fap. Ðry In fho foIds of fIIfor papors. Tho
yIoId Is abouf 1.5 g. ÐoformIno fho soIubIIIfy of fho poIymor In bonzono, acofono, 5% suIfurIc
acId and nIfrIc acId.
Note ¡: If somo suIfur romaIns undIssoIvod fIIfor fho soIufIon.
8.19.3 Polymerization of Styrene
PoIymorIzafIon of sfyrono fo poIysfyrono Is an oxampIo of addIfIon poIymorIzafIon.
PoIysfyrono Is proparod by a froo radIcaI poIymorIzafIon usIng bonzoyI poroxIdo as a radIcaI
InIfIafor.
Trado namo for poIysfyrono Is thermocole.
Procedure: In a 100 mI soparafory funnoI pour 15 mI of commorcIaI sfyrono and shako
wIfh 25 mI of wafor and 5 mI of 10% sodIum hydroxIdo soIufIon. ÐIscard fho aquoous Iayor
and wash fho sfyrono Iayor fhrIco wIfh 10 mI porfIons of wafor. Ðry If ovor anhyd. caIcIum
chIorIdo In a smaII ÐrIonmoyor fIask. ThIs procoss romovos fho anfIoxIdanf usuaIIy 2, 6-dI
tcrt-bufyIphonoI addod fo sfabIIIzo sfyrono.
Ðocanf sfyrono from fho ÐrIonmoyor fIask Info a boIIIng fubo, add 0.3 g bonzoyI poroxIdo
and 25 mI foIuono. AIIow fho fubo fo sfand In a boakor of boIIIng wafor maInfaInod af
90÷95
o
C. Romovo fho fosf fubo affor 1 hr and aIIow If fo cooI fo room fomporafuro. Pour fho
soIufIon Info 200 mI of mofhyI aIcohoI confaInod In a boakor. !IIfor fho whIfo procIpIfafo of
poIysfyrono on a Buchnor funnoI and wash wIfh 50 mI of mofhyI aIcohoI and dry In aIr.
ÐoformIno fho soIubIIIfy of poIysfrono In bonzono, ofhyI aIcohoI, carbon fofrachIorIdo and
wafor.
Question
8.35 How doos sodIum hydroxIdo romovo fho anfIoxIdanf from sfyrono7
ORGANIC PREPARATIONS 233
8.19.4 Preparation of Nylon-66
NyIon-66 Is a fypIcaI condonsafIon poIymor. If Is proparod by condonsIng
hoxamofhyIonodIamIno wIfh adIpIc acId In fho prosonco of sodIum hydroxIdo.
In fho Iaborafory fhIs poIymor Is proparod bofwoon adIpoyI chIorIdo dIssoIvod In a
wafor ImmIscIbIo organIc soIvonf and a wafor soIufIon of fho dIamIno. Tho roacfIon occurs
af fho Inforfaco of fho fwo soIufIons and Is fhus caIIod lnterIuclul polymerlzutlon.
Procedure: PIaco a soIufIon of 2 mI of adIpoyI chIorIdo In 100 mI hoxano In a 200 mI
boakor. Mako a soIufIon of 2 g hoxamofhyIonodIamIno and 1.5 g sodIum hydroxIdo In 50 mI
wafor In anofhor boakor. Pour fhIs soIufIon on fho adIpoyI chIorIdo soIufIon carofuIIy. A
poIymorIc fIIm sfarfs formIng ImmodIafoIy af fho Inforfaco of fho fwo IIquIds. Romovo fho
poIymorIc fIIm wIfh a forcops and raIso If from fho boakor as a confInuousIy formIng a ropo.
Wash fho poIymor wIfh wafor fhoroughIy. !InaIIy wash If wIfh 50% aquoous acofono and
aIIow If fo dry In aIr. PIaco a smaII amounf of fho drIod fIIm on a wafch gIass and moIf If
carofuIIy on a hof pIafo so fhaf If doos nof gof charrod. PuII fho moIfon poIymor wIfh a gIass
rod fo draw If Info a fIbro.
Question
8.36 ÐoscrIbo InforfacIaI poIymorIzafIon.
8.20 CATALYTIC HYDROGENATION
CafaIyfIc hydrogonafIon Is an Imporfanf roacfIon bofh In fho rosoarch Iaborafory and Indusfry.
Tho porformanco of such an oxporImof, howovor, roquIros fho uso of spocIaI apparafus and
pofonfIaIIy hazardous hydrogon gas. A safo and aIfornafIvo procoduro wIII bo doscrIbod
horo for fho cafoIyfIc hydrogonafIon of cInnamIc acId.
8.20.1 Conversion of Cinnamic Acid to Hydrocinnamic Acid
Method A: !or fhIs roacfIon paIIadIum on acfIvafod carbon Is usod In fofraIIn. Tho Iaffor
roagonf funcfIons bofh as a soIvonf and as a sourco of hydrogon.
234 LABORATORY MANUAL OF ORGANIC CHEMISTRY
TofraIIn Is smoofhIy dohydrogonafod fo naphfhaIono and hydrogon Is roIoasod. Tho
roacfIon fakos pIaco undor rofIuxIng condIfIons and af afmosphorIc prossuro.
Procedure: PIaco 5 g of cInnamIc acId In 25 mI fofraIIn In a 100 mI round-boffomod fIask.
To fhIs add 0.1 g of 30% paIIadIum on acfIvafod carbon. !If fho fIask wIfh an aIr-condonsor
and rofIux fho mIxfuro for 1.5 hr. CooI and dIIufo wIfh 25 mI ofhor. !IIfor fho paIIadIum
cafaIysf and oxfracf fho fIIfrafo wIfh fwo 10 mI porfIons of 10% sodIum hydroxIdo soIufIon.
Tho hydrocInnamIc acId dIssoIvos In fho aquoous Iayor, savo fho organIc Iayor for fho
IsoIafIon of naphfhaIono tNofo I). AcIdIfy fho aIkaIIno oxfracf wIfh conc. hydrochIorIc acId
unfII If Is acIdIc fo Congo rod papor. CooI and oxfracf agaIn wIfh fwo 30 mI porfIons of
ofhor. Ðry fho ofhor soIufIon ovor anhydrous caIcIum chIorIdo. ÐIsfII off ofhor on a sfoam-
bafh and aIIow fho rosIduo fo crysfaIIIzo.
RocrysfaIIIzo fho acId from hof ofhanoI. Tho yIoId Is 2÷2.5 g, m.p. 48.5
o
C.
Note ¡: NaphfhaIono may bo obfaInod from fho organIc Iayor by makIng Ifs pIcrafo wIfh pIcrIc
acId.
Method B: Tho socond mofhod consIsfs of fho roducfIon of cInnamIc acId by dIImIdo gonorafod
In sltu by fho coppor cafaIyzod oxIdafIon of hydrazIno In fho prosonco of an oxIdIzIng
agonf tH
2
O
2
).
ORGANIC PREPARATIONS 235
Tho roducfIon of C = C bond wIfh dIImIdo InvoIvos a sforoospocIfIc addIfIon of hydrogon
oia a non-poIar cycIIc fransIfIon sfafo. Though In fho abovo roacfIon bofh cis and trans-
forms of dIImIdo aro formod buf fho formor form Is InvoIvod In roducfIon.
Procedure: ÐIssoIvo 2 g of cInnamIc acId In 2.5 g hydrazIno tor 4.0 g of hydrazIno
hydrafo) In a 500 mI boakor. To fho cIoar soIufIon add 25 mI of wafor and shako tNofo I).
Immorso fho boakor In an Ico-bafh and fo If add wIfh sfIrrIng a fow crysfaIs of cuprIc
suIfafo. To fho cooIod soIufIon add 10 g hydrogon poroxIdo t30%) sIowIy such fhaf fho
fomporafuro romaIns boIow 30
o
C as an oxofhormIc roacfIon commoncos tNofo II). Affor
fho addIfIon Is compIofo aIIow fho boakor fo sfand In fho Ico-bafh for 30 mIn foIIowod by 10
mIn af room fomporafuro. AgaIn cooI fho boakor and add a fow mI of 1 : 1 conc. hydrochIorIc
acId wIfh sfIrrIng. HydrocInnamIc acId soparafos ouf froquonfIy as an oII. CooI fo crysfaIIIzo
fho oII. RocrysfaIIIzo from wof ofhor, yIoId 0.8 g, m.p. 48.5
o
C.
Notes ¡: Add wafor onIy affor cInnamIc acId has dIssoIvod In hydrazIno hydrafo.
¡¡: Add cooIod hydrogon poroxIdo dropwIso ofhorwIso farry producfs wouId bo obfaInod.
Question
8.37 Namo ofhor roducIng agonfs whIch add In a syn mannor fo aIkonos.
8.21 PHOTOCHEMICAL REACTIONS
A fhormaI roacfIon Is promofod by hoaf whoroas a phofochomIcaI roacfIon dorIvos Ifs onorgy
from fho absorpfIon of IIghf radIafIon. !or a phofochomIcaI roacfIon fo fako pIaco, fho
subsfanco musf absorb onorgy In fho wavoIongfh rogIon In whIch If Is IrradIafod. ThIs can
bo doformInod by fho absorpfIon spocfrum of fho compound. PhofochomIcaI roacfIons havo
provon InvaIuabIo In organIc synfhosos.
8.21.1 Preparation of Benzopinacol
PhofochomIcaI proparafIon of bonzopInacoI from bonzophonono Is ono of fho oIdosf mofhods.
Tho roacfIon can bo InIfIafod by sunIIghf.
Procedure: PIaco 10 g of bonzophonono In a 100 mI round-boffomod fIask and dIssoIvo In
60÷70 mI of IsopropyI aIcohoI by warmIng. !III fho fIask fo fho nock wIfh moro aIcohoI and
236 LABORATORY MANUAL OF ORGANIC CHEMISTRY
add ono drop of gIacIaI acofIc acId tNofo I). Sfoppor fho fIask fIghfIy whIch Is wIrod In pIaco.
Invorf fho fIask In a 100 mI boakor and oxposo If fo dIrocf brIghf sunIIghf. Tho formafIon of
bonzopInacoI can bo foIIowod by fho appoaranco of coIorIoss crysfaIs around fho waIIs of fho
fIask, as If Is onIy sparIngIy soIubIo In aIcohoI. Affor 4÷5 hrs somo crysfaIs soparafo ouf,
and 95% of fho roacfIon Is compIofo In abouf four days tNofo II). ChIII fho fIask and fIIfor
fho crysfaIs on a Buchnor funnoI. Wash fho soIId wIfh a smaII amounf of coId ofhanoI.Tho
producf Is gonoraIIy puro, m.p. 188÷189
o
C.
Notes ¡: A drop of gIacIaI acofIc acId musf bo addod, ofhorwIso onough aIkaII may bo dorIvod from
fho fIask fo cIoavo fho dIoI fo bonzhydroI and bonzophonono.
¡¡: If any bonzophonono crysfaIIIzos ouf If musf bo dIssoIvod In aIcohoI by warmIng.
8.21.2 Photochemical Isomerization of Azobenzene
Tho IsomorIzafIon of azobonzono can bo accompIIshod phofochomIcaIIy. Tho cis-azobonzono
Is fhormodynamIcaIIy unsfabIo and fho posIfIon of oquIIIbrIum doponds on fho wavoIongfh
of fho IncIdonf IIghf. !sIng a radIafIon of = 365 mm, prodomInanfIy t90%) cis-compound Is
obfaInod. SunIIghf can aIso bo usod as a sourco of radIafIon for fhIs IsomorIzafIon.
Procedure: ÐIssoIvo 0.5 g commorcIaI azobonzono In 500 mI bonzono and sforo fho soIufIon
In a sfopporod brown boffIo. Tako fwo fhIn-Iayor chromafography tTLC) pIafos and spof
oach of fhoso pIafos, usIng an ordInary capIIIary fubo abouf 1 cm from fho boffom of fho
pIafo. PIaco ono pIafo In fho Iockor whoro If can bo profocfod from IIghf buf oxposo fho
ofhor fo sunIIghf for 1 hr. Thon dovoIop bofh fho pIafos In a chambor confaInIng 3 : 1
cycIohaxano-bonzono tv/v) fo a dopfh of abouf 0.5 cm.
Romovo fho pIafos affor fho soIvonf fronf has fravoIIod fo wIfhIn 1 cm of fho fop of fho
sIIIca Iayor on fho pIafos. Two spofs of yoIIow compound wouId bo vIsIbIo on oach pIafo. Tho
spof noar fho sfarfIng poInf Is fhaf of fho moro poIar cis-azobonzono whIIo fho spof wIfh a
Iargor P
F

vaIuo Is duo fo fho non-poIar trans-Isomor. Moasuro fho roIafIvo aroas of fho fwo
spofs on oach pIafo. If may bo nofIcod fhaf dopondIng on fho provIous hIsfory of azobonzono,
fho cis-compound may bo obfaInod on fho IrradIafod pIafo.
ORGANIC PREPARATIONS 237
8.22 THE HALOFORM REACTION
Whon mofhyI kofonos roacf wIfh haIogons tX
2
) In aquoous sodIum hydroxIdo
soIufIon fhoy aro cIoavod fo yIoId a carboxyIIc acId and haIoform tCHX
3
). AccordIngIy,
Iodoform Is obfaInod usIng IodIno haIogon and a mofhyI kofono.
8.22.1 Preparation of Iodoform
Procedure: PIaco 3 mI of acofono, 30 mI wafor and 15 mI of sodIum hydroxIdo t10%)
soIufIon In an ÐrIonmoyor fIask. To fho mIxfuro add IodIno soIufIon t12.5 g of IodIno dIssoIvod
In a soIufIon of 25 g of pofassIum IodIdo In 100 mI of wafor) dropwIso wIfh consfanf shakIng
fIII fho coIor of IodIno porsIsfs. Hoaf fho confonfs on a wafor-bafh af 60
o
C. Add moro IodIno
If fho coIor dIsappoars. Hoaf fIII yoIIow procIpIfafos soffIo down. CooI, fIIfor and rocrysfaIIIzo
from aquoous mofhanoI, fho yIoId Is 5 g, m.p. 199
o
C.
8.23 ISOLATION EXPERIMENTS
Mofhods of IsoIafIon aro sImpIo onough fo bo oasIIy adapfabIo and fhoy do nof InvoIvo any
compIIcafod roacfIons. Tho Inforosf In fho IsoIafIon of compounds from nafuraI sourcos
oxIsfs bocauso of fhoIr many pracfIcaI appIIcafIons. If Is aIso nofoworfhy fhaf nafuraI producfs
prosonf somo of fho groafosf chaIIongos fo modorn organIc chomIsfs.
8.23.1 Isolation of Caffeine from Tea
CaffoIno t1, 3, 7-frImofhyIxanfhIno) Is an aIkaIoId prosonf In coffoo boans, foa Ioavos, onorgy
drInks and dIof coIa.
238 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Procedure: BoII on a Bunson burnor 20 g of foa Ioavos In a 500 mI boakor wIfh 250 mI of
dIsfIIIod wafor for 25 mIn. !IIfor fhrough a Buchnor funnoI wIfhouf usIng fho fIIfor papor af
fho pump fo romovo fho sponf foa Ioavos. To fho cIoar fIIfrafo add, whIIo sfIrrIng 60 mI of
10% Ioad acofafo soIufIon fo procIpIfafo fannIns tnafuraIIy occurrIng poIyphonoIs). Loavo
fho mIxfuro undIsfurbod for 2÷3 days. Affor fhIs porIod fIIfor If fhrough a gIass wooI pIug
and conconfrafo fho fIIfrafo on a sand-bafh fo abouf 30 mI. CooI fho rosIduaI soIufIon and
oxfracf If fhrIco wIfh 25 mI profIons of chIoroform tNofo I). CombIno fho chIorform oxfracfs
and romovo mosf of fho chIoroform by sImpIo dIsfIIIafIon. CooI fho rosIduo and add 40 mI of
pofroIoum ofhor and sfIr fho mIxfuro for 5 mIn.
Tho yoIIow coIor of fho organIc oxfracf can bo docoIorIzod by shakIng wIfh 2 mI of 10%
sodIum hydroxIdo soIufIon foIIowod by washIng wIfh fho samo voIumo of wafor. Ðry fho
washod oxfracf and romovo fho soIvonf undor vacuum. RocrysfaIIIzo fho crudo caffoIno
from mInImum t< 1 mI) quanfIfy of boIIIng wafor. ÐoformIno fho yIoId ad fho moIfIng poInf
of fho producf, m.p. 235÷237
o
C.
TesI jor Cujjeine
Warm a fow mIIIIgrams of caffoIno wIfh K
4
¦!otCN)
6
¦ and HNO
3
, a PrussIan bIuo coIor
Is obfaInod.
Note ¡: In caso an omuIsIon forms, pass fhrough a fIIfor papor fo facIIIfafo fho soparafIon of fwo
Iayors.
Question
8.38 Sfafo fwo sourcos of caffoIno and Ifs coIor fosf.
8.23.2 Isolation of Lycopene from Tomatoes
Lycopono Is a rod pIgmonf whIch Is oxfracfod from fomafoos and has fho foIIowIng sfrucfuro:
In fhIs oxorcIso you wIII Ioarn fo IsoIafo a producf from nafuraI sourco and purIfy If
usIng coIumn chromafography.
Procedure: WoIgh abouf 10 g of rod fomafo pasfo trIpo fomafoos can bo mashod fo proparo
a pasfo) Info a 250 mI round-boffomod fIask. Add 25 mI of mofhanoI and 30 mI of
ORGANIC PREPARATIONS 239
dIchIoromofhano. Hoaf fho mIxfuro undor rofIux for 5 mIn on a sfoam-bafh wIfh froquonf
shakIng. !IIfor fho mIxfuro undor sucfIon and fransfor fho fIIfrafo fo a soparafory funnoI.
Wash fhIs mIxfuro confaInIng Iycopono wIfh fhroo porfIons of 150 mI oach wIfh sodIum
chIorIdo soIufIon. Ðry fho organIc Iargor ovor anhydrous magnosIum suIfafo. !IIfor and
ovaporafo mosf of fho soIvonf In vacuum wIfhouf hoafIng.
To soparafo Iycopono from fho crudo pIgmonf oxfracf, pack fho chromafographIc coIumn
wIfh abouf 40 g of TLC grado sIIIca goI usIng hoxano. ÐIssoIvo fho crudo rod pIgmonf Is 5 mI
of IIghf pofroIoum and fransfor on fho fop of fho coIumn wIfh a pIpoffo. ÐIufo If wIfh
hoxano fIII a yoIIow band appoars. Af fhIs sfago, chango fho oIuonf fo 10% acofono In hoxano.
An orango-rod coIor band wIII sfarf fo appoar. CoIIocf a sampIo of fho oIuafo from fho
confor of fhIs band. Ðvaporafo fo drynoss undor vacuum. ÐoformIno fho approxImafo yIoId
of Iycopono.
8.23.3 Isolation of Casein from Milk
CasoIn Is fho phosphoprofoIn prosonf In mIIk and confaIns af Ioasf 15 amIno acIds. If Is an
amorphous and hygroscopIc whIfo soIId InsoIubIo In organIc soIvonfs. If Is prosonf fo fho
oxfonf of 3% In cow mIIk. Tho pH of frosh mIIk Is approxImafoIy 6.6 and whon If Is acIdIfIod
fo pH 4.5 casoIn procIpIfafos. CasoIn Is fho chIof profoIn of mIIk and Is fho basIs of curds
and chooso.
Procedure: ÐIIufo 140 mI of cow mIIk wIfh 500 mI wafor In a 1000 mI boakor and warm fo
40
o
C. Thon add dropwIso wIfh consfanf sfIrrIng 10% acofIc acId fo obfaIn aII fho casoIn
procIpIfafos. AIIow fo sfand fho boakor undIsfurbod for 5 mIn. !IIfor fho procIpIfafo on a
Buchnor funnoI and wash succossIvoIy fhrIco wIfh 5 mI porfIons of wafor, 20 mI of ofhanoI
and 10 mI of ofhor fo romovo aII fho fafs. Ðry fho wof soIId In a vacuum dosIccafor and
woIgh fho dry powdor. Tosf fho soIubIIIfy of casoIn In wafor, bonzono, 5% hydrochIorIc acId
and 5% sodIum hydroxIdo soIufIon.
8.23.4 Isolation of Piperine from Pepper
PIporIno Is an aIkaIoId found In bIack poppor fo fho oxfonf of 10% by woIghf and Is known fo
bo an amIdo. If possossos fho foIIowIng sfrucfuro:
Tho ofhor consfIfuonfs of poppor boIng voIafIIo oIIs t1.3%), sfarchos t20÷40%) and
wafor t8÷13%). PIporIno can bo IsoIafod by oxfracfIon of ground poppor wIfh 95% ofhanoI.
In an IdoaI caso fho oxfracfIon shouId bo carrIod ouf In a Soxhlet uppurutus as shown In
!Ig. 8.4. ThIs mofhod roquIros onIy a smaII amounf of fho organIc soIvonf.
240 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Fig. 8.4 Soxhlet extractor for the extraction of solids.
Procedure: In a 500 mI round-boffomod fIask fIffod wIfh a rofIux condonsor add abouf
350 mI of 95% ofhanoI. Pack fho fhImbIo wIfh 30 g of powdorod poppor and pIaco If In fho
apparafus as shown. Tho fIask Is hoafod for 3 hrs. MaforIaI Is oxfracfod ouf of fho soIId Info
fho hof soIvonf. !IIfor fho ofhanoI soIufIon and conconfrafo fho fIIfrafo fo 25 mI by dIsfIIIafIon.
To fhIs rosIduo add 30 mI of warm 2 N ofhanoIIc pofassIum hydroxIdo soIufIon. SfIr fho
warm mIxfuro and fIIfor fo romovo any InsoIubIo maforIaI. Warm fho soIufIon on a sfoam-
bafh and add 15÷20 mI of wafor. Af fhIs sfago furbIdIfy appoars and yoIIow noodIos may
soparafo. Koop fhIs soIufIon fIII fho noxf Iaborafory porIod and fIIfor fho crudo pIporIno.
RocrysfaIIIzo from acofono fo obfaIn fIno yoIIow noodIos, m.p. 129÷131
o
C.
Question
8.39 Is fho pIporIno IsoIafod oxpocfod fo bo opfIcaIIy acfIvo7
8.23.5 Isolation and Estimation of Aspirin
AspIrIn Is acofyIsaIIcycIIc acId. If Is bofh an osfor and a carboxyIIc acId. Tho acId was fIrsf
synfhosIzod In 1853 and was Infroducod by Baoyor In 1899 undor fho frado namo usplrln.
If soon bocamo fho worId`s mosf popuIar drug. AspIrIn Is known fo Iowor fovor, roIoIvo paIn
and roduco InfIammafIon. Tho spocIfIc funcfIon of aspIrIn In fho body was roporfod In 1971.
If was proposod fhaf aspIrIn InhIbIfs fho ovorproducfIon of prosfagIandIns In fho body.
ProsfagIandIns aro hormono÷IIko compounds fhaf roguIafo body funcfIons. An ovorsuppIy
ORGANIC PREPARATIONS 241
of corfaIn prosfagIandIns can promofo fho formafIon of bIood cIofs fhaf Ioad fo hoarf affack
and sfrokos whIIo ofhors causo paIn, fovor and InfIammafIon. Thus, fhoro Is a posIbIIIfy
fhaf aspIrIn roducos fhoso probIoms by bIockIng fho ovorproducfIon of prosfagIandIns In
fho body. AspIrIn aIso brIngs abouf a roducfIon of swoIIIng In fho joInfs and Ioads fo roIIof of
paIn In poopIo sufforIng from arfhrIfIs.
Isolation
Procedure: An aspIrIn fabIof confaIns aspIrIn and a sfarch bIndor. Powdor an aspIrIn fabIof
on a fIIfor papor and fransfor If fo a 25 mI. ÐrIonmoyor fIask. To fhIs add 10 mI of absoIufo
aIcohoI and boII fho mIxfuro on a sfoam-bafh. AspIrIn wIII dIssoIvo. !IIfor fho hof soIufIon
and agaIn hoaf fo drynoss. RocrysfaIIIzo fho rosIduo from bonzono, m.p. 130÷135
o
C.
Estimation
Tho amounf of aspIrIn In a commorcIaI fabIo Is doformInod by fIfrafIon of Ifs soIufIon In
aIcohoI agaInsf sfandard sodIum hydroxIdo soIufIon.
Procedure: WoIgh an aspIrIn fabIo accurafoIy. Powdor If on a fIIfor papor and dIssoIvo If In
10 mI of absoIufo aIcohoI by boIIIng. !IIfor fho hof soIufIon In a 150 mI ÐrIonmoyor fIask.
Wash fho InsoIubIo rosIduo on fho fIIfor papor wIfh 3 addIfIonaI 5 mI porfIons of hof ofhanoI.
Mako suro aII fho washIngs aro dono carofuIIy. Add 20 mI of dIsfIIIod wafor and 3 drops of
phonoIphfhaIoIn fo fho combInod fIIfrafos. TIfrafo fho soIufIon agaInsf 0.1 M sodIum
hydroxIdo soIufIon fo a faInf pInk coIor ond-poInf. Nofo fho voIumo of aIkaII consumod, fho
fofaI voIumo of soIufIon Is 25 mI. CaIcuIafo fho amounf of aspIrIn by usIng fho oquafIon:
N × V = N
1
× V
1
8.24 PREPARATION OF TRIPTYCENE
TrIpfycono Is proparod by fho famIIIar ÐIoIs-AIdor roacfIon bofwoon anfhracono and a hIghIy
roacfIvo dIonophIIo namoIy bonzyno. !or fhIs purposo bonzyno Is gonorafod from anfhranIIIc
acId.
242 LABORATORY MANUAL OF ORGANIC CHEMISTRY
In fhIs proparafIon, anfhranIIIc acId Is dIazofIsod In fho prosonco of IsoamyI aIcohoI.
BonzonodIazonIum-2-carboxyIafo Is formod. If suffors docomposIfIon fo yIoId bonzyno whIch
Is frappod by anfhracono fo form frIpfycono.
Procedure: In a fwo-nockod round-boffomod fIask oquIppod wIfh a rofIux condonsor and a
droppIng funnoI, pIaco 4 g anfhracono and 4 mI IsoamyI nIfrIIo In 40 mI 1, 2-
dImofhyoxyofhano. Now fako a soIufIon of 10.4 g of anfhranIIIc acId In 40 mI of 1, 2-
dImofhyoxyofhano In fho droppIng funnoI. Hoaf fho fIask gonfIy and pour haIf of fho soIufIon
dropwIso ovor a porIod of 20÷30 mIn fo fho fIask. Romovo fho burnor and add 4 mI IsoamyI
nIfrIfo fhrough fho condonsor. AgaIn hoaf and run In fho romaInIng anfhranIIIc acId soIufIon
dropwIso wIfhIn a porIod of 30 mIn. Affor fho addIfIon of anfhranIIIc acId Is compIofo, rofIux
fho mIxfuro for 15 mIn. CooI and add Info If 20 mI of ofhanoI and 6 g of sodIum hydroxIdo
soIufIon In 80 mI wafor. CooI fho mIxfuro fhoroughIy In Ico. !IIfor and wash fho rosIduo
wIfh Ico coId aquoous mofhanoI t4 : 1) and dry, yIoId 4 g. ThIs producf Is confamInafod wIfh
anfhracono. ThIs ImpurIfy can bo romovod by makIng Ifs ÐIoIs-AIdor adducf wIfh maIoIc
anhydrIdo.
Tako fhIs crudo soIId In a 250 mI round-boffomod fIask fIffod wIfh an aIr condonsor. To
If add 2 g maIoIc anhydrIdo and 40 mI of frIofhyIono gIycoI dImofhyI ofhor tfrIgIymo, b.p.
222
o
C). RofIux fho mIxfuro for 5÷10 mIn. Thon cooI fo 100
o
C and fo If add 20 mI of ofhanoI
and 1 g sodIum hydroxIdo In 80 mI wafor. CooI In Ico and fIIfor. Wash fho rosIduo wIfh
aquoous mofhanoI t4 : 1) and dry. YIoId of frIpfycono Is 3 g, m.p. 254
o
C.
Question
8.40 WouId you oxpocf fho frIpfycyI anIon fo bo sfabIo7
8.25 ADDITION OF DICHLOROCARBENE TO CYCLOHEXENE
Carbonos aro noufraI dIvaIonf carbon compounds. Tho confraI carbon afom has sIx oIocfrons
and Is oIocfron dofIcIonf. Thoy acf as roacfIvo InformodIafos. Thoy havo onIy fransIonf
oxIsfonco and aro frappod by aIkono dorIvafIvos. ThIs fypo of roacfIon Is of groaf synfhofIc
ufIIfIy In fho proparafIon of cycIopropanos. CycIohoxono, for Insfanco, roacfs wIfh
dIchIorocarbono whIch Is gonorafod by froafIng chIoroform wIfh a sfrong baso IIko pofassIum
t-bufoxIdo, fo gIvo 7, 7-dIchIoro ¦4.1.0¦ hopfano.
Procedure: PIaco 20 mI of t-bufyI aIcohoI In an ÐrIonmoyor fIask and fo If add 7 g of
pofassIum mofaI tNofo I) In smaII porfIons wIfh sfIrrIng. Affor aII fho pofassIum has roacfod,
cooI fho fIask. To fho coId pofassIum t-bufoxIdo add 16 mI of dry cycIohoxono foIIowod by
fho addIfIon of 3.2 mI chIoroform dropwIso wIfh consfanf shakIng. Affor fho addIfIon of
ORGANIC PREPARATIONS 243
chIoroform Is compIofo, confInuo shakIng for 30 mIn. Pour fho roacfIon mIxfuro Info a
soparafory funnoI confaInIng 25 mI wafor. Shako and coIIocf fho aquoous Iayor In a boakor.
Ðxfracf fho aquoous Iayor fhrIco wIfh 25 mI porfIons of pofroIoum ofhor tb.p. 40÷50
o
C).
CombIno fho oxfracfs and dry fhIs soIufIon ovor anhydrous sodIum suIfafo. !IIfor and
ovaporafo fho soIvonf on a hof pIafo. ÐIsfII fho rosIduo af roducod prossuro fo obfaIn fho
puro producf. Tho producf Is obfaInod as a coIorIoss IIquId. ÐoformIno Ifs yIoId.
Note ¡: Romovo fho oIIy Iayor on fho pofassIum mofaI by prossIng If bofwoon fho foIds of fIIfor
papors boforo uso.
8.26 MISCELLANEOUS PREPARATIONS
SovoraI addIfIonaI proparafIons aro dIscussod In fhIs socfIon.
8.26.1 Preparation of Methyl Benzoate
CarboxyIIc acIds aro convorfod dIrocfIy fo osfors by fho !Ischor osforIfIcafIon mofhod.
If Is an acId-cafaIyzod osforIfIcafIon of a carboxyIIc acId In fho prosonco of aIcohoI and
a mInoraI acId as cafaIysf. HoafIng Is nocossary for fho succoss of osforIfIcafIon.
Tho mochanIsm of osforIfIcafIon procoods In fho foIIowIng sfops:
244 LABORATORY MANUAL OF ORGANIC CHEMISTRY
!Ischor osforIfIcafIon Is an oquIIIbrIum roacfIon. Tho yIoId of fho producf may bo
Improvod by usIng an oxcoss of ono of fho roacfanfs toxcoss aIcohoI Is froquonfIy usod) or
by romovIng wafor as If Is formod.
Procedure: In a 100 mI round-boffomod fIask, pIaco 8 g of bonzoIc acId and 27 mI mofhanoI.
Add 0.7 mI of conc. suIfurIc acId, mIx and add a fow boIIIng chIps. Affach a wafor condonsor
and rofIux fho mIxfuro for 1 hr on a sfoam-bafh. CooI fho fIask and fransfor fho soIufIon fo
a soparafory funnoI. Ðxfracf fho osfor fwIco wIfh 25 mI porfIons of ofhor. Wash fho combInod
ofhoroaI soIufIon wIfh 30 mI wafor foIIowod by washIng wIfh 5% sodIum bIcarbonafo soIufIon
unfII noufraI. !InaIIy wash onco wIfh wafor. Ðry fho soIufIon ovor anhydrous sodIum suIfafo,
fIIfor and romovo ofhor on a wafor-bafh. ÐIsfII fho rosIduo usIng an aIr condonsor. CoIIocf
fho dIsfIIIafo boIIIng af 198÷200
o
C. Tho yIoId Is 8 g.
Question
8.41 Suggosf a mofhod for fho formafIon of an osfor In whIch an oquIIIbrIum of fho abovo
fypo Is nof InvoIvod7
8.26.2 Preparation of Acetanilide (Acetylation)
Tho acofyIafIon procoss Is Imporfanf bocauso If provIdos a mofhod for fho osfImafIon of
amIno- and hydroxy-groups.
Procedure: PIaco 10 mI of anIIIno, 10 mI of acofIc anhydrIdo tNofo I) and 10 mI of gIacIaI
acofIc acId In a dry 200 mI round-boffomod fIask oquIppod wIfh a rofIux condonsor. MIx fho
confonfs, somo hoaf Is ovoIvod duo fo fho roacfIon of acofIc anhydrIdo wIfh anIIIno. Hoaf
fho fIask on a Bunson burnor for 15÷20 mIn. Pour fho hof mIxfuro sIowIy wIfh consfanf
sfIrrIng on 200 mI of Ico coId wafor fakon In a boakor. !IIfor fho soIId on a Buchnor funnoI
and wash wIfh pIonfy of coId wafor. RocrysfaIIIzo fho crudo acofanIIIdo from boIIIng wafor,
m.p. 115
o
C fho yIoId Is 10 g.
Note ¡: AcofIc anhydrIdo Is Iachramafory, fhoroforo, work In a fumo hood.
8.26.3 Preparation of Aspirin (Acetylation)
AspIrIn Is acofyIsaIIcyIIc acId and was fIrsf synfhosIzod In 1853.
AcofyIafIon of a phonoI can bo carrIod ouf In fho prosonco of acofIc anhydrIdo and an
acId as cafaIysf fo obfaIn aspIrIn. Tho roacfIon foIIows fho foIIowIng mochanIsm:
ORGANIC PREPARATIONS 245
AspIrIn roacfs wIfh sod. hydroxIdo soIufIon fo form a saIf, sod. acofyIsaIIcyIafo whIch
Is soIubIo In wafor. AspIrIn Is fho mosf popuIar drug In fho worId. If Iowors fovor, roIoIvos
paIn and roducos InfIammafIon. Thoro Is ovIdonco avaIIabIo fhaf aspIrIn InhIbIfs fho
producfIon of prosfagIandIns thormono-IIko compounds fhaf roguIafo body funcfIons) In
fho body.
Procedure: ÐIssoIvo 7.5 g of saIIcyIIc acId to-hydroxybonzoIc acId) In 11.5 g of froshIy
dIsfIIIod acofIc anhydrIdo In an ÐrIonmoyor fIask. Add 3÷4 drops of conc. suIfurIc acId and
shako fho confonfs fhoroughIy. Immorso a fhormomofor and hoaf fho fIask bofwoon
50÷60°C for 15÷20 mIn. CooI and add 100 mI wafor. !IIfor fho soIId af fho pump on a Buchnor
funnoI and wash If fwIco wIfh coId wafor. Pross bofwoon fho foIds of fIIfor papors and
rocrysfaIIIzo from aquoous ofhanoI fo obfaIn coIorIoss crysfaIs of aspIrIn. Tho yIoId Is
8.8 g, m.p. 135÷136°C.
Question
8.42 How wIII you dIfforonfIafo quaIIfafIvoIy bofwoon aspIrIn and saIIcyIIc acId7 Suggosf a
coIor fosf.
8.26.4 Preparation of p-Nitroaniline
Tho amIno group on fho bonzono nucIous of an anIIIno sfrongIy acfIvafos bofh fho ortho
and para posIfIons. Thoroforo, dIrocf nIfrafIon of anIIIno Ioads fo a mIxfuro of bofh fho
Isomors. To avoId fho formafIon of fho mIxfuro, fho acfIvafIng offocf of fho amIno group Is
roducod fIrsf by acofyIafIng If. ThIs Is foIIowod by nIfrafIon of fho rosuIfIng acofanIIIdo and
fInaIIy hydroIysIs of fho p-nIfroacofanIIIdo fo p-nIfroanIIIno. Tho proparafIon of acofanIIIdo
wIII bo carrIod ouf by an aIfornafIvo mofhod, fhan fho ono doscrIbod In 8.26.2.
246 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho proparafIon InvoIvos fho foIIowIng fhroo sfops:
Step A: PrepuruIion oj uceIuniIiJe
Procedure: Add 4.6 mI of conc. hydrochIorIc acId In a 250 mI ÐrIonmoyor fIask confaInIng
125 mI wafor and 5.1 g t5.0 mI) of anIIIno. SfIr unfII anIIIno has compIofoIy dIssoIvod as Ifs
hydrochIorIdo saIf. To fhIs soIufIon add 6.9 g t6.4 mI) of froshIy dIsfIIIod acofIc anhydrIdo
tNofo I) shakIng If fIII If dIssoIvos. Thon ImmodIafoIy add a soIufIon of 8.3 g of sodIum
acofafo In 25 mI wafor. Tho sodIum acofafo noufraIIzos fho hydrochIorIc acId fo form sodIum
chIorIdo and acofIc acId. Shako vIgorousIy and fhon cooI In Ico. !IIfor fho soIId on a Buchnor
funnoI and wash wIfh 15 mI of coId wafor and dry. Tho yIoId Is 4.9 g, m.p. 144°C.
Step B: PrepuruIion oj p-niIrouceIuniIiJe
Procedure: Powdor 5 g of acofanIIIdo proparod abovo and dIssoIvo In 5 mI gIacIaI acId In a
250 mI broakor. Hoaf fo dIssoIvo If nocossary. To fho soIufIon add 15 mI conc. suIfurIc acId
wIfh vIgorous sfIrrIng. Immorso fho fIask In a cooIIng mIxfuro of Ico and saIf fo brIng fho
fomporafuro fo 0°C. Add dropwIso from a droppIng funnoI a pro-cooIod mIxfuro of 2.6 g
t1.8 mI) of conc. nIfrIc acId and 2.3 g t1.3 mI) of conc. suIfurIc acId wIfh vIgorous sfIrrIng
tNofo I). Adjusf fho rafo of addIfIon so fhaf fho fomporafuro doos nof rIso abovo 10°C. Affor
fho addIfIon Is compIofo, aIIow fho boakor fo sfand af room fomporafuro for 30 mIn. Pour
fho confonfs of fho fIask Info 150 g of crushod Ico. Tho o-nIfroacofanIIIdo may aIso bo
formod In a smaII amounf, boIng soIubIo, romaIns In soIufIon whIIo p-nIfroacofanIIIdo
procIpIfafos ouf. !IIfor fho soIId on a Buchnor funnoI and wash fhoroughIy wIfh coId wafor.
RocrysfaIIIzo from aIcohoI. Tho yIoId Is 5.0 g, m.p. 214°C.
Step C: PrepuruIion oj p-niIrouniIine
Procedure: PIaco 2.5 g of p-nIfroacofanIIIdo and 13 mI of 70% suIfurIc acId In a 100 mI
round-boffomod fIask and rofIux fho mIxfuro for 20 mIn or unfII a fosf sampIo romaIns
cIoar upon dIIufIon wIfh 1÷3 fImos Ifs voIumos of wafor. Pour fho hof soIufIon Info 250 mI
of coId wafor fakon In a boakor and noufraIIzo wIfh 10% sodIum hydroxIdo soIufIon. CooI
and fIIfor fho yoIIow crysfaIIIno producf on a Buchnor funnoI. Wash If fhoroughIy wIfh
wafor. RocrysfaIIIzo from hof wafor. Tho yIoId Is 1.6 g, m.p. 148°C.
Notes ¡: Add a IIffIo oxcoss of acofIc anhydrIdo.
¡¡: If avaIIabIo uso a mochanIcaI sfIrror.
Questions
8.43 Why oxcoss of acofIc anhydrIdo Is usod In fho proparafIon of acofanIIIdo 7
8.44 Bofwoon o-nIfroanIIIno and p-nIfroanIIIno, whIch Is moro hIgh boIIIng 7
ORGANIC PREPARATIONS 247
8.26.5 Preparation of Mandelic Acid
ThIs Is a hydroxy acId whIch Is proparod from bonzaIdohydo by convorfIng If Info a nIfrIIo
and subsoquonf hydroIysIs. Tho InformodIafo roacfIon bofwoon pofassIum cyanIdo and fho
bIsuIfIfo adducf oIImInafos fho hazard of workIng wIfh fho voIafIIo and foxIc hydrocyanIc
acId.
Procedure: ÐIssoIvo 5.5 g of sodIum bIsuIfIfo In 15 mI wafor by shakIng If In a 125 mI
ÐrIonmoyor fIask. To fho soIufIon add 5 mI bonzaIdohydo, cork fho fIask and shako vIgorouIy
fIII fho oIIy Iayor of bonzaIdohydo Is convorfod Info fho crysfaIIIno bIsuIfIfo compound. CooI
fo room fomporafuro and add 7 g pofassIum cyanIdo In 13 mI of wafor and aIIow fho mIxfuro
fo cooI. SfIr agaIn and If nocossary broak fho Iumps wIfh a gIass rod. MandoIonIfrIIo soparafos
as an oII. Transfor fho mIxfuro fo a soparafory funnoI, rInso fho fIask wIfh a smaII amounf
of wafor and ofhor and fhon shako fho mIxfuro vIgorousIy for 1 mIn fo onsuro compIofo
roacfIon. Add 10 mI of ofhor, shako agaIn and dIscard fho aquoous Iayor tNofo I). Wash fho
ofhor oxfracf wIfh 15 mI wafor foIIowod by 15 mI of safurafod sodIum chIorIdo soIufIon.
Transfor fho soIufIon fo a dIsfIIIIng fIask confaInIng 7 mI oach of conc. hydrochIorIc acId
and wafor. ÐIsfII on a sfoam-bafh and coIIocf fho dIsfIIIafo In Ico-coId rocoIvor. Affor aII fho
ofhor has dIsfIIIod ovor, romovo fho condonsor and confInuo hoafIng wIfh froquonf sfIrrIng
fo InIfIafo hydroIysIs. Hoaf for 1.5 hr fo compIofo fho hydroIysIs and af fhIs sfago a cIoar
soIufIon Is obfaInod. CooI fo room fomporafuro. Transfor fho acId soIufIon fo a soparafory
funnoI and rInso fho fIask wIfh a IIffIo ofhor, shako and wIfhdraw fho aquoous Iayor Info a
fIask. Run fho ofhor Iayor Info a dIsfIIIIng fIask confaInIng 50 mI bonzono. Ðxfracf fho
aquoous Iayor sImIIarIy wIfh fwo 15 mI porfIons of ofhor and add fho ofhoroaI soIufIon fo
fho fIask confaInIng bonzono. ÐIsfII fho soIufIon agaIn Info an Ico coId rocoIvor fo romovo
wafor by azoofropIc dIsfIIIafIon. Tho boIIIng poInf rIsos as ofhor and wafor aro romovod.
ConfInuo hoafIng fho fIask fIII fho soIufIon bocomos cIoar agaIn. ÐIsconnocf fho condonsor
and docanf fho hof soIufIon Info a 250 mI ÐrIonmoyor fIask whoroby fho acId soparafos as a
soIId. Tho yIoId Is 5.0 g, m.p. 118÷119°C.
Note ¡: ÐIscard fho aquoous Iayor Info fho draIn In fho sInk.
248 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Question
8.45 How do you oIImInafo fho producfIon of hydrocyanIc acId In fho abovo proparafIon7
8.26.6 Preparation of Anthranilic Acid
AnfhranIIIc acId Is proparod by fho Hoffmann bromamIdo tHoffmann roarrangomonf)
roacfIon. PhfhaIImIdo Is fIrsf proparod bofwoon a roacfIon of phfhaIIc anhydrIdo and uroa.
!or fhIs proparafIon phfhaIImIdo Is offon ompIoyod as fho sfarfIng maforIaI.
AnfhranIIIc acId proparafIon roquIros fwo sfops:
Step A: PrepuruIion oj phIhuIimiJe
Procedure: In a posfIo and morfar mIx fhoroughIy 6 g puro phfhaIIc anhydrIdo wIfh 1.2 g
of uroa and Infroduco fho mIxfuro In a 200 mI Iong-nockod round-boffomod fIask. Hoaf fho
fIask In an oII-bafh af 130÷135°C. Tho confonfs moIf and an offorvosconco commorcos whIch
graduaIIy bocomos vIgorous. Affor 15÷20 mIn frofhIng sfarfs fakIng pIaco whIch Is
accompanIod by a rIso In fomporafuro fo 150÷160°C. Tho confonfs of fho fIask aImosf bocomo
soIId af fhIs sfago. Romovo fho fIamo and aIIow fo cooI fho fIask In fho oII-bafh. Add 10 mI
of wafor and broak fho soIId. !IIfor af fho pump. Wash wIfh a smaII quanfIfy of wafor and
dry fho producf af 100°C. RocrysfaIIIzo from hof ofhanoI. Tho yIoId Is 5.1 g, m.p. 233°C.
Step B: PrepuruIion oj unIhruniIic uciJ
Procedure: ÐIssoIvo 10 g of sodIum hydroxIdo In 40 mI of wafor In 100 mI ÐrIonmoyor
fIask and cooI fho soIufIon fo 0°C In an Ico-bafh. To fhIs add 8.7 g t2.8 mI) of bromIno
carofuIIy In ono Iof and shako fho fIask gonfIy unfII aII fho bromIno has roacfod. SInco fho
roacfIon Is oxofhormIc koop fho fIask af 0°C.
In anofhor ÐrIonmoyor fIask dIssoIvo 7.2 sodIum hydroxIdo In 25 mI of wafor and cooI
fho soIufIon. To fho coId soIufIon add 8 g powdorod phfhaIImIdo In ono porfIon and shako.
To fho coId soIufIon add sodIum hydrobromIfo soIufIon proparod abovo and swIrI fho fIask.
Tho fomporafuro may rIso fo 70°C. Warm fho mIxfuro fo 80°C for 2 mIn and fIIfor If nocossary,
fo romovo any suspondod ImpurIfIos. CooI fhIs soIufIon In an Ico-bafh and add 30 mI conc.
hydrochIorIc acId sIowIy wIfh consfanf sfIrrIng unfII fho soIufIon Is jusf noufraI fo IIfmus.
Transfor fho mIxfuro fo a 500 mI boakor and procIpIfafo anfhranIIIc acId by fho addIfIon of
gIacIaI acofIc acId tNofo I). !IIfor fho anfhranIIIc acId and wash woII wIfh coId wafor.
RocrysfaIIIzo from boIIIng wafor, dry In an ovon af 100°C. Tho yIoId Is 4.5 g, m.p. 145°C.
Note ¡: Somo fumIng fakos pIaco durIng fhIs procoss.
ORGANIC PREPARATIONS 249
Question
8.46 WrIfo a mochanIsm for fho formafIon of phfhaIImIdo from phfhaIIc anhydrIdo and
uroa.
8.26.7 Preparation of Phenylurea
AnIIInIum cyanafo roarrangos fo phonyIuroa af room fomporafuro.
Procedure: Proparo a soIufIon of 6 g anIIInIum hydrochIorIdo In 80 mI of wafor by addIng
1.8 g conc. hydrochIorIc acId fo 4.4 a anIIIno In a 250 mI ÐrIonmoyor fIask. To fhIs add a
soIufIon of 2 g sodIum cyanafo In 20 mI of wafor and aIIow fo sfand af room fomporafuro
for 1 hr fIII fho soIId has soparafod ouf. !IIfor If on a Buchnor funnoI and wash wIfh coId
wafor. Ðry In an ovon. Tho yIoId Is 4.9 g, m.p. 146°C.
8.26.8 Preparation of 2, 4-Dinitrophenylhydrazine
By froafmonf of 2, 4-dInIfrochIorobonzono wIfh hydrazIno af Iow fomporafuro, fho abovo
compound Is obfaInod.
Tho proparafIon InvoIvos fho foIIowIng fwo sfops:
Step A: PrepuruIion oj 2, 4-JiniIrochIorobenzene
Procedure: In a 100 mI round-boffomod fIask fIffod wIfh an aIr-condonsor, pIaco 5 mI
chIorobonzono and 8 mI conc. suIfurIc acId. Hoaf fho mIxfuro on a wafor-bafh and fo fhIs
add a mIxfuro of 10 mI conc. nIfrIc acId and 7 mI conc. suIfurIc acId. SfIr fho mIxfuro durIng
250 LABORATORY MANUAL OF ORGANIC CHEMISTRY
addIfIon maInfaInIng a fomporafuro boIow 100°C. Affor fho addIfIon Is compIofo hoaf fho
mIxfuro on a wafor-bafh for 1.5 hr. CooI and pour fho confonfs of fho fIask on 500 g of
crushod Ico fakon In a ono IIfro boakor. !IIfor fho soIId and rocrysfaIIIzo from hof aIcohoI.
Tho yIoId Is 7.0 g, m.p. 53°C.
Step B: PrepuruIion oj 2, 4-JiniIrophenyIhyJruzine
Procedure: ÐIssoIvo 5.0 g of puro 2, 4-dInIfrochIorobonzono In 10 mI of ofhyIono gIycoI
tNofo I) In a 100 mI round-boffomod fIask. Warm, If nocossary, fo obfaIn a cIoar soIufIon.
CooI fho fIask In an Ico-bafh fo 10°C. Add 1.4 mI of 64% aquoous hydrazIno soIufIon dropwIso
wIfh consfanf sfIrrIng. AddIfIon Is dono af such a rafo fhaf fho fomporafuro doos nof rIso
abovo 15°C. Whon fho addIfIon Is compIofo, add 5 mI of mofhanoI and hoaf fho fIask on a
wafor-bafh for 15÷20 mIn. CooI and coIIocf fho soIId af fho pump, wash wIfh a IIffIo mofhanoI
and dry. Tho yIoId Is 4.4 g, m.p. 192÷193°C.
Note ¡: ÐIoxano as soIvonf may bo ompIoyod Insfoad.
8.26.9 Preparation of 7-Hydroxy-4-Methylcoumarin
RosorcInoI Is condonsod wIfh acofoacofIc osfor In fho prosonco of poIyphosphorIc acId for
fho proparafIon of fho fIfIo compound.
Procedure: In a 250 mI ÐrIonmoyor fIask dIssoIvo 2.8 g of rosorcInoI, 3.3 g ofhyI acofoacofafo
In 50 mI of wafor. To fho soIufIon add 40 g of poIyphosphorIc acId and hoaf on a wafor-bafh
af 70÷80°C sfIrrIng wIfh a fhormomofor. Affor 20 mIn, pour fho mIxfuro Info 200 mI of
wafor confaInod In a boakor. CoIIocf fho yoIIow soIId af fho sucfIon. Wash wIfh coId wafor
and dry In fho ovon af 60°C. RocrysfaIIIzo from hof ofhanoI. Tho yIoId Is 4.1 g, m.p. 105°C.
8.26.10 Preparation of Soap from Fat
CarboxyIIc acIds wIfh Iong, unbranchod carbon chaIns aro caIIod faffy acIds.
!afs and oIIs boIong fo fho famIIy of osfors parfIcuIarIy gIycoroI and Iong chaIn carboxyIIc
acIds. Tho gIycoroI osfors of safurafod acIds aro soIIds whIIo fhoso of unsafurafod acIds aro
IIquIds af ordInary fomporafuros and aro roforrod fo as oIIs. HydroIysIs of a faf In fho
ORGANIC PREPARATIONS 251
prosonco of a baso tsaponIfIcafIon) Ioads fo gIycoroI and soap, i.c., sodIum saIf of fho Iong
chaIn faffy acId. Soaps consfIfufo jusf ono fypo of doforgonf. A detergent Is any subsfanco
ompIoyod for cIoanIng an objocf.
Whoro R = a Iong carbon chaIn.
Procedure: In a 250 mI ÐrIonmoyor fIask, woIgh 25 g of coffon sood oII or any ofhor faf,
add 15 mI of ofhanoI and 6 g sodIum hydroxIdo dIssoIvod In 25 mI wafor. Hoaf fho confonfs
of fho boakor on a wafor-bafh maInfaInIng a bafh fomporafuro bofwoon 80÷90°C. SfIr fho
mIxfuro froquonfIy wIfh a gIass rod and confInuo hoafIng for 1 hr. Affor fhIs porIod add 200
mI of safurafod sodIum chIorIdo soIufIon and cooI fho mIxfuro fo procIpIfafo ouf soap.
!IIfor If fhrough doubIo fho fhIcknoss of chooso cIofh. Wash fho soap on fho cIofh wIfh
50 mI of coId wafor and mouId If Info a cako In a smaII chIna dIsh.
To rocovor gIycoroI ta by-producf) sIIghfIy acIdIfy fho fIIfrafo from abovo wIfh
hydrochIorIc acId and ovaporafo If fo drynoss. Ðxfracf gIycoroI wIfh 20 mI of absoIufo aIcohoI.
Ðocanf fho aIcohoI soIufIon from fho saIf and ovaporafo on a hof pIafo. A smaII rosIduo of
gIycoroI romaIns.
To a IIffIo soap soIufIon add a fow drops of dIIufo hydrochIorIc acId soIufIon. Whaf Is
fho soIId procIpIfafo7
Questions
8.47 ÐoscrIbo a soap. ÐxpIaIn fho fochnIquo 'saIfIng ouf`.
8.48 Whaf Is fho roacfIon of soap wIfh hard wafor7
8.26.11 Preparation of p-Bromoaniline
BromInafIon of anIIIno Ioads fo poIysubsfIfufod compound, i.c., 2, 4, 6-frIbromoanIIIno as
fho soIo producf. ThIs Is duo fo fho facf fhaf fho amIno group Is hIghIy acfIvafIng. Howovor,
monosubsfIfufIon may bo achIovod by dImInIshIng fho oIocfron-donafIng capacIfy of fho
amIno group. !or fhIs purposo fho amIno group Is fIrsf convorfod fo an acofamIdo wIfh
acofIc anhydrIdo fo form acofanIIIdo. Tho acofanIIIdo on bromInafIon yIoIds
p-bromoacofanIIIdo and fho acyI group Is fInaIIy romovod Iafor by acIdIc or basIc hydroIysIs.
252 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho proparafIon InvoIvos fhroo sfops:
Step A: PrepuruIion oj uceIuniIiJe.
Procedure: Add 4.6 g of conc. hydrochIorIc acId fo 250 mI ÐrIonmoyor fIask confaInIng
125 mI wafor and 5.1 g t5.0 mI) of anIIIno. SfIr unfII anIIIno has compIofoIy dIssoIvod. To
fhIs soIufIon add 6.9 g t6.4 mI) of froshIy dIsfIIIod acofIc anhydrIdo shakIng fIII fho soIufIon
Is cIoar. ImmodIafoIy pour fho confonfs of fho fIask Info a soIufIon of 8.3 g of sodIum
acofafo In 25 mI of wafor. Shako vIgorousIy and fhon cooI In Ico. !IIfor fho soIId on a
Buchnor funnoI and wash wIfh 15 mI of coId wafor and dry In aIr. Tho yIoId Is 4.9 g, m.p.
114°C.
Step B: PrepuruIion oj p-bromouceIuniIiJe
Procedure: Tako 3.4 g of acofanIIIdo In a 250 mI ÐrIonmoyor fIask and dIssoIvo In 25 mI of
acofIc acId. In a socond fIask dIssoIvo 1.3 mI t4.2 g) of bromIno In 10 mI of acofIc acId
tNofo I). Add fho bromIno soIufIon graduaIIy wIfh consfanf sfIrrIng fo fho acofanIIIdo soIufIon
ovor a porIod of 5 mIn koopIng fho fIask cooIod In Ico-bafh. Tho bromIno coIor dIsappoars
and crysfaIs bogIn fo appoar. AIIow fho fIask fo sfand af room fomporafuro for 30 mIn. and
fhon pour fho confonfs Info 250 mI of wafor. SfIr fho mIxfuro woII, and cooI and add 1÷2 g
of sodIum bIsuIfIfo fo romovo any oxcoss bromIno. !IIfor fho soIId on a Buchnor funnoI,
wash fhoroughIy wIfh wafor. RocrysfaIIIzo from ofhanoI. Tho yIoId Is 4.5 g, m.p. 167°C.
Step C: PrepuruIion oj p-bromouniIine
Procedure: PIaco 4 g of p-bromoacofanIIIdo In a 100 mI round-boffomod fIask and fo fhIs
add 35 mI of 5 N hydrochIorIc acId. !Ix a rofIux condonsor and aIIow fho mIxfuro fo boII
unfII aII fho soIId has dIssoIvod. RofIux for anofhor 15÷20 mIn. CooI fho soIufIon In Ico and
carofuIIy add 25% of sodIum hydroxIdo soIufIon fo mako If jusf aIkaIIno tNofo II). Tho
p-bromoanIIIno soon soparafos ouf. !IIfor fho soIId and rocrysfaIIIzo from hof aIcohoI. Tho
yIoId Is 3.1 g, m.p. 66°C.
Notes ¡: Work carofuIIy wIfh bromIno In fho fumo hood.
¡¡: !so a pH papor.
Question
8.49 WrIfo a mochanIsm for fho acId hydroIysIs of p-bromoacofanIIIdo fo p-bromoanIIIno.
ChupIer 9
SPECTROSCOPIC METHODS
Tho anaIyfIcaI mofhods dIscussod In fho oarIIor chapfors havo boon avaIIabIo fo organIc
chomIsfs sInco Iong, and undoubfodIy havo provon of Immonso vaIuo In fho IdonfIfIcafIon
and sfrucfuro doformInafIon of organIc compounds. Thoso aro, howovor, oxcoodIngIy fImo
consumIng and fho InformafIon obfaInod Is offon InconcIusIvo. Nowadays varIous
spocfroscopIc mofhods havo groafIy facIIIfafod fho anaIysIs and fhoy suppIomonf fho cIassIcaI
mofhods. SpecIroscopy Is a fochnIquo for fho moasuromonf of fho amounf of radIafIon
absorbod by fho subsfanco af varIous wavoIongfhs. Tho spocfrum ovoIvos usofuI InformafIon
abouf fho funcfIonaI group and fho moIocuIar sfrucfuro. OnIy fwo fochnIquos, namoIy,
Infrarod (i.r.) and nucIoar magnofIc rosonanco (n.m.r) wIII bo dIscussod bocauso fhoso aro
probabIy roadIIy avaIIabIo and In conjuncfIon wIfh fho "wet unulysls" offon provIdo suffIcIonf
InformafIon fo compIofo fho sfrucfuraI IdonfIfIcafIon of moIocuIos. Tho spocfroscopIc mofhods
possoss fho addod advanfago In fhaf fho moasuromonfs can bo mado In a shorf fImo wIfh a
vory smaII amounf of fho maforIaI.
9.1 INFRARED SPECTROSCOPY (i.r.)
ThIs fochnIquo Is boIng usod mosf wIdoIy for fho IdonfIfIcafIon of organIc compounds sInco
fho oarIy 1950`s. Tho spocfrum Is usuaIIy vory compIox and If IdonfIfIos fho funcfIonaI
group In a moIocuIo as woII as fho fypo of bondIng bofwoon varIous afoms. OrganIc moIocuIos
aro nof rIgId; fhoy rafhor confInuousIy undorgo vIbrafIonaI and rofafIonaI mofIons. Tho
moIocuIar vIbrafIons aro of fwo fypos, namoIy, sfrofchIng and bondIng t!Ig. 9.1). Thoso
vIbrafIons havo corfaIn froquoncIos whIch aro roIafod fo fho massos of fho afoms InvoIvod
and upon fho fypo of chomIcaI bondIng joInIng fho afoms.
Thoso froquoncIos of moIocuIar vIbrafIons corrospond fo fho Infrarod radIafIon. Whon
fho froquoncy of radIafIon corrosponds fo corfaIn characforIsfIc froquoncy of moIocuIar
vIbrafIon, IIghf Is absorbod. If Is fhus possIbIo fo IdonfIfy fho funcfIonaI group from fho
appoaranco of fho absorpfIon bands.
!or a moIocuIo fo absorb Infrarod radIafIon fhoro Is a roquIromonf fhaf absorpfIon of
onorgy shouId rosuIf In a nof chango In fho dIpoIo momonf of fho moIocuIo. Thus carbon
monoxIdo, buf nof bromIno or IodIno, absorbs Infrarod IIghf.
254 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Fig. 9.1: Vibrational modes of groups of atoms.
Tho Infrarod rogIon of fho oIocfromagnofIc spocfrum of Inforosf fo fho organIc chomIsf
occurs rafhor In a narrow rango, i.c., 2 µ t4000 cm
÷1
) fo 15 µ t666 cm
÷1
), 1 µ = 10
÷4
cm
t10, 000 A ) and Is capabIo of provIdIng usofuI InformafIon. Bofh wavoIongfh and froquoncy
aro commonIy usod fo doscrIbo an Infrarod absorpfIon. Tho convorsIon of wavoIongfh fo
froquoncy can bo affocfod by fho foIIowIng oquafIon:
( )
) In (
10
cn v
1
1

=
9.1.1 Instrumentation
An Infrarod Insfrumonf may bo dosIgnod oIfhor on a sIngIo boam or a doubIo boam prIncIpIo.
A sIngIo boam spocfromofor consIsfs of a radIafIon sourco, an oIocfrIcaIIy hoafod carborundum
rod, a Nornsf fIIamonf whIch Is passod fhrough fho sampIo and fho omorgonf boam fhaf Is
dIsporsod by a monochromafor Info Ifs IndIvIduaI wavoIongfhs. Tho spocfrum Is fhon scannod
on a spocIaI charf papor.
A doubIo boam Insfrumonf works on a sImIIar prIncIpIo, oxcopf fhaf fho orIgInaI radIafIon
Is dIvIdod Info fwo boams, ono of whIch passos fhrough fho sampIo whIIo fho ofhor fhrough a
roforonco coII. Such an Insfrumonf rocords fho dIfforonco In fho InfonsIfIos of fho fwo boams.
9.1.2 Preparation of Sample
Tho handIIng of sampIo for rocordIng Ifs Infrarod doponds on fho physIcaI sfafo of fho
compound, i.c., whofhor gas, IIquId or soIId. A gas sampIo Is pIacod In a gas fIghf coII. Tho
coII Is mado of pofassIum bromIdo or rock saIf and oxamInod dIrocfIy. PofassIum bromIdo Is
fransparonf In fho Infrarod rogIon. Tho confacf of a coII wIfh moIsfuro musf bo scrupuIousIy
avoIdod, ofhorwIso If bocomos cIoudy and fransmIfs vory IIffIo IIghf. SInco gIass absorbs
sfrongIy In fho usofuI Infrarod rogIon, If cannof bo usod for fho opfIcaI parf of a
spocfrophofomofor. LIquId sampIos fhaf aro non-voIafIIo aro gonoraIIy oxamInod as a fhIn
fIIm bofwoon fwo pofassIum bromIdo saIf pIafos. Ono or fwo drops of fho sampIo aro pIacod
bofwoon fho pIafos, rubbod unIformIy and fhon pIacod In fho pafh of IIghf. SoIIds aro gonoraIIy
handIod on a poIIof producod from a sampIo and dry pofassIum bromIdo In a hydrauIIc
pross. Tho Infrarod spocfra of soIIds as woII as IIquIds may aIso bo run as soIufIons In a
suIfabIo soIvonf. Tho conconfrafIon rango ompIoyod Is usuaIIy bofwoon 2 fo 10% by woIghf.
Tho choIco of fho soIvonf doponds on fho soIubIIIfy of fho sampIo and characforIsfIc
absorpfIons of fho soIvonf. If Is vory much dosIrabIo fo uso a soIvonf havIng fho Ioasf
SPECTROSCOPIC METHODS 255
amounf of absorpfIon In fho i.r. rogIon, soIvonfs offon ompIoyod aro carbon fofrachIorIdo,
chIoroform and carbon dIsuIfIdo ofc. Tho soIvonf usod shouId bo compIofoIy dry. In addIfIon
fo fho sampIo coII, a roforonco coII fIIIod wIfh fho samo soIvonf Is pIacod In fho roforonco
boam of fho Insfrumonf. If fho soIvonf absorbs woakIy In a gIvon rogIon of fho spocfrum, Ifs
absorpfIon may bo cancoIIod ouf.
9.1.3 Interpretation of Spectra
An Infrarod spocfrum Is a pIof of wavoIongfh tIn µ) or froquoncy twavo numbor) as abscIssa
and a funcfIon moasurIng fho absorpfIon of fho compound af varIous wavoIongfhs as ordInafo.
ThIs funcfIon Is fho porconf fransmIffanco, I.o., |1|
o
× 100 whoro | Is fho InfonsIfy of IIghf
passIng fhrough fho sampIo, |
o
Is fho InfonsIfy of fho IncIdonf IIghf. Tho rogIon of maxImum
absorpfIon, fhoroforo, appoars as ruIIeys In fho spocfrum. An Infrarod spocfrum Is usuaIIy
compIox bocauso of fho muIfIfudo of vIbrafIons fhaf can occur In a moIocuIo confaInIng
sovoraI afoms and bonds. Tho InforprofafIon of fho spocfrum commoncos wIfh fho
oxamInafIon of fho major bands tsoo TabIo 9.1). Tho rogIon oxfondIng from 7 fo 11 µ Is
offon roforrod fo as fho jingerprinI region of fho spocfrum. If Is characforIsfIc and unIquo
for ovory compound. In fhIs rogIon fho spocfra of fwo dIssImIIar compounds parfIcuIarIy
dIffor. A porfocf sImIIarIfy In fhIs rogIon and In ofhor parfs of fho spocfrum tI.o., fho spocfra
aro compIofoIy suporImposabIo) IndIcafos fhaf fho fwo organIc moIocuIos aro IdonfIcaI.
ComparIson of spocfra of 'unknown` compounds wIfh fhoso of 'known` compounds can fhus
bo ono vory usofuI fochnIquo for sfrucfuro doformInafIon.
Lof us consIdor fho spocfrum of 2-bufanoI t!Ig. 9.2). If shows
absorpfIons owIng fo C ÷ O and O ÷ H sfrofchIng vIbrafIons af 1120 cm
÷1
t8.92 µ) and
3350 cm
÷1
t2.98 µ), rospocfIvoIy, In addIfIon fo fho hydrocarbon chromophorIc groups prosonf.
Fig. 9.2: Infrared spectrum of 2-butanol.
256 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho sfrong absorpfIon af 3350 cm
÷1
t2.98 µ) Is fypIcaI of fho poIymorIc assocIafIon of hydroxyI
groups. Tho non-bondod absorpfIon poak Is baroIy porcopfIbIo. If fho Infrarod spocfrum Is
run In a vory dIIufo soIufIon of aIcohoI In carbon fofrachIorIdo In ordor fo docroaso fho
chancos of hydrogon bond, fho band wouId appoar af a shorfor wavoIongfh thIghor onorgy)
duo fo fho sfrofchIng modo of a froo hydroxyI group. Tho sfrofchIng modo of hydrogon
bondod ÷OH bonds occurs af a Iowor onorgy.
!Iguro t9.3) roprosonfs a spocfrum of cycIohoxanono In fhIs spocfrum,
sfrofchIng appoars af 1715 cm
÷1
t5.83 µ). Tho posIfIon of absorpfIon Is sonsIfIvo fo rIng sIzo and
fo fho dogroo of conjugafIon. Thus In cycIoponfanono, fho group absorbs af 1751 cm
÷1
t5.7 µ) i.c., af a hIghor wavo numbor. In caso of conjugafIon, absorpfIon occurs af a Iowor wavo
numbor fhus mofhyI foIyI kofono, absorbs af 1675 cm
÷1
t5.95 µ).
Fig. 9.3: Infrared spectrum of cyclohexanone.
Fig. 9.4: Infrared spectrum of benzamide.
SPECTROSCOPIC METHODS 257
Anofhor oxampIo whIch domonsfrafos fho ufIIIfy of i.r. Is fhaf of bonzamIdo t!Ig. 9.4).
Tho N÷H sfrofchIng absorpfIons appoar as fwo bands af 3356 cm
÷1
t2.98 µ) and
3110 cm
÷1
t3.182 µ). Tho
+
sfrofchIng appoars af 1670 cm
÷1
t5.98 µ).
Table 9.1: Characteristic Infrared Absorptions of Selected Functional Groups
Functlonul group Runge
p r (cm
~1
)
C÷H taIkano, ÷CH
3
) 3.38 ÷ 3.51 2962 ÷ 2853
C÷H taIkono, C=C=
0
0
+ ) 3.29 ÷ 332 3040 ÷ 3020
C÷H taIkyno, ÷C=C÷H) 3.03 3300
C÷H taromafIc) 3.30 3030
O÷H tmonomorIc aIcohoIs, phonoIs) 2.74 ÷ 2.79 3650 ÷ 3590
Hydrogon bondod 2.72 ÷ 3.12 3650 ÷ 3200
N÷H tamInos) 2.77 ÷ 3.12 3600 ÷ 3200
÷C=C÷ taIkono)
÷CC÷ taIkyno) 5.95 ÷ 6.17 1680 ÷ 1620
÷C=C ÷ taromafIc) 6.25 ÷ 6.67 1600 ÷ 1500
4.57 ÷ 4.76 2260 ÷ 2100
+ taIdohydos, kofonos, 5.68 ÷ 5.92 1300 ÷ 1050
carboxyIIc acId, osfors)
+ tcarboxyIIc acIds) 5.80 ÷ 5.88 1760 ÷ 1690
+ tosfors) 5.71 ÷ 5.76 1725 ÷ 1750
+
taIdohydos) 5.87 ÷ 5.95 1750 ÷ 1735
+ tkofonos) 5.80 ÷ 5.87 1705 ÷ 1680
C -Iacfono 5.62 ÷ 5.68 1725 ÷ 1705
C ÷ NO
2
6.37 ÷ 6.67 1780 ÷ 1760
C ÷ CI 12.5 ÷ 16.7 1760 ÷ 1690
800 ÷ 600
C ÷ Br 16.6 ÷ 20.0 600 ÷ 500
C ÷ I ~ 20 ÷ 500
S ÷ H 3.82 ÷ 3.92 2600 ÷ 2550
258 LABORATORY MANUAL OF ORGANIC CHEMISTRY
9.2 NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY (n.m.r.)
Tho absorpfIon of radIo froquoncy radIafIon by nucIoI Is formod as nucIoar magnofIc rosonanco
and fhIs fochnIquo gonoraIIy bocamo avaIIabIo sInco oarIy 1960. If has provod fo bo a poworfuI
fochnIquo for sfrucfuraI sfudIos and moro so fhan ovon Infrarod spocfroscopy.
AII nucIoI possoss chargo and mass buf nucIoI of corfaIn afoms possoss nucIoar spIn. A
hydrogon afom, for Insfanco, havIng an unovon numbor of profons and noufrons In fho
nucIous, has a spIn numbor | = 1/2. ThIs spInnIng nucIous may bo onvIsagod as a spInnIng
fop wIfh an axIs passIng fhrough fho confor t!Ig. 9.5). Such a nucIous fhus bohavos as a
fIny magnof and possossos magnofIc momonf.
Fig. 9.5: Spinning of a nucleus in magnetic field.
Whon fho spInnIng nucIous Is pIacod In an oxfornaI magnofIc fIoId H
0
, fho magnofIc
dIpoIo may oIfhor orIonf wIfh or agaInsf fho fIoId. Tho formor orIonfafIon Is a sfafo of hIgh
onorgy whIIo fho Iaffor fhaf of Iow onorgy. Tho axIs of fho spInnIng profon undor fho
InfIuonco of fho oxfornaI fIoId procossos abouf fho axIs of fho appIIod fIoId. Tho froquoncy,
M

of procossIon Is gIvon by:
0 0 0
2 H πν γ ω = =
whoro C Is a consfanf known as fho magnofogyrIc rafIo ta fundamonfaI nucIoar consfanf)
for fho hydrogon nucIous and v
0
Is fho froquoncy of procossIon. Tho froquoncy M

fhus
Incroasos as H
0
Incroasos. If oIocfromagnofIc radIafIon of froquoncy

Is appIIod af rIghf
SPECTROSCOPIC METHODS 259
angIos fo fho appIIod fIoId, fho appIIod froquoncy Is saId fo bo In resonunce wIfh fho
procossIonaI froquoncy whon M

=

. Af fhIs sfago fho radIafIon Is absorbod by fho nucIous
and If undorgoos a 'Illp' fo fho noxf hIghor onorgy IovoI. An absorpfIon poak Is obfaInod
whIch can bo dofocfod oIocfronIcaIIy and rocordod as a poak on a charf. ThIs Is achIovod
oxporImonfaIIy by appIyIng froquoncIos whIch In fho caso of profon aro In fho radIo froquoncy
rango, gonoraIIy 60 MHz tmoga Horfz) and corrosponds fo a wavoIongfh of 5 × 10
2
cm af a
magnofIc fIoId of 14,092 gauss. Tho condIfIon of rosonanco for a profon can bo achIovod
oIfhor by hoIdIng H
0
consfanf and varyIng or by maInfaInIng af a consfanf vaIuo and
changIng H
0
. Tho Iaffor approach, howovor, Is moro convonIonf. NucIoI fhaf havo spIn and
aro Imporfanf fo an organIc chomIsf aro
1
H,
13
C,
19
!, ofc. Mosf n.m.r. sfudIos havo boon
carrIod ouf on hydrogon tprofon) nucIoI and fho fochnIquo Is fhus roforrod fo as profon
magnofIc rosonanco tp.m.r. or 'H n.m.r.).
In an n.m.r. spocfrum an absorpfIon poak Is obfaInod for oach fypo of profon In fho
moIocuIo and af a dIfforonf froquoncy of rosonanco. ThIs doponds on fho onvIronmonf In
whIch fho nucIoI aro prosonf, I.o., fho noIghbourIng nucIoI and oIocfrons. A profon In a
moIocuIo Is surroundod by a cIoud of oIocfronIc chargo. In a magnofIc fIoId fho oIocfrons
orIonf In such a way fhaf fhoIr mofIon Inducos a magnofIc momonf fhaf ordInarIIy opposos
fho appIIod fIoId. As a rosuIf fho nucIous Is oxposod fo an offocfIvo fIoId fhaf Is somowhaf
smaIIor tbuf In somo casos Iargor aIso) fhan fho oxfornaI fIoId. In ofhor words, fho nof
magnofIc fIoId Is sIIghfIy Ioss fhan fho appIIod fIoId. SInco fho nucIous oxporIoncos a smaIIor
fIoId If Is saId fo bo shlelded. A hIghor magnofIc fIoId musf fhus bo appIIod fo achIovo
rosonanco. ThIs gIvos rIso fo chemlcul shlIt whIch Is doscrIbod as fho dIfforonco In fho
absorpfIon posIfIon of a parfIcuIar profon of a sampIo from fhaf of fho roforonco profon.
Thoro aro sovoraI fypos of roforonco compounds buf for profons fho posIfIons of fho absorpfIon
poaks aro nofod wIfh roforonco fo foframofhyIsIIano tTMS) a voIafIIo IIquId, b.p. 26.4°C
usod as an InfornaI sfandard. !or fhIs compound a sIngIo sharp rosonanco IIno occurs af fho
hIghosf fIoId ond of fho rango of obsorvod profon shIffs whoro If Is unIIkoIy fo obscuro any
ofhor profon rosonanco arIsIng from fho sampIo. ThIs sfandard Is assIgnod a chomIcaI shIff
of 0 Hz.
Tho chomIcaI shIff of a profon Is doformInod In unIfs of cps, dopondIng on fho oscIIIafor
froquoncy. If has boon found convonIonf fo convorf such shIff Info froquoncy Indopondonf
unIfs, oxprossod as doIfa (@ ):
@
= ×
6
Chemical shift in cps
10
Oscillator frequency in cps
260 LABORATORY MANUAL OF ORGANIC CHEMISTRY
Tho @ vaIuos aro oxprossod as parfs por mIIIIon tppm). An aIfornafIvo scaIo Is tuu (J)
scaIo. TMS Is assIgnod an arbIfrary vaIuo of 10.00. To convorf a chomIcaI shIff gIvon on fho
doIfa scaIo fo tuu scaIo, sImpIy subfracf fho shIff as moasurod on fho doIfa scaIo from 10, I.o.,
J = 10.00 – @
Tho chomIcaI shIffs (J) for a wIdo varIofy of hydrogons aro gIvon In TabIo 9.2.
Fig. 9.6: Diagram of nuclear magnetic resonance spectrometer.
9.2.1 Instrumentation and Sample Handling
Tho sampIo Is mIxod In a gIass fubo whoso InfornaI dIamofor Is 2÷3 mm. A fow drops of
TMS aro addod and fho fubo Is fhon pIacod In fho sampIo hoIdor bofwoon fho poIo facos of a
dc oIocfromagnof t!Ig. 9.6) spacod 1.75 Inchos aparf. Tho radIo froquoncy sIngIo producod
by fho rosonafIng nucIoI Is dofocfod by moans of a coII fhaf surrounds fho sampIo. Tho
sampIo hoIdor Is rofafod whIch sorvos fo avorago ouf fho offocfs of InhomogonIfIos; sharpor
IInos aro obfaInod as a consoquonco.
SPECTROSCOPIC METHODS 261
Table 9.2: Typical Chemical Shifts of Hydrogens
Chemlculs shlIt
J (ppm @)
RCH
3
9.1 0.9
R
2
CH
2
8.7 1.3
R
3
CH 8.5 1.5
C=C÷H 4.5 ÷ 5.4 4.6 ÷ 5.9
Ar÷H 1.5 ÷ 4 6 ÷ 8.5
C=C÷CH
3
8.3 1.7
C=C÷CH
3
8.2 1.8
CIC÷H 6.7 3.4
CI
2
CH 4.2 5.8
Br÷C÷H 6 ÷ 7.5 2.5 ÷ 4
O
2
NC÷H 5.4 ÷ 5.8 4.2 ÷4.6
OC÷H taIcohoI, ofhor) 6 ÷ 6.7 3.3 ÷ 4
OC÷H tosfors) 5.9 ÷ 6.3 3.7 ÷ 4.1
4 a + a 0
4
7 ÷ 38 2 ÷ 2.7

4a+a0
0 ÷ 1 9, 10
RO÷H 4.5 ÷ 9 1 ÷ 5.5
Ar÷OH ÷ 2 ÷ 6 4 ÷ 12

4+a0
÷ 2 fo ÷ 0.5 10.5 ÷ 12
RNH
2
5 ÷ 9 1 ÷ 5
)H+a0

÷ 0.1 10.1
262 LABORATORY MANUAL OF ORGANIC CHEMISTRY
9.2.2 Interpretation of Spectra
Lof us consIdor fho spocfrum of anIsoIo fo domonsfrafo fho ufIIIfy of n.m.r. fochnIquo. Tho
hydrogons of fho ÷OCH
3
groups aro chomIcaIIy oquIvaIonf fhus a sIngIo poak appoars af
6.92 J. Tho sIgnaIs down fIoId aro fhoso of fho aromafIc rIng. Tho orIho profons boIng
cIosor fo ÷OCH
3
groups aro moro shIoIdod fhan ncta and para profons and fhus appoar
downfIoId. Affor fho spocfrum Is doformInod If Is Infografod fo osfImafo fho roIafIvo numbor
of profons In oach absorpfIon.
Fig. 9.7: NMR spectrum of anisole.
Tho InfograI fracIng Is rocordod from Ioff fo rIghf. Tho hoIghf fo whIch fho fracIng
rIsos for oach group of profons Is proporfIonaI fo fho aroa oncIosod by oach poak, and
fhoroforo, fo fho numbor of profons.
Tho spocfrum of ofhanoI tnoaf) Is shown boIow t!Ig. 9.8). As Is ovIdonf from fho
sfrucfuro of ofhanoI If confaIns fhroo fypos of profons and fhoy absorb af dIfforonf τ vaIuos
and corrospond fo ÷OH t4.63 J), ÷CH
2
t6.58 J) and ÷CH
3
t8.83 J). Tho aroa bonoafh oach
poak corrosponds fo a numorIcaI rafIo of 1 : 2 : 3. Thus n.m.r. Is a convonIonf moasuro of
nof onIy fho fypo buf aIso fho numbor of dIfforonf profons In fho moIocuIo.
SPECTROSCOPIC METHODS 263
Fig. 9.8: NMR spectrum of ethanol (CH
3
CH
2
OH).
If fho spocfrum of ofhanoI Is rocordod undor hIgh rosoIufIon t!Ig. 9.9) If Is found fhaf
fho spocfrum Is spIIf, I.o., oach poak Is spIIf Info sovoraI poaks. Thus mofhyI group Is spIIf
Info a frIpIof and fho mofhyIono group Info a quarfof. ThIs spIIffIng Is affrIbufod fo fho facf
fhaf fho magnofIc fIoId of ono sof of nucIoI Is InfIuoncod by fho spIn arrangomonfs of fho
nucIoI In fho noIghbourIng group. In ofhor words, fhoro Is a smaII InforacfIon or coupIIng
bofwoon fho fwo groups of nucIoI. ThIs phonomonon Is known as spln-spln spllttlng. Tho
spacIng tIn cps) of fho fhroo compononfs of fho mofhyI group frIpIof Is found fo bo oquaI fo
fho spacIng of fho four compononfs of fho mofhyIono group quarfof. ThIs spacIng Is roforrod
fo as coupIIng consfanf, J, and Is a moasuro of fho offocfIvonoss of coupIIng bofwoon fwo
profons wIfh dIfforonf chomIcaI shIffs.
Fig. 9.9: NMR spectrum of ethanol under high resolution.
264 LABORATORY MANUAL OF ORGANIC CHEMISTRY
!Iguro 8.10 roprosonfs fho spocfrum of =-bromobufyrIc acId, CH
3
CH
2
CHBrCOOH and
domonsfrafos fho spIIffIng by noIghbourIng profons. MofhyI profons appoar af 8.92 tfrIpIof),
mofhyIono profons af 7.93 tquInfof) and fho mofhono profons af a Iowor fIoId af 5.77 tfrIpIof).
Af InforosfIng foafuro Is fho carboxyI profon whIch appoars af J = 10. 97 ppm
t÷ 0.97 J). CarboxyIIc acIds usuaIIy absorb In fho rogIon ÷ 2.0 fo ÷ 0.5 J.
Fig. 9.10: NMR spectrum of =-bromobutyric acid.
Questions
9.1 Whaf Is fho Imporfanco of ¯fIngorprInf¨ rogIon In i.r.7
9.2 Whaf Is fho purposo of TMS In n.n.r.7
9.3 A compound wIfh fho moIocuIar formuIa C
7
H
6
O
2
has fho foIIowIng i.r. and n.n.r. spocfra.
Proposo a sfrucfuro.
SPECTROSCOPIC METHODS 265
266 LABORATORY MANUAL OF ORGANIC CHEMISTRY
9.4 Tho n.n.r. spocfrum of compound wIfh moIocuIar formuIa C
2
H
3
CI
3
Is shown boIow,
suggosf a suIfabIo sfrucfuro.
9.5 An aromafIc compound wIfh moIocuIar formuIa C
10
H
12
O
2
gIvos fho hydroxamIc acId
fosf and on acId hydroIysIs yIoIds C
8
H
10
O and C
2
H
4
O
2
. Tho n.n.r. spocfrum Is gIvon
boIow. Suggosf a sfrucfuro for fhIs compound.
SPECTROSCOPIC METHODS 267
9.6 In fho foIIowIng fwo n.n.r spocfra, ono corrosponds fo 3-mofhyI-3-hydroxy-2-bufanono
and fho ofhor fo 2-mofhyI-3-bufyn-1-oI. !Ind ouf whIch Is whIch.
This page
intentionally left
blank
SELECTED REFERENCES
1. R.L. ShrInor, R.C. Iuson and Ð.Y. CurfIn, The 8ystenatic lJentijication oj Organic
ConpounJs, 5fh odn., John WIIoy, Now York t1964).
2. N.Ð. ChoronIs and J.B. EnfrIkon, lJentijication oj Organic ConpounJs, 2nd odn., John
WIIoy, Now York t1963).
3. Ð.J. Iasfo and C.R. Johnson, Organic 8tructure Deternination, IronfIco-HaII, EngIowood
CIIIIs, N.J. t1969).
4. K.T. IInIoy and J.WIIson, Laboratory Manua/ in FunJanenta/ Organic Chenistry, IronfIco-
haII, EngIowood CIIIIs, N.J. t19?0).
5. ta) I.E. Ianfa and C.S Wang, ¯LImIfafIons oI HInsborg Mofhod Ior IrImry AmInos¨, J.
Chen. EJuc. 41, 280 t1964).
tb) C.R. OambIII, T.Ð. Roborfs and H. Shochfor, ibiJ, 49, 28? t19?2).
6. M. Voora and OasparIo, Detection anJ lJentijication oj Organic ConpounJs, IIonum Iross,
Now York t19?1).
?. H.T. CIark A HanJbooh oj Organic Ana/ysis, Longman, Rochosfor, N.Y. t1966).
8. A.I. VogoI, Qua/itatioe Organic Ana/ysis, Longman tELBS). London t19?2).
9. J.R. Ðyor, App/ications oj Absorption 8pectroscopy oj Organic ConpounJs, IronfIco-HaII,
EngIowood, N.J. t1969).
10. R.M. SIIvorsfoIn and O.C. BassIor, 8pectroscopic lJentijication oj Organic ConpounJs,
2nd odn., John WIIoy, Now York t196?).
11. L.J. BoIIamy, The lnjrareJ 8pectra oj Conp/ex Organic Mo/ecu/es, 2nd odn., John WIIoy,
Now York t1958).
12. K. NakanIshI, lnjrareJ Absorption 8pectroscopy, HoIdon-day, San IrancIso t1962).
13. L.M. Jackman and S. SfornhaII, Nuc/ear Magnetic Pesonance 8pectroscopy, 2nd odn.,
Iorgamon Iross, Now York t1969).
14. A.I. VogoI, E/enentary Fractica/ Organic Chenistry, Iarf I, 2nd odn., Longman, London
t1966).
270 LABORATORY MANUAL OF ORGANIC CHEMISTRY
15. O.BrIogor, A Laboratory Manua/ jor MoJern Organic Chenistry, Harpor and Row, Now
York t1969).
16. I.T.S. Law and M.Kosfnor, ¯IroparafIon oI HoforocycIIcs¨, J. Org. Chen. 33, 4426 t1968).
1?. Ð.L. IavIa, ¯CaIIoIno IsoIafIon¨ J. Chen. EJuc. 50, ?91 t19?3), aIso soo R. O. Connor, J.
Chen. EJuc. 42, 492 t1965).
18. K.L. Lockwood, ¯SoIvonf EIIocf on Kofo-EnoI EquIIIbrIum oI AcofoacofIc Esfor, ¯J. Chen.
EJuc. 42, 481 t1965).
19. R.K. BansaI, A Textbooh oj Organic Chenistry, 5fh odn., Now Ago InfornafIonaI, Now
ÐoIhI t200?).
20. O.K. HoImkamp and H.W. Johnson, Jr., 8e/ecteJ Experinents in Organic Chenistry, W. H.
Irooman and Co., San IrancIsco t1964).
21. R.Q. Browsfor, C.A. VandorworI and W.E. McEwon, Uniti:eJ Experinents in Organic
Chenistry, 2nd odn., Van Nosfrand, Now York t1964).
22. W.I. Soronson and T.W. CampboII, Freparatioe MethoJs oj Fo/yner Chenistry, John WIIoy,
Now York t1963).
23. I. Yafos and I. Eafon, ¯LowIs-AcId CafaIyzod Ð. A. RoacfIon,¨ J. An. Chen. 8oc., 82, 4436
t1960); AIso soo R.K. BansaI, A.W. McCuIIoch, I.W. Rasmusson and A.O. McInnos, CanaJ,
J. Chen. 53, 138 t19?5).
24. K.B. WIborg, Laboratory Techniques in Organic Chenistry, McOraw-HIII, Now York t1960).
25. J. Casanova, ¯RoIafIvo Rafos oI EIocfrophIIIc SubsfIfufIon¨ J. Chen. EJuc., 41, 341 t1964).
26. R.M. Roborfs, L.B. RodowaId and A.S. WIngrovo, An lntroJuction to MoJern Experinenta/
Organic Chenistry, HoIf, RInoharf and WInsfon, Now York t1985).
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28. J.W. Hass, J. Chen, EJuc., 61, 346, t19?4).
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RossIfor. Ed., WIIoy InforscIonco, Now York t19?1), VoI. 1, Iarf 5. Chapfor 3.
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RIvor, Now Jorsoy.
AppenJix 1
PREPARATION OF REAGENTS
1. ¡sothlouronlum chlorlde reugent
RoIIux a mIxfuro oI 2 g bonzyI chIorIdo and 1.2 g oI fhIouroa In 30 mI mofhanoI Ior 30 mIn.
Thon cooI fho IIask In an Ico-bafh. CoIIocf fho soIId on a Buchnor IunnoI. Wash fho soIId
sovoraI fImos wIfh smaII porfIons oI ofhyI acofafo and dry.
2. Cerlc ummonlum nltrute solutlon
ÐIssoIvo 20 g oI corIc ammonIum nIfrafo In 500 mI oI warm 2 N nIfrIc acId.
3. Lucus reugent
ÐIssoIvo wIfh cooIIng 136 g oI anhyd. zInc chIorIdo In 89 mI oI conc. hydrochIorIc acId.
4. 2, 4-Dlnltrophenylhydruzlne
ÐIssoIvo 2 g 2, 4-dInIfrophonyIhydrazIno In 15 mI oI conc. suIIurIc acId. Add fho soIufIon fo
50 mI oI 95% ofhanoI, fhon dIIufo fho mIxfuro fo 15 mI wIfh dIsfIIIod wafor. MIx fhoroughIy
and IIIfor II nocossary.
5. ¡odlne solutlon
ÐIssoIvo 20 g pofassIum IodIdo and 10 g IodIno In 100 mI wafor.
6. Ammonlum vunudute reugent
ÐIssoIvo 30 mg oI ammonIum vanadafo In 100 mI oI wafor.
?. 8-Hydroxyqulnollne
ÐIssoIvo 2.5 g oI 8 hydroxyquInoIIno In 100 mI oI 6% acofIc acId.
8. Qulnhydrone reugent solutlon
Shako abouf 0.5 g oI p-bonzoquInono wIfh 10 mI oI wafor and fo fhIs add a soIufIon oI 0.5
g oI hydroquInono In 10÷15 mI wafor. Tho groonIsh-bIack crysfaIs oI quInhydrono aro
Iormod by an addIfIon roacfIon.
9. Chlorlne wuter
Iass chIorIno gas In coId wafor fIII a safurafod soIufIon Is obfaInod.
10. Mollsch reugent
ÐIssoIvo 1 g =-naphfhoI In 100 mI oI 95% ofhanoI.
272 LABORATORY MANUAL OF ORGANIC CHEMISTRY
11. Methyl orunge lndlcutor
ÐIssoIvo 1 g oI mofhyI orango In 100 mI oI wafor.
12. Phenolphthuleln lndlcutor
ÐIssoIvo 1 g phonoIphfhaIoIn In 100 mI oI 95% aIcohoI.
13. SchlII' s reugent
ÐIssoIvo 1 g rosanIIIno hydrochIorIdo In 100 mI wafor and pass suIIur dIoxIdo fIII fho
soIufIon bocomos coIorIoss.
14. Sturch solutlon
Mako a pasfo oI 1 g soIubIo sfarch In 50 mI oI boIIIng wafor wIfh Iroquonf sfIrrIng. BoII fho
mIxfuro fIII a cIoar soIufIon Is obfaInod.
15. Benedlct's solutlon
ÐIssoIvo 86.5 g crysfaIIIzod sodIum cIfrafo and 50 g anhydrous sodIum carbonafo In abouf
350 mI dIsfIIIod wafor. IIIfor II nocossary. Add a soIufIon oI 8.65 g oI crysfaIIIzod cuprIc
suIIafo In 50 mI wafor wIfh consfanf sfIrrIng. ÐIIufo fo 500 mI.
16. Fluoresceln test puper
In can bo proparod by dIppIng IIIfor papor sfrIps In a dIIufo ofhanoIIc soIufIon oI
IIuoroscoIn. Tho papor drIos roadIIy and possossos a Iomon yoIIow coIor.
1?. Dlchromute solutlon
ÐIssoIvo 10 g oI sodIum dIchromafo In a mIxfuro oI ?5 mI wafor and 25 mI conc. suIIurIc
acId.
18 Ferrlc chlorlde solutlon
ÐIssoIvo 1 g IorrIc chIorIdo In 100 mI oI dIsfIIIod wafor.
19. Sodlum hydroxlde solutlon (uqueous)
ÐIssoIvo 10 g oI sodIum hydroxIdo poIIofs In 100 mI wafor.
20. Sodlum hydroxlde solutlon (ulcohollc)
ÐIssoIvo 10 g sodIum hydroxIdo poIIofs In 100 mI aIcohoI.
AppenJix 2
PURIFICATION OF SOLVENTS
Acetlc ucld, b.p. 118°C
AcofIc acId Is usod as a roagonf In haIogonafIon roacfIons. CommorcIaI acId confaIns fracos oI
acofaIdohydo and ofhor oxIdIzabIo ImpurIfIos. Thoso ImpurIfIos can bo oIImInafod by roIIuxIng fho
acId wIfh 2÷5% tby woIghf) oI pofassIum pormanganafo soIufIon Ior a porIod oI 2÷6 hrs. Tho acId Is
fhon dIsfIIIod and fho IracfIon passIng af 11?÷118°C Is coIIocfod. Tracos oI wafor, II prosonf, can bo
romovod Irom fho acId by froafIng If wIfh frIacofyIborafo proparod by warmIng 1 parf oI borIc acId
wIfh 5 parfs tby woIghf) oI acofIc anhydrIdo and hoafIng fo 60°C IoIIowod by cooIIng and IIIfrafIon fho
rosuIfIng soIId. Wafor roacfs wIfh frIacofyI borafo fo Iorm borIc and acofIc acId.
Any confacf oI fho acId wIfh fho skIn shouId bo avoIdod.
Acetone, b.p. 56.5°C
Iuro acofono Is usod as a soIvonf In many dIspIacomonf and oxIdafIon-roducfIon roacfIons. Tho
commorcIaI sampIo confaIns IsopropyI aIcohoI as an ImpurIfy.
CommorcIaI acofono Is roIIuxod wIfh soIId pofassIum pormanganafo Ior 4÷5 hrs. II fho purpIo
coIor doodorIzos, add a pInch oI pofassIum pormanganafo and hoaf agaIn. ÐIsfII fho soIvonf and koop
ovornIghf ovor anhydrous pofassIum carbonafo. IIIfor and dIsfII agaIn. CoIIocf fho IracfIon passIng
af 56÷5?°C.
Kthyl ulcohol, b.p. ?8.4°C
EfhyI aIcohoI Is usod as a roagonf In a wIdo varIofy oI proparafIons. AIcohoI Is a mIxfuro oI 95.5%
aIcohoI and 0.5% wafor. AbsoIufo aIcohoI Is aIways ompIoyod fo obfaIn sodIum ofhoxIdo roquIrod Ior
condonsafIon roacfIons.
IroparafIon oI absoIufo aIcohoI Is accompIIshod by froafIng aIcohoI wIfh quIckIImo. In fhIs
mannor 99.5% aIcohoI Is obfaInod. Tho romaInIng fracos oI wafor aro romovod by dIsfIIIIng fho
azoofropIc mIxfuro wIfh bonzono or magnosIum furnIngs and a crysfaI oI IodIno.
QuIckIImo Is IroshIy proparod by hoafIng Iumps oI cIoan marbIo In a Iurnaco and fhon sforod In
sfopporod boffIos. In caso commorcIaI quIckIImo If usod Is shouId bo froafod sImIIarIy boIoro uso.
Abouf 200 g IroshIy hoafod quIckIImo Is addod fo 1 IIfro oI commorcIaI ofhanoI In a round-boffomod
IIask IIffod wIfh a roIIux condonsor and dryIng fubo, and roIIuxod Ior 5÷6 hrs on a wafor-bafh. If Is
fhon aIIowod fo sfand ovornIghf. Tho mIxfuro Is IIIforod fhough gIass wooI and fho IIIforod aIcohoI Is
274 LABORATORY MANUAL OF ORGANIC CHEMISTRY
dIsfIIIod wIfh fho oxcIusIon oI moIsfuro. Tho aIcohoI so obfaInod shouId bo proporIy sfopporod.
ExfromoIy dry ofhyI aIcohoI Is proparod by froafIng fho aIcohoI obfaInod wIfh magnosIum
furnIngs and IodIno. Tho IoIIowIng roacfIons fako pIaco:
2C
2
H
5
OH + Mg Mg(OC
2
H
5
)
2
+ H
2
Mg(OC
2
H
5
)
2
+ 2H
2
O 2C
2
H
5
OH + Mg(OH)
2
Ono IIfro oI aIcohoI Is fakon In a Iound-boffomod IIask, and 3.5 oI puro dry magnosIum furnIngs
and a pInch oI IodIno crysfaIs aro Infroducod Info fho IIask and fho mIxfuro roIIuxod. HoafIng Is
confInuod fIII aII fho mofaIIIc magnosIum has boon convorfod Info Ifs ofhyIafo. AddIfIonaI amounf oI
IodIno Is Infroducod, II nocossary. Tho absoIufo aIcohoI Is dIsfIIIod oII dIrocfIy Info a confaInor and
sfopporod proporIy. EfhyI aIcohoI Is a hIghIy InIIammabIo soIvonf.
Benzene, b.p. 80°C
Bonzono Is usod as a soIvonf In fho IrIodoI-CraIfs roacfIon and In many organIc proparafIons. If Is
aIso ompIoyod In chromafographIc soparafIons. Tho prIncIpaI ImpurIfy In commorcIaI bonzono Is
fhIophono tb.p. 84°C).
ThIophono can bo romovod Irom bonzono by shakIng wIfh conc. suIIurIc acId t80 mI / I oI bonzono)
In a soparafory IunnoI. Tho doop yoIIow Iayor oI fho acId Is wIfhdrawn and fho procoss Is ropoafod fIII
fho acId Iayor Is no moro coIorod. In fhIs procoss advanfago Is fakon oI fho Iacf fhaf fhIophono Is moro
roadIIy suIIonafod fhan bonzono. Bonzono Is fhon washod wIfh wafor fo romovo acId and drIod ovor
anhydrous caIcIum chIorIdo. AIfor docanfIng, bonzono Is dIsfIIIod wIfh fho oxcIusIon oI moIsfuro.
Bonzono may bo sforod Ior somo fImo ovor sodIum wIro boIoro dIsfIIIafIon.
Bonzono Is a hIghIy InIIammabIo and foxIc soIvonf.
Curbon dlsulIlde, b.p. 46°C
Carbon dIsuIIIdo Is usod as a soIvonf In organIc proparafIons and In fho IrIodoI-CraIfs roacfIon. Tho
commorcIaI grado carbon dIsuIIIdo confaIns sovoraI unwanfod suIIur compounds.
To purIIy carbon dIsuIIIdo If Is IIrsf shakon wIfh morcury mofaI IoIIowod by a safurafod soIufIon
oI morcurIc chIorIdo and IInaIIy pofassIum pormanganafo soIufIon. If Is fhon drIod ovor anhydrous
caIcIum chIorIdo or phosphorus ponfoxIdo ovornIghf and dIsfIIIod. LIko bonzono If Is aIso InIIammabIo
and foxIc.
Curbon tetruchlorlde, b.p. ??°C
Carbon fofrachIorIdo Is usod In sovoraI haIogonafIon as a soIvonf. Carbon dIsuIIIdo Is usuaIIy prosonf
as an ImpurIfy.
CommorcIaI carbon fofrachIorIdo Is shakon wIfh abouf ono-fonfh Ifs voIumo oI a mIxfuro
confaInIng conconfrafod soIufIon oI pofassIum hydroxIdo In ofhanoI af 60°C. ThIs procoss Is ropoafod
fwIco and fhon washod wIfh a smaII quanfIfy oI conc. suIIurIc acId unfII fho acId Iayor Is no moro
coIorod. If Is subsoquonfIy washod wIfh wafor and dIsfIIIod aIfor dryIng ovor anhydrous caIcIum
chIorIdo.
Carbon fofrachIorIdo Is usoIuI as a IIro oxfInguIshor buf In no caso Is fo bo uso ovor sodIum IIro,
as a vIoIonf oxpIosIon may fako pIaco.
APPENDIX 275
Chlorobenzene, b.p. 132°C
ThIs soIvonf Is usod In corfaIn voIumofrIc fIfrafIons and Ior rocrysfaIIIzIng sparIngIy soIubIo
subsfancos.
If can bo purIIIod by a caroIuI dIsfIIIafIon.
ChloroIorm, b.p. 61°C
ChIoroIorm Is a roacfanf In fho RoImor-TIomann roacfIon. If confaIns 0.5÷1% oI ofhanoI addod as a
sfabIIIzor.
ChIoroIorm Is shakon wIfh conc. suIIurIc acId and fhon washod wIfh wafor. If Is fhon dIsfIIIod
aIfor dryIng ovor anhydrous caIcIum chIorIdo. ChIoroIorm shouId novor bo drIod ovor sodIum wIro as
If may rosuIf In an oxpIosIon.
DlmethylIormumlde, b.p. 153°C
ÐImofhyIIormamIdo Is usod as a soIvonf In fho OabrIoI synfhosIs, docarboxyIafIon and !IImann
roacfIons.
If Is purIIIod by shakIng wIfh soIId pofassIum hydroxIdo In a soparafory IunnoI and fhon wIfh
IImo. Tho soIvonf Is fhon dIsfIIIod.
Dloxune, b.p. 101°C
ÐIoxano Is usod In a Iargo numbor oI organIc roacfIons parfIcuIarIy In soIvoIyfIc dIspIacomonf roacfIons.
If Is mIscIbIo wIfh wafor In aII proporfIons. If Iorms compIoxos wIfh OrIgnard roagonfs and, fhoroIoro,
cannof bo usod as a subsfIfufo Ior ofhor. CommorcIaI dIoxano confaIns wafor and smaII quanfIfIos oI
acofaIdohydo and gIycoI acofaI OIycoI Is hydroIyzod on koopIng wIfh fho rosuIfanf
IormafIon oI poroxIdo.
A mIxfuro oI 1 IIfro commorcIaI dIoxano, 13.5 mI conc. hydrochIorIc acId and 100 mI wafor Is
roIIuxod Ior 12 hrs. A sfroam oI dry nIfrogon gas Is sImuIfanoousIy bubbIod fo entrain acofaIdohydo.
Tho soIufIon Is aIIowod fo cooI fo room fomporafuro and soIId pofassIum hydroxIdo Is addod fIII no
moro oI If dIssoIvos and a socond Iayor soparafos ouf. ÐIoxano Iayor Is docanfod and roIIuxod wIfh
sodIum mofaI Ior 10÷12 hrs and dIsfIIIod. IoroxIdo prosonf as ImpurIfy, II dosIrod, can bo romovod
by passIng fho dIsfIIIod soIvonf fhrough a coIumn oI aIumIna t80 g Ior 100÷200 mI oI dIoxano).
ÐIoxano vapors aro vory poIsonous.
t-Butyl ulcohol, b.p. 83°C
If Is IargoIy ompIoyod In osforIIIcafIon and In fho proparafIon oI pofassIum t-bufoxIdo.
Tho aIcohoI can bo purIIIod IIrsf by dryIng ovor anhyd. caIcIum suIIafo IoIIowod by dIsfIIIafIon
ovor caIcIum hydrIdo.
Kther, b.p. 34.5°C
Efhor Is usod oxfonsIvoIy In fho organIc chomIsfry Iaborafory. Ior mosf purposos fho commorcIaI
grado Is safIsIacfory. Wafor, ofhanoI and poroxIdo prosonf In ofhor can bo romovod fo obfaIn anhydrous
osfor Ior spocIIIc purposos.
276 LABORATORY MANUAL OF ORGANIC CHEMISTRY
IroIImInary dryIng Is carrIod ouf by koopIng ofhor ovor anhyd. caIcIum chIorIdo Ior 24 hrs.
AIcohoI and wafor can fhus bo romovod fo a groaf oxfonf. If Is IIIforod Info anofhor cIoan boffIo and
sodIum wIro Is Infroducod Info If dIrocfIy Irom fho sodIum pross and aIIowod fo sfand Ior anofhor
24 hrs. Tho boffIo Is sfoppod whon ovoIufIon oI hydrogon has coasod. Efhor may bo dIsfIIIod on a hof
pIafo In fho hood. II If Is oxposod fo aIr, sIIghf oxIdafIon oI ofhor occurs wIfh fho IormafIon oI poroxIdo
C
2
H
5
÷O÷O÷C
2
H
5
. ThIs may causo oxpIosIon II ofhor Is dIsfIIIod fo drynoss. Tho prosonco oI poroxIdo
In ofhor may bo dofocfod by fho IIborafIon oI IodIno tbrown coIorafIon or bIuo coIor wIfh sfarch) whon
a smaII sampIo Is shakon wIfh an oquaI voIumo oI pofassIum IodIdo t2%) soIufIon and a Iow drops oI
dII. hydrochIorIc acId. IoroxIdos can bo dosfroyod by shakIng ofhor wIfh 5% soIufIon oI Iorrous suIIafo
whIch Is woakIy acIdIIIod wIfh suIIurIc acId. AIfornafIvoIy, oIfhor can bo passod ovor a coIumn oI
aIumIna t80 g oI aIumIna Ior ?50 mI oI ofhor) whoroby fho poroxIdo Is rofaInod by aIumIna.
If Is vory Imporfanf fo nofo fhaf whIIo workIng wIfh ofhor fhoro shouId bo no IIamo In fho
vIcInIfy.
Toluene, b.p. 110.6°C
ToIuono aIso confaIns suIIur compounds as ImpurIfy as doos bonzono. Tho maIn ImpurIfy Is mofhyI
fhIophono tb.p. 112÷113°C).
Ior purIIIcafIon 1 IIfro oI foIuono and 80 mI conc. suIIurIc acId aro sfIrrod mochanIcaIIy tor
magnofIc sfIrror) af 30°C by occasIonaI cooIIng. ToIuono Is fhon docanfod and froafod agaIn wIfh fho
acId fIII no moro coIor Is oxfracfod. IInaIIy, If Is washod wIfh wafor and drIod ovor anhyd. caIcIum
chIorIdo and fhon dIsfIIIod.
Kthyl ucetute, b.p. ??°C
EfhyI acofafo Is usod In rocrysfaIIIzafIon and In chromafographIc soparafIons. CommorcIaI sampIos
oI ofhyI acofafo confaIn ofhanoI, wafor and acofIc acId as ImpurIfIos.
Tho soIvonf, 100 mI oI acofIc anhydrIdo and 8÷10 drops oI conc. suIIurIc acId aro roIIuxod Ior
4 hrs IoIIowod by dIsfIIIafIon. Thon washod wIfh 5% soIufIon oI sodIum carbonafo. IInaIIy fho soIvonf
Is dIsfIIIod aIfor dryIng ovor anhyd. pofassIum carbonafo. Tho Iasf fracos oI wafor may bo romovod
by koopIng ovor phosphorus ponfoxIdo.
Kthylene glycol, b.p. 19?°C
ThIs Is a usoIuI soIvonf Ior wafor InsoIubIo organIc compounds fhrough IfsoII If Is mIscIbIo wIfh
wafor. If Is aIso an oxcoIIonf Inorf modIum. IurIIIcafIon may bo aIIocfod by dIsfIIIafIon ovor sodIum.
Dlglyme , O
CH OCH CH
CH OCH CH
2 2 3
2 2 3








b.p. 160°C
ÐIgIymo tdIofhyIono gIycoI dImofhyI ofhor) Is an oxcoIIonf modIum Ior roducfIon by dIborano. If
Is purIIIod by dIsfIIIIng Irom IIfhIum aIumInum hydrIdo.
Llgroln und Petroleum ether, b.p. rango 40÷120°C
Thoso soIvonfs tb.p. 40÷60°, 60÷80°, 80°÷120°C) aro chIoIIy ompIoyod Ior rocrysfaIIIzafIon purposos
and aro obfaInod Irom pofroIoum. Thoy confaIn somo safurafod hydrocarbons whIch fhrough do nof
InforIoro wIfh crysfaIIIzafIon buf aro undosIrabIo bocauso oI fhoIr roacfIvIfy.
A Iargo numbor oI unsafurafod compounds can bo romovod by shakIng wIfh conc. suIIurIc acId.
Tho soIvonf Is subsoquonfIy shakon wIfh a mIxfuro oI pofassIum pormanganafo soIufIon and 10%
APPENDIX 277
conc. suIIurIc acId fo romovo fho oxIdIzabIo compononfs. IInaIIy, If Is washod wIfh wafor drIod ovor
anhyd. caIcIum and dIsfIIIod. IoroxIdos aro romovod as In fho caso oI ofhor by runnIng ovor a coIumn
oI aIumIna.
TetruhydroIurun, b.p. 65.4°C
Tho soIvonf IInds uso In fho proparafIon oI OrIgnard roagonfs. If Is purIIIod by IIrsf froafIng wIfh
pofassIum hydroxIdo poIIofs IoIIowod by dIsfIIIafIons ovor IIfhIum aIumInum hydrIdo.
Prldlne, b.p. 115°C
IyrIdIno Is commonIy usod Ior acofyIafIon.
Anhydrous pyrIdIno can bo proparod by dIsfIIIIng commorcIaI soIvonf Irom barIum oxIdo.
AIfornafIvoIy, pyrIdIno can bo drIod ovor pofassIum hydroxIdo poIIofs.
Nltrobenzene, b.p. 210°C
NIfrobonzono Is usod as a modIum In fho IrIodoI-CraIfs roacfIon bocauso aIumInum chIorIdo Is
modorafoIy soIubIo In If. II If Is usod Ior rocrysfaIIIzafIon, fho crysfaIs shouId bo washod wIfh ofhor
or ofhyI aIcohoI fo romovo fho Iasf fracos oI soIvonf. Ifs vapors aro poIsonous. ÐInIfrobonzono and
anIIIno aro fho maIn ImpurIfIos prosonf In nIfrobonzono.
Tho soIvonf Is purIIIod by sfoam dIsfIIIafIon ovor dII. suIIurIc acId. If Is fhon drIod ovor anhyd.
caIcIum chIorIdo and dIsfIIIod agaIn.
Methunol, b.p. 64.5°C
ThIs soIvonf Is usod Ior rocrysfaIIIzafIon, In fho proparafIon oI sodIum mofhoxIdo and osforIIIcafIon.
Acofono and wafor aro fho prIncIpaI ImpurIfIos.
To romovo acofono or any ofhor carbonyI ImpurIfy a mIxfuro oI mofhanoI 0.51, IurIuraI t25 mI)
and 10% sodIum hydroxIdo soIufIon t80 mI) Is roIIuxod Ior sovoraI hr. ÐurIng hoafIng, a rosIn Is
Iormod whIch romovos aII fho compounds. Tho soIvonf Is fhon IracfIonafod.
Wafor Is prosonf fo fho oxfonf oI 1÷2%. To obfaIn absoIufo mofhyI aIcohoI, If Is aIIowod fo
sfand ovor magnosIum furnIngs t5÷? g Ior 1 IIf oI aIcohoI) acfIvafod by IodIno Ior sovoraI hr. AIfor fho
ovoIufIon oI hydrogon has coasod fho mIxfuro Is fransIorrod fo a cIoan round-boffomod IIask and
roIIuxod Ior 2÷3 hrs. MagnosIum hydroxIdo and magnosIum mofhoxIdo aro Iormod and fho aIcohoI Is
dIsfIIIod wIfh fho oxcIusIon oI aIr.
MofhyI aIcohoI sImIIar fo ofhyI aIcohoI Is hIghIy InIIammabIo.
Methylene chlorlde, b.p. 41°C.
MofhyIono chIorIdo Is usod In fho IrIodoI-CraIfs roacfIon as woII as In LowIs acId cafaIyzod ÐIoIs-
AIdor roacfIon. Iurfhormoro, If may bo usod as a subsfIfufo Ior ofhor whon dosIrod as a soIvonf Ior
oxfracfIon.
CommorcIaI soIvonf Is washod wIfh 5% sodIum carbonafo soIufIon IoIIowod by wafor. If Is
IracfIonafod aIfor dryIng ovor anhyd.
s-Tetruchloroethune, b.p. 146°C
If Is usod as a soIvonf Ior rocrysfaIIIzafIon and In fho proparafIon oI fhIokoI.
Tho fochnIcaI soIvonf Is warmod and sfIrrod Ior 30 mIn wIfh 8% conc. suIIurIc acId. Tho uppor
Iayor Is docanfod and fho procoss Is ropoafod fIII no moro coIor Is oxfracfod In fho acId. If Is fhon
sfoam dIsfIIIod, drIod ovor anhyd. caIcIum chIorIdo and dIsfIIIod agaIn.
AppenJix 3
ATOMIC MASSES OF SOME ELEMENTS
Klement Atomlc wt. Klement Atomlc wt.
AIumInum tAI) 26.98 MagnosIum tMg) 24.31
BarIum tBa) 13?.36 Morcury tHg) 200.61
Boron tB) 10.02 NIfrogon tN) 14.00?
BromIno tBr) ?9.916 Oxygon tO) 15.99
CaIcIum tCa) 40.08 Ihosphorus tI) 30.59
Carbon tC) 12.01 IIafInum tIf) 195.23
ChIorIno tCI) 35.45 IofassIum tK) 39.102
Coppor tCu) 63.54 SodIum tNa) 22.99
ChromIum tCr) 52.01 SIIvor tAg) 10?.8?
IIuorIno tI) 18.99 SuIIur tS) 32.06
Hydrogon tH) 1.008 ZInc tZn) 65.3?
IodIno tI) 126.90 Iron tIo) 55.85
Load tIb) 103.19 LIfhIum tLI) 6.94
AppenJix 4
PHYSICAL CONSTANTS OF SOME COMMON COMPOUNDS
Compound B.P. Denslty Dlelectrlc constunt Huzurds
(°C) (g/ml, 20°C) (A)
AcofIc acId 11?.9 1.049 6.2 IrrIfanf
AcofIc anhydrIdo 140.0 1.08? 20.? Lachrymafor
Acofono 56.2 0.?90 20.? IIammabIo
AcofonIfrIIo 81.6 0.?86 3?.5 IIammabIo
AnIIIno 184.0 1.021 1?.8 IrrIfanf
Bonzono 80.0 0.8?4 2.3 IIammabIo
BonzaIdohydo 1?9.0 1.041 23.0
BonzoyI chIorIdo 19?.0 1.219 Lachrymafor
BonzyI cyanIdo 233.5 1.015
Bromobonzono 156.0 1.495 5.4
BromIno 3.119 3.09 IrrIfanf
1-BufanoI 11?.3 0.810 1?.5 IIammabIo
tn-bufyI acIohoI)
Carbon fofrachIorIdo ?6.5 1.4601 2.2 InIIammabIo
CycIohoxano 80.? 0.??9 1.42 IIammabIo
ChIorobonzono 132.0 1.105 5.63
CycIohoxanoI 161.0 0.962 15.0
CycIohoxanono 156.0 0.94? 18.3
MofhyIono chIorIdo 39.8 1.32? 8.9 InIIammbIo
280 LABORATORY MANUAL OF ORGANIC CHEMISTRY
1, 4-ÐIoxano 101.3 1.034 2.2 IIammabIo
ÐIofhyI ofhor 34.5 0.?14 4.3 IIammabIo
ÐImofhoxyofhano 83.0 0.863 ?.2 IIammabIo
N, N-dImofhyIIorm- 15?.0 0.949 36.? IrrIfanf
amIdo
ÐImofhyI suIIoxIdo 189.0 1.101 46.? IrrIfanf
EfhyI acofoacofafo 181.0 1.025 15.?
EfhyI acofafo ??.1 0.900 5.63 IIammabIo
OIycoI 1.108 3?.0 IIammabIo
OIycoroI 290.0 1.263 42.5 IIammabIo
EfhanoI ?8.5 0.?89 24.6 IIammabIo
n-Hoxano 69.0 0.660 1.9 IIammabIo
MofhanoI 65.0 0.?91 32.? IIammabIo
n-Ionfano 36.1 0.626 1.8 IIammabIo
NIfrobonzono 211.0 1.203 34.8 InIIammabIo
IhonoI 182.0 1.550 9.?8 IrrIfanf
IyrIdIno 115.5 0.982 12.4 IIammabIo
TofrahydroIuran 6?.0 0.889 ?.6 IIammabIo
ToIuono 110.6 0.86? 2.4 IIammabIo
AppenJix 5
PHYSICAL CONSTANTS OF ACIDS AND BASES
Property HCl HNO
3
CH
3
COOH H
2
SO
4
H
3
PO
4
NH
4
OH
MoIocuIar 36.5 63 60 98 98 35
woIghf
SpocIIIc 1.18 1.41 1.06 1.84 1.69 0.90
gravIfy
MoIarIfy tM) 12 16 16 18 14.? ?.4
NormaIIfy tN) 12 16 16 36 44 ?.4
VoIumo tmI) 84 63 62.5 56 68 134
oI fho acId
roquIrod fo mako
1 IIf oI app. 1M
soIufIon
AppenJix 6
MIXTURE FOR COOLING BATHS
Mlxture Rutlo Lowest temperuture (upp)
(Sult + lce) (Sult + lce) (°C)
1. Crushod Ico + wafor
twafor shouId covor fho Ico) 0 ÷ ÷5
2. CaCI
2
. 6H
2
O + Ico 1 : 2.5 ÷10
3. NaCI + Ico 1 : 3 ÷20
4. CaCI
2
. 6H
2
O + Ico 1 : 0.8 ÷40
Ðry Ico + soIvonf mIxfuro
5. Ðry Ico + CHCI
3
÷60
6. Ðry Ico + acofono or ofhanoI ÷?5
?. LIquId nIfrogon ÷196
SELECTED JOURNALS
1. JournaI oI AmorIcan ChomIcaI SocIofy
2. JournaI oI OrganIc ChomIsfry
3. JournaI oI ChomIcaI EducafIon
4. JournaI oI ChomIcaI SocIofy tLondon)
5. Tofrahodron
6. Tofrahodron Loffors
?. AnnaIon dor ChomIo
8. BorIchfo dor Ðoufchon ChomIschon OosoIIschaIf
9. Angowandfo ChomIo InfornafIonaI EdIfIon
10. CanadIan JournaI oI ChomIsfry
11. IndIan JournaI oI ChomIsfry
12. AusfraIIan JournaI oI ChomIsfry
13. BuIIofIn do Ia SocIofo ChImIquo do Iranco
14. RocuoII dor Travaux ChImInquos do Iays-Bas
15. BuIIofIn ChomIcaI SocIofy Japan
16. Oazoffa ChImIca IfaIIana
1?. HoIvofIca ChImIca Acfa
18. SynfhosIs
19. JournaI oI HoforocycIIc ChomIsfry
20. HoforocycIos
21. ChomIsfry In BrIfaIn
22. ChomIsfry and Indusfry
23. ChomIsfry and EngInoorIng Nows
This page
intentionally left
blank
INDEX
A
AldorhnIdon dryIng µIsfoI, l3
AcofnmIdo, 95
AcofnnIIIdo, 96, 244
AcofIc ncId, ?3
Acofoµhonono, 82
AcofoµhononoµhonyIhydrnzono, 2l3
AcofyIsnIIcyIIc ncId, l35
AcfIvnfod chnrconI, 24
Adnµfors, l4
AdIµIc ncId, ??, l96
AdIµoyI chIorIdo, 233
Adsorlonf, 225
AIkono dorIvnfIvo, ll6
AIkyno dorIvnfIvo, ll6
AIIyI nIcohoI, 64
AIumInum chIorIdo fosf, 59
AmnIgnmnfod mngnosIum, 223
F-AmInolonzoIc ncId, ?8
-AmInoµhonoI, ?2
F-AmInoµhonoI, ?2
2-AmIno-4-nIfrodIµhonyInmIno, 2l5
AmmonIn ovoIufIon fosf, 55
AsµIrIn, ?5, 244
F-AnIsnIdohydo, 84
AnIIIno, 9l
AnIIIno hydrochIorIdo, l04
AnIsIc ncId, ?8
FAnIsIdIno, 93
AnfhrnnIIIc ncId, ?6, l44, 2l?, 22l, 24l, 248
AnfhrnquInono, l96
AsµIrnfor, ll
Azoofroµo, l?
AzoofroµIc mIxfuro, l?
Azolonzono, l02, 200, 236
B
Inyor`s fosf, 60
Iockmnnn ronrrnngomonf, l86
IoIIsfoIn fosf, 33
IonodIcf`s soIufIon, 2?2
IonodIcf`s fosf, 46, 5l
IonznmIdo, 96, 2?2
IonznnIIIdo, l86, l90
IonznIdohydo, 82
IonzonosuIfonnmIdo, l03
IonzonosuIfonIc ncId, l02
IonzhydroI, 200
IonzII, l92
IonzIIIc ncId, l9l
IonzIIIc ncId ronrrnngomonf, l9l
IonzoIc ncId, ?5, l9?
IonzoIn, 85, l92
Ionzoµhonono, 85, 235
IonzoµInncoI, 235
F-IonzoquInono, l03, 2l4
-IonzoyIlonzoIc ncId, l82
>-IonzoyIµroµIonIc ncId, l84
I-IonzyIIsofhIouronIum chIorIdo, l09
IonzyI nIcohoI, 66
286 LABORATORY MANUAL OF ORGANIC CHEMISTRY
IIndor, 22?
IIurof, 9?
IIurof fosf, 6l
IoIIIng chIµs, l?
IoIIIng µoInf, l6, ll9
-IromonnIIIno, 92
-IromonnIIIno, 92
F-IromonnIIIno, 93, 25l
-IromolonzoIc ncId, ??
-IromolonzoIc ncId, ?6
F-IromoµhonoI, 69
-IromoµhonoI, 65
-IromofoIuono, 99
-IromofoIuono, 99
F-IromofoIuono, 205
IumµIng, l6
C
CnffIono, 23?
Cnmµhor, 85, 209
Cnmµhor oxImo, 208
CnnnIzznro roncfIon, l88
CnrlyInmIno fosf, 53
CnsoIn, 239
CnfnIyfIc hydrogonnfIon, 223
CnfochoI, ?0
CorIc nmmonIum nIfrnfo fosf, 3?
ChomIcnI shIff, 259
ChomIcnI oxygon domnnd (C.O.Ð.)
doformInnfIon, l65
ChIornI hydrnfo, 85
F-ChIoroncofoµhonono, 83
F-ChIoronnIIIno, 94
-ChIoronnIIIno, 92
-ChIoronnIIIno, 92
F-ChIorolonznIdohydo, 85
-ChIorolonzoIc ncId, ?62, 2l?
F-ChIorolonzoIc ncId, ?9
F-ChIoroµhonoI, 68
-ChIoroµhonoI, 66
-ChIoroµhonoI, 65
F-ChIorofoIuono, 99, 2l6
-ChIorofoIuono, 99
-ChIorofoIuono, 99
Chromn, 224
ChromnfogrnµhIc mofhods, 224
ChromIc ncId fosf, 46
CInnnmIc ncId, ?5, l8?, 233
CInnnmyI nIcohoI, 6?
CIfrnI, 84
CIfrIc ncId, ?4
CIfronoIIoI, 6?
CInIson fInsk, 9
CInIson dIsfIIInfIon hond, l4
CoIumn chromnfogrnµhy, 225
Condonsors, l0
!IolIg, l0
F-CrosoI, 68
-CrosoI, 6?
-CrosoI, 66
CrofonnIdohydo, 8l
CrofonIc ncId, ?3
CrysfnIIIznfIon, 23
CycIohoxnnono, l94
D
ÐohydrnfIon, 206
ÐorIvnfIvos, l05
µroµnrnfIon of,
I-lonzyIIsofhIouronIum snIfs, l09
F-lromoµhonncyI osfors, lll
3, 5-dInIfrolonzonfos, l0?
2, 4-dInIfroµhonyIhydrnzonos, l08
=-nnµhfhyIcnrlnmnfos, l06
F-nIfrolonzonfos, l06
oxImos, l09
µhonyIhydrnzonos, l09
µIcrnfos, ll5
somIcnrlnzIdos, l08
F-foIuonosuIfonnmIdos, ll4
ÐoformInnfIon of nscorlIc ncId conconfrnfIon, l?l
ÐoformInnfIon of oquIvnIonf woIghf of n cnrloxyIIc
ncId, l4?
ÐoformInnfIon of moIocuInr woIghf of n sulsfnnco
(!nsf`s mofhod), l62
ÐInzofIsnfIon couµIIng, 53, 5?, 2l5
F-ÐIchIorolonzono, l00
ÐIchIorocnrlono, l93, 242
l, 2-ÐIchIoroofhnno, 23l
?, ?-ÐIchIoro |4.l.0] hoµfnno, 242
ÐIoIs-AIdor roncfIon, l85
ÐIofhyIono gIycoI, l99
ÐIofhyIono gIycoI dImofhyI ofhor, soo dIgIymo
ÐIgIymo, 2?5
2, 5-ÐIhydroxyncofoµhonono, l89
ÐIImIdo, 234
2, 3-ÐImofhyI-l, 3-lufndIono, 226
2, 3-ÐImofhyI-2, 3-lufnnoI, 222
2, 3-ÐImofhyI-2, 3-lufnnono, 222
-ÐInIfrolonzono, 202
2, 4-ÐInIfrolonzonosuIfonyI chIorIdo, ll6
2, 4-ÐInIfrochIorolonzono, 249
2, 4-ÐInIfroµhonyIhydrnzIno, 44, 249
INDEX 287
l, 2-ÐIµhonyI-5-nIfrolonznmIdnzoIo, 2l5
ÐIµhonyInmIno, 93
ÐIµhonyImofhnno, l83
ÐIsfIIInfo, l5
ÐIsfIIInfIon, l5
frncfIonnI, l8
roducod µrossuro, 20
sImµIo, l6
sfonm, 2l
2, 6-ÐI J-lufyIµhonoI, 232
ÐrIorIfo, 25
ÐroµµIng funnoI, l0
ÐryIng ngonfs, 25
E
IfhyI lonzonfo, 88
IfhyI F-hydroxylonzonfo, 90
IIufIon, 225
IosIn, 22l
IrIonmoyor fInsk, 9
IsforIfIcnfIon, 243
IsfImnfIons, l43
IsfImnfIon of n kofo grouµ, l50
IsfImnfIon of nmIno grouµ, l56
IsfImnfIon of nn nIdohydo, l5l
IsfImnfIon of nsµIrIn, 240
IsfImnfIon of gIycIno (nmIno ncId), l58
IsfImnfIon of hydroxyI grouµ In nIcohoIs, l43
IsfImnfIon of kofo-onoI oquIIIlrIum, l66
IsfImnfIon of mofhoxy grouµ, l68
IsfImnfIon of nIfrogon (IjoIdnhI mofhod), l54
IsfImnfIon of H, l64
IsfImnfIon of suIfur (Mossongor`s mofhod), l53
IsfImnfIon of unsnfurnfIon, l62
F
IohIIng`s soIufIon, l60
IorrIc chIorIdo fosf, 6l
Iorrous hydroxIdo fosf, 52
IIngor µrInf rogIon, 255
IIschor-IndoIo synfhosIs, 2l2
IIuoroscoIn fosf µnµor, 2?l
IIuoroscoIn, 220
IInsks, 8
IormnIIn fosf, 58
IrncfIonnI dIsfIIInfIon, l8
IrIodoI-Crnffs roncfIon, l8l
IrIos ronrrnngomonf, l89
IuchsIno (F-rosnnIIIno hydrochIorIdo), 45
IunnoIs, l0
luchnor, ll
droµµIng, l0
hIrsch, l0
soµnrnfory, l0
G
CoI chromnfogrnµhy, 225
CoI IIquId chromnfogrnµhy, 225
CoI fIIfrnfIon, 225
CornnIoI, 6?
CrIgnnrd roncfIon, 203
H
HnIoform roncfIon, 23?
HInslorg fosf, 54
Hoffmnnn lromnmIdo roncfIon, 248
HydrnzIno, 234
HydrocInnnmIc ncId, 233
HydroquInono, 2l4
HydroquInono dIncofnfo, l89
HydroxnmIc ncId fosf, 56
F-HydroxylonznIdohydo, 8l
5-Hydroxy-l,3-lonzoxnzoI-2-ono, 2l4
HydroxylonzoIc ncId, ?9
F-HydroxylonzoIc ncId, ?9
?-Hydroxy-4-mofhyIcoumnrIn, 250
8-HydroxyquInoIIno, 2?0
I
IdonI soIufIon, l?
IndoµhonoI, 42
Infrnrod sµocfroscoµy, 253
InforfncInI µoIymorIznfIon, 233
IodIno soIufIon, 2?0
Iodoform, l00, 23?
Iodoform fosf, 46
F-IodonIfrolonzono, 2l6
I-IonyIIsofhIouronIum chIorIdo, ll0
K
Iofo-onoI fnufomorIsm, l66
IjoIdnhI's fInsk, l55
L
!nssnIgn's fosf, 32
288 LABORATORY MANUAL OF ORGANIC CHEMISTRY
!Iolormnnn roncfIon, 42
!IolIg's condonsor, l0
!IgroIn, 2?5
!InnIooI, 65
!IquId-IIquId chromnfogrnµhy,
!IquId-IIquId µnrfIfIon chromnfogrnµhy, 224
!Ifmus µnµor fosf, 49
!ucns rongonf, 2?0
!ycoµono, 238
M
MngnofIc sµInnor lnr, l2
MngnofIc sfIrror, l2
MngnofogyrIc rnfIo, 258
MnndoIIc ncId, ?5, 24?
MnnnIfoI, ?l
MochnnIcnI sfIrror, l3
MoIfIng µoInf, ll?
Monfhono, 83
Mossongor's mofhod, l53
F-MofhyIncofoµhonono, 83
MofhyI lonzonfo, 8?, 243
MofhyI F-hydroxylonzonfo, 90
MofhyI ornngo, 2l8
MofhyI oxnInfo, 88
MofhyI µhonyI ncofnfo, 88
MofhyI rod, 22l
MofhyI snIIcyInfo, 88
MIxod moIfIng µoInf, ll?
MoIIsch rongonf, 2?0
MoIIsch fosf, 50
Monomor, 230
Mofhor IIquor, 25
N
=-ÞnµhfhoI, 69
>-ÞnµhfhoI, 53, ?l
=-ÞnµhfhoIc ncId, ??
>-ÞnµhfhyInmIno, 94
=-ÞnµhfhyInmIno, 93
=-ÞnµhfhyIcnrlnmnfo, l06
ÞInhydrIn, 229
F-ÞIfroncofnnIIIdo, 245
F-ÞIfroncofoµhonono, 202
-ÞIfronnIIIno, 94
-ÞIfronnIIIno, 94, 202
F-ÞIfronnIIIno, 95, 245
-ÞIfronnIsoIo, l0l
F-ÞIfronnIsoIo, l02
F-ÞIfrolonznmIdo, 9?
ÞIfrolonzono, l0l
-ÞIfrolonznIdohydo, 85
-ÞIfrolonznIdohydo, 84
F-ÞIfrolonzoIc ncId, ?9, l95
-ÞIfrolonzoIc ncId, ?6
-ÞIfrolonzoIc ncId, ?6
-ÞIfroµhonofoIo, l02
F-ÞIfroµhonofoIo, l02
-ÞIfroµhonoI, 69, l02, l?8
-ÞIfroµhonoI, ?0
F-ÞIfroµhonoI, ?0, l02, l?8
F-ÞIfrofoIuono, l02, l95
-ÞIfrofoIuono, l0l
ÞorIf, 24
ÞucIonr mngnofIc rosonnnco
sµocfroscoµy, 258
ÞyIon, 233
O
OIfncfIon, 2?
OµfIcnI ncfIvIfy, 209
OrdInnry funnoI, l0
OxnIIc ncId, ?4
OxnmIdo, 98
OxIdnfIon nnd roducfIon, l94
P
Inµor chromnfogrnµhy, 229
InrfIfIon chromnfogrnµhy, 2
IorkIn roncfIon, l8?
IhonoI, 68
IhonoI-formnIdohydo rosIn, 23l
IhonoIµhfhnIoIn µroµnrnfIon, 2l9
IhonoIµhfhnIoIn fosf, 42, 49
IhonyIncofnmIdo, 96
IhonyI ncofnfo, 8?
IhonyIncofIc ncId, ?4
IhonyI lonzonfo, 90
IhonyI cInnnmnfo, 90
=-IhonyIofhyI nIcohoI, 66
=-IhonyIofhyInmIno, 2l0
IhonyIhydrnzIno, 2l2, 2l3
2-IhonyIIndoIo, 2l2
l-IhonyI-3-mofhyI-5-µyrnzoIono, 2l3
IhonyI snIIcyInfo, 89
IhonyI uron, 249
IhIorogIucInoI, ?2
IhofochomIcnI roncfIon, 235
IhfhnIoIn fosf, 42
IhfhnIIc ncId, ?8
INDEX 289
IhfhnIImIdo, 9?, 248
IIcrIc ncId, l?9
IInncoI, 223
IInncoI-µInncoIono ronrrnngomonf, 222
IIcrIc ncId, ?l
IInncoIono, 223
IIµorIno, 239
IIµoffos, 9
grndunfod, 9
Insfour, 9
IIvnIIc ncId, l98
IoInrImofor, 209
IoIymor, 230
IoIyµhosµhorIc ncId, 2l2
IoIysfyrono, 232
IofnssIum forrocynnIdo fosf, 6l
IroµnrnfIon of -nnd F-nIfroµhonoIs, l?8
IroµnrnfIon of dIµhonyImofhnno, l83
IroµnrnfIon of nIfrolonzono (nIfrnfIon), l?6
IroµnrnfIon of µIcrIc ncId, l?9
IroµnrnfIon of 2, 4, 6-frIlromonnIIIno
(IromInnfIon), l?9
IyrognIIoI, ?l
Q
QuInhydrono, ?2
QuInhydrono rongonf, 2?0
QuInoI, ?2
QuInoIIno, 2ll
R
!nsf's mofhod, l?3
!oducIng sugnr, l59
!
I
vnIuo, 22?
!oImor-1Iomnnn roncfIon, l93
!oInfIvo rnfos of oIocfroµhIIIc nromnfIc
sulsfIfufIons, l80
!osorcInoI, ?0
!ochoIIo snIf, l59
S
SnIIcyInIdohydo, 82, l93
SnIIcyInmIdo, 96
SnIIcyIIc ncId, (-hydroxylonzoIc ncId), 244
SnIfIng-ouf offocf, ll
Snndmoyor roncfIon, 2l6
SnµonIfIcnfIon vnIuo, l6l
SchIff's rongonf, 2?l
SchIff's fosf, 45
Schöffon-Inumnnn roncfIon, l90
SoodIng, 24
Soµnrnfory funnoI, l0
SImµIo dIsfIIInfIon, l5
SIIvor dInmIno comµIox, 34, 44
SIIvor snIf mofhod, l4?
Skrnuµ synfhosIs, 2ll
Sonµ, 250
SodIum lIcnrlonnfo fosf, 49
SodIum lorohydrIdo, 203
SodIum fusIon oxfrncf, 3l
SoIulIIIfy, 29
SoxhIof nµµnrnfus, 239
SµocIfIc rofnfIon, 209
Sµocfroscoµy, 253
SµIn-sµIn sµIIffIng, 263
Sfnrch soIufIon, 2?l
Sfonm dIsfIIInfIon, 22
SfIIIhond, l4
SfIrrors, l2
Sfyrono, 232
SuccInIc ncId, ?8
SuccInImIdo, 98
SuIfnnIIIc ncId, l04
T
1nrfnrIc ncId, ?8
1nufomors, l66
1osf for nnIIIdo grouµ, 5?
1orµInooI, 68
1ofrnIIn, 234
1ofrnmofhyIsIInno, 259
1hoorofIcnI µInfo, l9
1hormocoIo, 232
1hIoIo fulo, ll8
1hIn Inyor chromnfogrnµhy, 22?
1hIokoI rullor, 23l
1hIouron, 6l
1oIIons` fosf, 44
F-1oIuIc ncId, 205
-1oIuonosuIfonnmIdo, l04
F-1oIuonosuIfonnmIdo, l03
F-1oIuonosuIfonyI chIorIdo, l03
-1oIuIc ncId, ?5
-1oIuIc ncId, ?4
F-1oIuIc ncId, ?8, 205
-1oIuIdIno, 92
F-1oIuIdIno, 93
-1oIuIdIno, 9l
1oxIc chomIcnIs, 3
1oxIcIfy, 4
290 LABORATORY MANUAL OF ORGANIC CHEMISTRY
2, 4, 6-1rIlromonnIIIno, l?9
2, 4, 6-1rIlromoµhonoI, 40
1rIofhyIono gIycoI, l99
1rIofhyIono gIycoI dImofhyI ofhor, 242
1rIgIymo, 242
2, 4, 6-1rInIfroµhonoI, l?9
1rImofhyIncofIc ncId, l98
1rIµhonyImofhnnoI, ?l, 204
1rIµfycono, 24l
U
!ron, 6l
!ron nIfrnfo, 6l
!rofhnno, l06
V
Vncuum dosIccnfor, l3
Vncuum dIsfIIInfIon, 2l
VnnndIum oxIno fosf, 38
Vnµor µrossuro, l5
VIlrnfIons, 253
londIng, 254
sfrofchIng, 254
VIgroux coIumn, l8
VIfnmIn C, l?l
W
Wnfor µumµ, ll
WIdmor coIumn, l8
WIz's soIufIon, l63
WoIff-IIshnor roducfIon, l99
X
Xnnfhnfo fosf, 3?