Chapter 46-51 PDF

Chapter 46
Fused Polynuclear Aromatic Hydrocarbons
Fused or condensed aromatic hydrocarbons contain more than one ring and hi'.e
two carbons shared by two (or three) aromatic rings. The most important members of this class
are naphthalene, anthracene and phenanthrene.
PHI/tAN riREi.E
,vlpHrh'A L f Nr
Naphthalcnc has two carbon atoms shared by two rings lindicatcd by thick dots).
Anthracene and phenanthrefle have two pairs of carbon atoms shared by two rings, each pair
being shared by a separate pair of rings.
NAPHTHALENE
Naphthalene is the largest single constituent to 10 per cent) of coal-tar. It is obtained

chilling the middle oil fraction (bp 10-230°C ). when crude naphthalene crys-
Industrially b y washing it successively with dilute uIpliuric acid (to remove basic
tallises out. It is pur i fied by
impurities), sodium hydroxide (to remove acidic impurities) and water. Finally the solid is
sublimed or steam-distilled to give pire naphthalene.
NOMENCLATUR E OF NAPHTHALENE DERIVATIVES

In naming derivatives oF naphthalene the numbering system shown below is used
The numbers selected to denote the position uI a suhstitUi.mt on the naphthalene rings should be
as small as possible.
Cit3
HC
t.ROMONAPHTHL'E 1, 6-D1MffHYVVA pm THAL ENE

NAPL4TOALFNE
1162
Fused Pot ynuctear Aromatic Hydrocarbons I 163
An alternative nomenclature system is occasionally used when there is only one substi-
tuent on the naphthalene skeleton. This system uses the Greek letters a (alpha) and P (beta) to
designate the two possible orientations of the single substituent.
NO
o( r
i4PHr.A LENE
cx5
-MTR01VP1 7H4L(N(

8. &WMLWAPy TIM fNf
STRUCTURE OF NAPHTHALENE
All ten carbon atoms in naphthalene are .rp 2 hybridized. The sp' hybrid orbitals over-
lap with each other and with s orbitals of the eight hydrogen atoms forming C—C and C—H
a bonds (Fig. 461). Since the a bonds result from the overlap of trigonal sp orbitals, all car-
bon and hydrogen atoms in naphthalene lie in one plane. This has been confirmed by X-ray
diffraction studies.
:xx
5fr2
Fig. 461 Formation of the bands in naphthalcne.
Also each carbon atom in naphthalene possesses an unhybridized p orbital containing

one electron. These p orbitals are perpendicular to the plane containing the a bonds. The lateral
overlap of the p orbitals produces a n molecular orbital containing ten electrons (Fig. 462).
One half of this it molecular orbital lies above and the other half lies below the plane of the
bonds. Naphthalene shows aromatic properties because the resulting it molecular orbital satis.
lies the Huckets rule (n=2 in 4n+2).
Advanced Organic Chemistry
I 164
1VHV8RIDIZED
it MO
-.
- H..
44/"
Fig. 462 Formation of the it molecular orbital in naphthalene.

A commonshorthand representation of naphthalene is simply two fused hexagons with
molecular orbital.
a circle inside each hexagon. The circles represent the Ti
rs-MOLECULAR
ORB#TAL
Or
C
According to the resonance theory, naphthalene is considered to be a hybrid of the
following three canonical forms.
MIX,
X-Ray diffraction studies show that, unlike benzene, all carbon-carbon bonds in naphtha-
lene are not of the same length. In particular, the Cl-C2 bond is considerably shorter (136
A)
This difference can be understood if we examine the three
than the C2-C3 bond (140 A).
resonance forms given above. Notice that the Cl-C2 bond is double in two structures (A and
C3 bond is single in two structures (A and B)
B) and single in only one (C); whereas the C2- .
and double in only one (C). We would, therefore, expect the ClC2 bond to have more double
bond character (shorter bond length), and the C2-C3 bond to have more singie-bond character
(longer bond length).
The resonance energy of naphthalene is about 61 Kcal/mole. This value is less than
twice the amount of a single benzene ring (36 Kcal/mole). As a result, naphthalene is some-
what less aromatic (more reactive) than benzene.
SYNTHESIS OF NAPHTHALENE
Naphthalene may be obtained
When petroleum fractions are passed over copper catalyst at
(1) From Petroleum.
'90° C, naphthalene and methylnaphthalenes are formed. Mcthylnaphtbalenes are separated
nd converted into naphthalene by heating with hydrogen under pressure (dealkylatian).
PITROI((,%' rAcr/oNs -
68A
00 +
'v4PHTHALENF M(THVL/APHTWAIENt
k,6,PR(53URE
(_CH.,
Prior to 1960 all naphthalene came from coal-tar, but now almost half of it is produced
from petroleum by the above method.
(2) From 4-Phenyl-1-buteiie. When 4-phenyl-1-butene is passed over red hot calcium
oxide, naphthalene is obtained
H2
HC2O 4- H2
1 A
©zc\ CH
NfP,lTMALENE
4 PIIENYL- -BUTENE
(3) From 4-.?heuyl-3-buteociC Acid. When 4..phenyl-3-butenoic acid is heated with con-
centrated sulphuric acid, 1-naphthol is formed. This on distillation with zinc dust gives
naphthalene.
-
HSO4 REARAA'GMENT
@C,CH,
C9
(—H20)
r Oq OH
4-PHENYL-3
ACID-8t/TftO/C
UNSTABLE
1- NAPHTHOL
Zn +ZnO
y .qPHT/IA LENE
(4) By Haworth Synthesis. This involves the following five steps
Step 1. Benzene and succinic anhydride are heated in the presence of aluminium chloride
to form -bcnzoylpropionic acid. (Friedel-Crafts Acylation)


1166
0
0 ii
- HCC\ AICI .
0
© +I II H0C
C2
II
8EN2INE 0
5UCLIN!C ANHYDRIDI ,.gENZOyLPp/ONIC
Ac ID
Step 2. S.Benzoylpropionic acid is treated with amalgamated zinc in the presence of

hydrochloric acid to give -phenylbutyric acid. (C!ern,nensen Reduction)
Ha
© "CH2 2rP4gl CI4i
HO—C
NCI (Y CH2
Ii
0
M1VZ0YtPk0PI0NK )'-PH(NYL80TY1C
ACID ACID
Step 3. y-Phenylbutyric acid is heated with concentrated sulphuric acid or polyphos-
Vhoric acid to form -tetralone. (Ring-closure Reaction)
142SO4
+ H20
CH
0
0
TETRA LONE
r pwyL8urrk'c
ACID
Step 4. -Tetralone is heated with amalgamated zinc and hydrochloric acid to give
tetralin. (CIen?nleflse n Reduction)
HCI
Mo
0 TETRALIN
-TfRALONE
(Aroinati-
Step J. Tetralin is heated with selenium or palladium to yield naphthalene
zat ion Reaction).
00 - co
T(TRALiiV
Se or
NAP/ITHAL[NE
+ 2,
Substituted naphthalenes can be obtained by using toluene, bromobenzene, or ansole

instead of benzene in Step (I).

Fused Polyrwctr Aromatic Hydrocarbons 1167
PROPERTIES OF NAPHTHALENE
(Physical). Naphthalene is a colourless crystalline solid. It melts at 82°C and boils

at 218°C. Naphthalene is insoluble in water, but dissolves in ether, benzene, and hot ethanol.
It sublimes readily when warmed and is volatile with steam. Naphthalene has a characteristic
'moth ball' odour.
(CIu'rnical). Some of the important chemical reactions of naphthalene are described
below.
A. ELECTROPH] LIC SUBSTITUTION REACTIONS

Naphthalene, like benzene, undergoes electrophilic substitution reactions. Substitution
occurs primarily at C-i (a-position). This can be understood if we examine the intermediate
carbonium ion Two resonance froms can be written for the intermediate carbonium ion obtained
from the attack at C-I (without involving the other ring), whereas only one such form is possi-
ble for substitution at C-2. E in the following equations represents an electrophile.
Attack at C.!
MORE 3rABLE f-5085 7/rifT/ON

PRODUCT
Attack at C-2
.-,..WH + WE
L(53.5TA&E 25U8.ST171./T/OA/
PRODUCT
Consequently the former intermediate is more stable and the product with a substittient
at C-I predominates. Substitution at C-2 (p-position) occurs only when the reactions are
carried at higher temperatures or when bulkier solvents are used.
(I) Nitration. Naphthalenc undergoes nitration with concentrated nitric acid in the
presence of sulphuric acid at 60° C to produce l-nitronaphthalene.
NO
+ HNO
//A PH THALEM' 1- NtrRON,P//THALEN(
MECHANISM. The mechanism of this reaction invo t ves the following three steps
Step I. The electrophile (NOn is generated.
2f-ISO 4 + HONO -p 4 2HSOI + H30

Step 2. The electrophile attacks naphthalene at C-I to form the resonance-stabilised

carbonium ion (only those resonance forms are shown below which do not involve the other
ring).
I.
C)
Step 3. A hydrogen ion is eliminated to yield l-nitronaphthalene.
I
NO2 H Nc) 2 NO2
H,
H 55
1-1V1TR01V4PHr/IA LENt
Similar steps may be written for other eleclrophilic substitution reactions of naphthalene.
(2) Sulphonation. Naphthalene undergoes sulphonation with concentrated sulphuric acid

at 60CC to form i-naphthalenesulphonic acid lithe reaction is carried at 165CC, 2-naphthalene-
suiphonic acid is obtained.
0
5031•i
1-NA P/-I THA LENt -

HSQ4
60CC
NA PI/TI/ALENE
H2504
65CC
W
2-NA PI/THALEVE -
511LPNO///C ACID .5 IJL.PHON/C ACID
(3) HIogenation. Naphthalene undergoes ch1rination or bromination i n boiling car-

bon tetrachloride to give 1-chloronaphthalene. Unlike benzene, no Lewis an catalyst is
required:
Cl
CCI 0 + HO
WI
NA,Ht/-iAcEI-4E
-I- Cl i -.
A
1- C/-LORONAPNrhNLENE
When the above reaction is carried at room temperature, naphthalene dichloride (1 4-

addition product) is obtained. On heating, naphthalene dichloride loses HCI to yield I -chloro-
naphthalenc.

I JOY
Fused Poiynuclear Aromatic Hydrocarbons
Cl
tIIrIJIII1J + ROO bI TEMP - H Cl
NAPM1HA1WE/C80R0NA P/I lilA (/V

NAP/'TRA I (NE O/CHIOR/Cé
Friedel-Crafts Acylation. Naphthalene undergoes acylation with acetyl chloride and
(4)
aluminium chloride in carbon disulphide to give l.acetylnaphthalene. When nitrobenzene is used
as a solvent. 2 acetylnaph l.halene is obtained.
CHCOCI,AC © CH3COCI,AI0H
-4---
[] IN CS IN C6HNO2
/VAPHTHALENE 2A(ErYLN,4PHTHALENE
I 4 CETYLNA PH T/IA I. fWE
(5) Friedel-Crafts Alkylation. Naphthalene undergoes alkylation with alkyl halides

(methyl halides do not react) in the presence of aluminium chloride to give 2-alkyl naphthalenes.
CH2CH3
00
AM PHT#A L (NC
+ CH,CH2CI ACl3

2-(1HYLNAPHrWAL(NE
+ HO
latiOfl. Naphthalene reacts with formaldehyde and HCI in the presence

(6) Cbloromethy
of zinc chloride to form lchloromethylflaPhthalefle.
H,Cl
Zn Cl2
co
+ --H + HCI
0
(D
1 CHL0P0ME1IY NAPHTAIENE
4pTq4EN( rORMALDEHYO
B. OTHER REACTIONS
Reduction. Naphthalene undergoes reduction more readily than benzene. With

(7) dihydronaphtbalene With sodium
sodium and ethyl alcohol hp 78°C) it gives 1,4-dialin or 1,4 .
and isopentanot (bp 130°C) it gives tetralin or l,2,3,4tetrahYdrOflaPht hale fle
cc
TETRALIN
Na,CsH1O
Bolt
N4P/-IIHAL(NE
Na,C2H5OH
BOIL 00
1,4-DIAL/N
Catalytic reduction completely hydrogenates both rings and produces decalin or deca-
hydrOflaphthalefle.
74 (4552/1982)

f 170 Adi.ined Oganc Csernstry
8
N rr Pt
cc
NAPHTHALENE
+ 5H2
tS PR(5$L/(
C^02
OCCALIN
Decalin consists of two c y clohesane molecules (in chair forms) fused together along a
common side. It cxiss in cis and trans isomeric forms which differ in the space relationship of
main
hydrogen atoms at C- 9 and C-- tO positions. When nickel is used as a catalyst, the
product is trans-decalin. When plainum is usedas a catal yst, the main product is cis.decalin.
Decaliri sold comniercialls is the mixture of both these forms, and is used as a solvent in the
varnish and lacquer trade
irons-decalin cir.tiecslin
(bp 185'C) (hp I5C)
(8) OxidIiou. Naphthalene is much more easily oxidised than benzene. With chro-
miurn trioxide in acetic acid at room temperature, it gives I ,.l-na1,hthac'uinone.
.4'APIiTHALIS'L
0
/,4 4i,,/f/fAOiIM7tV(
Oxidation of naphthalene with oxygen :uid .auadium 1citxde at 45 C y ields phthaiic.

anhydride. This method is used industrially.
©©
44 °hTHAIExE
©1
0
.O/140C A,VHYORIOt
Phthalic acid is an important industrial material. It is used in the manufacture of resins

paints, dyes and plastics.
Uses. Naphthalene as moth balls has been used to protect woolen goods from moths
for many rears. Recentl y , p-dichlorohenzene has replaced naphthalene in the manufacture of
moth hails. as it has a less abnoxinUS odour- It is used for increasing the iliumnatng power
of co-l gas NaDhthakne i used in the manufacture of phthalic anhydride, carbarl for
insecticides. 2-naphihol. d y es, and several medicinal products

Fused PlynucIeor Aromotic Hydrocarbons 1171
Classical Derivation of the Structure of Naphthalene

The structure of naphthalene was arrived at from a consideration of facts and coric lu.
sions such as the following.
(I) Elemental analysis and molecular weight deterrnj oat ions show that the molecular
formula of naphthalene is C10Hv
(2( Dipole moment of naphthalene is zero. This indicates that the naphthalene mole-
cule is symmetrical.
Oxidation of naphthalene with oxygen arid . vanadium pentoside at 4704 C yields
plithalk anhydride. This indicates the presence of a heneenc ring with two ortiio side-chains
in the molecule.
a:
(4) Nitration of naphthalene produces a nitronaphthalene which when oxidised gives
3.nitrophthalic acid. Reduction of the nitronaphthalcne gives an anitnonaphthaltne which when
oxidised yields only phthalic acid.
NO2 NO2
KMO/H
I'
m
NAPHTHALENE
NO3
H2SO4
B I
lN/TRO(VAPHTHAL INC
80(1.
^ COO-i
3-N,TRornrHn,c ACID
Isn/ -ici
_________a
COO frI
Ki-1-rO/
A B A j
80/L
COOH
I. 4M/vONAP/1rNALFA'5 PI-iTHAIIC AC/fl
The electrophilic nitro group stabilises the benzene ring to which it is attached (ring B), and
the other benzene ring is preferentiall y oxidised. On the other hand, the nucleophilic amino
group makes the benzene ring to which it is attached (ring B) more susceptible to oxidation.
These results clearly indicate that naphthalene consists of two fused benzene rings.
C)o
1V4PI1TWALEN5

II'
The above structure of naphthalene has been confirmed by several synthesis (p 144).
Naphthalene is a hybrid of three resonance structures, These structures along with
molecular orbital picture are given on page 1143.
Substitution in Naphthalene Derivatives

The introduction of a second substituent into t. naphthalene ring follows essentially
the same rules as for benzene. The nature of the group already present determines the position
of the entering group.
Rule 1. If the first group is an ortho-para director in the benzene sense (e.g , —OH,
—NH 3, — CH1 ) and is located at C-I, it will direct the incoming group to the C-2 or C.4
positions.
CH3
H2SO4 00
I METNYLVAPT"
Rule 2. If the first group is ortho para director and is located at C-2, it will direct
the incoming group to the C-i position.
NC
WCH, CH;
HNO
iiiiij
2-4IETHVLNAP/.(T/1AL(NC NIrO-2-
MET//YLNAPHTHAL&VE
Rule 3. If the first group is a meta director (e.g., —NO3 , — SO3H, —COOH) and is
located at C-I or C-2, it will direct the incoming group to the C-S or C-I positions in the
other ring.
NO2 NO2 NO
NO2
C6
NiT,WNAPHTALbVE
HNO2
H2SO4
NO
I,5-DJNI70'
+ 66 NAPHTHALENE
LENE
NAPKTHAE,E
The above rules do not always hold in sulphonation. In this case the reaction is rever-
sible and at high temperatures tends to take place at a p-position in either ring.
IMPORTANT DERIVATIVES OF NAPHTHALENE

NAPHTHOLS
The hydroxy derivatives of naphthalene are known as naphthols.

1173
Fused Polynuc leer Aromatic
Hydrocarbons
01-I
1- NAPHTHOL 2-,1./APFITHOL
fr-NA PHT/-oL) (fl-NAPWrHQ)
1-Naphthol (s-Naphthol)
Preparation. l.Naphthol maybe obtained:

When sodium 1.naphthalenesUlPhonate is
(1) From Sodium i-NaphihaienesulphoPtafe.
fused with sodium hydroxide at 300 C, it gives sodium 1•naphthoxtde. Treatment of this with
dilute sulphuric acid yields 1-naphthol.
-4.
503N ONa H
Na OH Di H2$Od
06 300'C
06 C
SODIUM1- NA PHTRALENE s O/UM i-/VA P/V THO
5ULF10 NA TI t-iVAPHTHCXWE
Sodium 1.nap4thalenesulphonate used in the above reaction may be obtained from

naphthalene as shown below.
-4.
SO3Na
Conc: H2SO^ NaOH

1jIJ 60,C C6
NAPHTHALENE IWAPHTPALC41 5001it! I-NAP/VT/fAcEilI
4(iQ
S UL PHONIC
5 UL PHON'I TH
(2) From 1-Naphihylarnine. When 1-naphthylamine is heated with dilute sulphuric acid
at
o
c under pressure, 1-naphthol is formed.
OH
NH
DI H2SO4
-I-
300 'C/RCJ5UkE
- 7-NAPHTHOL
J.NAPWTWYIAMIN(
1.Naphthylamme used in the above ruction may be prepared from naphthalene as

ahown -below.

DL Advanced Qrgonc Chemistry
NO, NH,
HN0
H 2 5O, 6O0 HCi
HAPk17f-AL(/1E JVJ7ROPiTHA( 1-/,4Pkf/y A i.7.'/E
Properties. (Physical). 1-Naphthol is a colourless solid, mp 94 C. it is only slightly

soluble in water, but dissolves readily in ethanol and ether.
(Chemical). 1-Naphthol resembles phenol in its chemical properties.

(1) AcIdic Character. ]-Naphthol is a weak acid. It dissolves in sodium hydroxide or
sodium carbonate solution owing to the formation of water-soluble sodium -naphthoxide.
OH ONa
06 06
'NAPI-I ri-/CL
NaOH
H2O
5001U/4 I-NAP/i-li/Ox WE
The reason for the weak acidic character of l-naphthol is that it ionises in water to yield
a resonance stabilized naphthoxide ion. However, it is a stronger aoid than phenol. The
increased acidity is due to the greater stability of the naphthoxide ion as compared to the phen-
oxide ion. in the naphthoxide ion thz negative charge is delocalized over two aromatic rings,
whereas in the phenoxide ion it is delocalized over one ring.
When sodium I•naphthoxide is heated with alkyl halides, the corresponding ethers are
formed. (Williamson's synthesis)
-1'
ON O—CH CH
+ C3C2 I : N: i
SOVIUM ETiiY /-41PHrJJE e711ER

rNAPIIIHOX/Of 0-P714OXY f/A PHI/MI I//f)
(2) Reaction with Phosphorous Pepitachioride. l-Naphthol reacts with PCI to form
I -chloronaphthalene.
0f4 I
+ PCIS + +
tWAPHTHOL ?.(HIORONAPHUi-AL (NE
(3) Rucherer Reaction. The reversible conversion of a naphthol into the corresponding
naphthylamine is called the Bucherer Reaction, t.Naphthol reacts with ammonia and ammonium
sulphite at 150G C under pressure to yield l-naphthylasnne.
Fused Po!ynuclear Aromatic Hydrocarbons Ills
C6 (D6
OH
(NH4)2 503
+
14H, 15C,PU55U(
I-NA PHTHYLA"JNE
INAPH THO,
(4) Azo-coupliog. l-Naphthol reacts with benrenediazoniurt chloride in a weakly alka-

line solution at 0-5°C to give 4.phenylazo.1.flaphthol.
OH
(D6
7- N#PH rNOL

+
81WZ(N(-
OIAZOPWJM CHLO/D(
NaOH
0-5°C 00 N =N__0
4 -mEAIYL AZO-/-NAPHTHQL
(5) Reaction with Nitrous Acid. l-Naphthol reacts with nitrous acid to give 2-oxime of
I, 2-naphthaquinone.
OH 0
(0:6
I- NA PH TROt.
-
HNO2
2-OA/P1E OF
7,2 -NA PH T#IAQU/NOftl(

NOM
(6) Sulphonation, 1-Naphthol reacts with concentrated sulphuric acid at 40°C to yield
a mixture of 1-naphthol-2-sulphonic acid (Schoeffer's acid) and 1-naphtho[-4-sulphonic acid
(Nevile-Winther's acid). Both these sulphonic acids are used in the manufacture of azo dyes.
C6 06 0
OH OH CH
S0H
Cc H:SO4
,1COC
00
l-NAPHTHOL J-NAPHTHQL. -2- 5Oe-4
5UL PHON /C ACID 1-NAP/ITHOL -4-
jULPMON/C 'dIO
(7) Nitration, 1-Naphthol reacts with concentrated nitric acid and sulphuric acid at
20° C to give 2, 4-dinitronaphthol.

Advjnced Organic Chemistry
1176
OH
H2SO4
3b 00
IOH
a
0
1-NAPHTHOL
+ HNO)
2O C
0^ NO
2,4 - DJNITRO- I- N4PH1ROL
The sodium salt of 2, 4.di nitro- l-naphthol is known as Martius Yellow. It is used as a
dye for wool and silk.
(8) Reduction. I-Naphtholundergoes reduction with lithium metal in liquid ammonia

to yield 5, 8.dihydro-l-naphthol. (Birch Reduction)
Li
06
+ 2H ---v
NH)
06
I- 4 PHTI.40t. ./ -//4P//7'1OL
Reduction of 1-naphthol with sodium and isopentanol gives a;-tetrahydro-]-naphthol

or ar-a-tctralol. In these names the prefix aT- stands for aromatic and indicates that the four
hydrogen aroms are not in the ring containing the —OH group.
OH
1-NsPHTHQL
Na
C5HnOH
06
cx-rFrR/HyDRO -, NAP.TH&L
(rEreALc)
(9) Oxidation. I-Naphthol reduces ammonical silver nitrate. It is oxidised by chromium
'
trioxide in acetic acid to 1, 4-naphthaquinonc, and by alkaline potassium permanganate to
phthalonic acid.
0 QH
-COOH
KMr0 CrQ
1-
OH CHCQoH
(a COOH
PHTHALONIC ACID 1. MAPHTHOL 0

1,4-NAPHIHAQUINONC
Oxidation o l-naphthol with ferric chloride yields a blue-violet precipitate of

4, 4'-bis-l-naphthol or -binaphthol.

Fused P.Iynuclear Aromatic Hydrocarbons Ill?
OH
OH1
2©óFec'3
i-MI PM fl-lOt.
ON
4,4 '- t"s- 1-AlA P/I THOL
(.64Pr,L)
Uses. I -Naphthol is used in the manufacture of insecticides and dyes.
2-Naphthol (-Naphthol).
Preparation. 2-Naphthol is obtained by fusing sodium 2-naphthalenesulphonate with
sodium hydroxide at 300°C. Sodium 2-naphthoxide is formed which on treatment with dilute
sulphuric acid yields 2-naphthol.
TS03Ns WO,1
NaOH 04 113SO,
300'C
QyONa
$ODIUM 50OUM 2-NAPfiTJ1O

2 NAPf4TNA&EN(SULPHOIt'ATE 2.AIAP/IT,IOX,DE
Sodium 2.naphthalenesulphonate used in the above reaction may be prepared fro.
naphthalene as shown below.
00
NAPH 1/-IA LF.7E
165*c
W S0
Z1vAPHTHALE4'E 5111 P110/I/C

W
SODIUM
ACID 2-IQAP1ITH4L(Nf .WLPl4UNI1
Properties. (Physical). 2-Naphthol is a colourless solid, mp 123°C. It is only slightly

soluble in water, but dissolves in ether and ethanol.
(Chemical). 2-Naphthol resembles l-naphthol in its chemical properties,
(I) Acidic Character. Like l-naphthol, it is also a stronger acid than phenol. It dis-
solves in sodium hydroxide or sodium carbonate solution to give water-soluble sodium 2-naphth-
oxide,
ffH _
NaOH
-4.
WONa
2 -NAP/I T/IOt. SODIUM 2-NA PHI/lOX/Off
Organic ( Iieniistry - 75
l!?8
When sodium 2-naphthoxide is treated with alkyl halides the corresponding ethers are
obtained. ( Williamsons Synthesis)
—+
ON O—CH7CH3
SoQLfM Z 'N4PHT/,0X IDE

+ CH3CN2I ... a —.I-
W
6NYL -Z-NPHTHL ETHER
Ethyl 2.naphthyl ether is known as nerolin. It is used as a perfume in artificial neroli

oil and eau de Cologne.
auction with Phosphorous Pcutschloride. 2-Naphthol reacts with PC], to give
(2)
2.chloronaPhthalefle.
OH
W Z-NAPHTHOL
+ P05
WC,
2LO)!0/VAP1ITIA LEN!
Reaction. 2-Naphthol reacts with ammonia and ammonium sulphite at

(3) Bocherer
150°C under pressure to yield 2-naphthylaflhifle.
OH
(NH4)2505WN112
+ M-I
50°C, PRE5.$oRr
2NAPNTNYAMINE
2-NAPHTHOL
(4) Azo-coupllng. 2-Naphthol reacts with benzencdiazofliUn chloride in a weakly

alklaine solution at 0-5°C to form 1 .pbenylazo-2.naPhthOl.
_=-© OH
OH
NaOH
2-NA/fri T4HO.
+
BENZENEDIAZONIUM
0-5°C I' -
C&
1_P8(NV1AZ0MPHTH0L
c#ILOR/DE
with Nitrous add, 2-Naphthol reacts with nitrous acid to give 1-oxime of
(5) Reactio n
, 2napbth0'
NOM
@9 - - OH
-- P.
HNO2 irxitr
0
I-OIME OF
2-NAPHTHOL
zNAPI1Tfr1A1N0

Fused Polynucfeor ANInoticNydrocotbons 179
(6) Sulphonation. 2-Naphthol reacts with concentrated sulphuric acid at 40'C to yield
2.naphthol.8.sulphonie acid (Crocein acid). When this reaction is carried at 100 0 C, croccin acid
undergoes rearrangement to give 2-naphthol-6-sulphonic acid (Schaeffers p-acid). Both these
suiphonic acids are used in the manufacture of azo dyes.
SO3H
©O
2-NAPI4THOL-6-
$ULPHON,C ACID
Conc H2SO
MO O OOnC40 C aI4O3S'
H 100'c
2-NMKTHOL
H5Q
6T
2-NAPI'ITNOL--
SLIt P/ION/C ACID
(7) Oxidation. 2-Naphthol reduces ammonical silver nitrate. It is oxidised by alkaline

potassium permanganate to phthalonic acid.
11' OOH
KMnO
^ro; ( acoo, c
2-NA°t1TH01- PN7HAL ON/C ACID
Oxidation of 2-naphthol with ferric chloride yields a green precipitate of 1,1' .bLs.2.naph-
thol or .binphathol.
2 (M OH
90H
FCi3
OH
1,1-815-2-NAPHTHO(
(fi- 818AP/1T/IO)
(8) Reduction. 2-Naphthol undergoes reduction with sodium and isopentanol to
give ac-tetrahydro-2-naphthol or ac--tetralo!. In these names the prefix ac-stands for ailcyclic
and indicates that the four hydrogen atoms are in the ring containing the —OH group.

t1r_ow OH

ca
z•J/AmT/joL ac -TErgAIIyoRO--NAmryoI
(8TEr4LoL)
Uses. 2-Naphthol is used (I) for making dyct (2) as an antioxidant in the maciu•
facture of synthetic rubber (3) as an antiseptic in the treatment of skin diseases ; and (4) for
preparing its methyl and ethyl ethers (nerolins) which are extensively used in perfumery.
1180
NAPHTHVLAMI'ES
The amino derivatives of naphthalene are known as the naphtbylamines.
N11
NH2
C60 Wo
2/IAPI4T.'YLAMlWt
NAPHTHYLM"
NAPHrHvAM/e) .(8 -WA P11 IN YL AM/NE)
1-Naphthylamlne (a.Naphlhylamifle)
Preparation. l.Naphthylamifle may be obtained:
(1) By the reduction of l.nitronaphthalcne with iron and hydrochloric acid.

(Commercial method)
(2) By heating 1-naphthol with ammonia and ammonium sulphite at 150°C under
pressure. (Bucherer reaction)
(3) By heating l-naphthol with ammonia and zinc chloride at 260° C.
NH2
OH
ZnCl2
+ NH 3 -
1-N4P/-ITHYLAM!NE
f- NpWr1-QL
1.Naphthylamifle is a colourless solid, mp 500 C. It turns brown

Properties (Physical).
on exposure to air. 1.Naphthylamifle is only slightly soluble in water, but dissolves readily in
ethanol and ether. It has an unpleasant odour.
(Chemical). 1.Naphthylamine resembles aniline in its chemical properties.

I. Basic Character. l.Naphthylamine is a weak base (pK=39). It dissloves in acids
to form the corresponding salts.
—) -
C:Ei
l-N4PHTHYLAMINE
+ HC
C6
I. NAPHIHYL4MMONIW4
CHLORIDE
The reason for the weak basic character of l-naphthylamine is that the lone pair of
electrons on nitrogen is involved in the formation of the delocalized it molecular orbital and is
not readily available for the formation of a new covalent bond with proton.
l.Naphthylamifle is a slightly weaker base than aniline (pK.46). This is due to the
more extensive delocalilatiOn in the case of l.naphthylamine.
Fused Poiynuc1eir Aromatic Hydrocarbons ''Si
,LE55 AVAILABLE MOR( AI4/LABLE

LONE PAIR ZONE PAIR
:NH2 NH2
o6
!-NAPIIT/IYLAMIIIE

6
AN/LINE
(WEAKER 8A() (5 TRON6ER 84.5E)
In l.naphthylamine the lone pair of electrons on nitrogen is delocalized over two rings,
whereas in aniline it is delocalized over one ring. As a result, the lone pair in l.naphthylamine
is even less available for the formation of a new bond with proton.
(2) Diazotization. l-Naphthylamine reacts with sodium nitrite in excess hydrochloric
acid at 0-5C to yield l.naphthalenediazonium chloride.
1--
NI42 N 1
C 16
7-NA PH TN YLAM (NE
Ne NO2
HCI,O5°C
06
t.4'AP#iTHALENEO/AZONIUAI
CHLORIDE
Like other diazonium salts, l.naphthalenediazonium chloride couples with phenols and
aromatic amines. It may also be converted into a large number of 1-substituted naphthalene
derivatives by the reactions we have already studied. For example,
11 2 0 Br gar
06 Qb CuBr
____1
Mg
ETRER
1-THAENEL442OWI41 !-8V4WrnffM4LENf I-NAPf/THYLHA6NE5IL/k

00 _______ MA WY
COMPOUNDS
8R0MIDE
(3) Azo-coupllng, l-Naphthylamine reacts with benzenediazonium chloride in a weakly

alkaline solution at 0-5C to give 4-phen, azo-1-naphtbylamine.
0
NNi
00
NH2
06+
tMApurH4M,NE
c—N1151--*
O-5C
BENZENE
OIAZONIW4 CHLORIDE
NaOH
N N
00
4 -P E1YL4ZO ,.NAPHrH?AM/NE


1181
(4) Sulphonatloa. l-Naphthylamine reacts with concentrated sulphuric acid at 140°C

to give 1.naphthylamine4-sulphonic acid or naphthionic acid.
NH
140°C
4PTHYLM!t
NAP14TH10NIC ACID
Naphthionic acid is used in the manufacture of Congo Red.
(5) Reduction. 1-NaphthyLamire undergoes reduction with sodium and isopentanol to

give ar.tetrahydro-l-naphthylamine (5,6,7,8tetrahYdrO1-naPhthYlam1fle)
WHi NM3
Pi.
@6 @
CH,1OH
0
a't.-tTRMO-l-
NAp4rrn'LAMINt
MAPFITHYZAkWE
(6) Oxlditlon. I-Naphthylamine reduces ammoniacal silver nitrate. It is oxidised by

chromium trioxide in acetic acid to 1,4.naphthaquinone, and by alkaline potassium permanganate
to phthalic acid.
H2
Cr03 KMr0
CH3COOI-I
1-7LAME
OH
^^ COOH
p,q THAVC.4C1D
1,4-WA PH TWA QWNQ WE
1-Napbthylamifle gives a blue precipitate with ferric chloride.
l.Naphthylaminc is used in the manufacture of dyes.

Use.
2-Niphthylimlne (-Naph1hylamine)
Preparation. 2-Naphthylamifle is obtained industrially by the Bucherer reaction. in
ammonium sulphite at 150° C under pres-
this method 2-naphthol is heated with ammonia and
sure.
2.Naphthylamine is a colourless solid, mp 112°C. It is only slight-
Properties. (Physical). open
ly soluble in warer, but dissolves in ether and ethanol. 2.Naphthylamifle is not sold in the
exposure to it leads to bladdar tumors.
market because prolonged
(Chemical). 2.NaphthyIamitIe resembles l-naphthylamine in its chemical properties

(1) Basic Character. 2-Naphthylatniflt (pK
1 = 41) is also a weaker base than aniline
and dissolves in acids to give the corresponding salts.
Fused Polynuclear Aromatic Hydrocarbons 1183
Nk1
+ HCI -

Z -NA PH7/1 YAMINE lNAPHTNYLAM/lOiV, t'tl
CHLORIDE
(2) Di2zotization. 2-Naphthylamrne reacts with sodium nitrite in excess hydrochloric

acid at 0-5°C to yield 2-naphthalenediazonium chloride.
1--
NCt
W
N a NO2
HC110-5°C
w
2-M4PR THYk4MIW( 2NAT'IAWL)iAZQN/La1

CHLORIDE
2.Naphthalenediazonium chloride couples with phenols and aromatic amines and can be
converted into a large number of 2-substituted naphthalene derivatives.
(3) Azo-coupling. 2-Naphthylamine reacts with benzcnediazonium chloride in a weakly

alkaline solution at 0-5°C to give L-phenylazo-2-naphthylamine.
NH, —0 NP1
09 + &
2
C&
NaOH
N C1
5'C'
Z- PHIWAAAf 8WZtNE -PHEI,1YLAZO Z- NAPgmy-

DIAON UM CHLOR/D AMINE
(4) Reduction. 2.Naphthylamine undergoes reduction with sodium and isopentanol to
yield ac-tetrahydro-2-naphthylamine (I ,234-tetr hydro.2-naphthyIamine).
NK
O3'Na HOH
cLC-7j7RAHYDR0-J.MAfl47NYLA4hV9F
(5) Oxidation. 2-Naphthylamine reduces ammonical silver nitrate. Like l-napthyl-

amine, it undergoes reduction with alkaline potassium permanganate to give phthahc acid.
(00*4
"COOH

2 *AP1-THYLA41,NE PH7HAL1C ACID
2.Naphtbylamine gives no colouration with ferric chloride.

We. 2.Naphthylamine is used in the manufacture of dyes.

1184 Advanced Organic Chemistry
NAPHTFIAQUI NONES
Three naphthaquinones are known:
a0
4
11
0
1,4 -AlA P/I TIIAQ WNONE
(-NAPHTHARNo--)
0
1,z NAPHTHAQWNONE
id/I PHI/IA QU/N014F)
0
-
Yo
OAA)
WAPHTHAQV/NONE
(l.1PI1l -NAP/I TI/A QUINON()
1,4-Naphtliiquinone (a-Naphthaquiiwne)
It is obtained by the oxidation of 4-amino . l-naphthol with potassium dichromate and
sulphuric acid.
OH 0
K, Cr2 0 7)
H2SO4 0EIII
co
NH
4-AMIN0-I-NAPHI40L 1,4 -NPiP/IIHAQU/NONE

1 14-Naphthaquinone may also be prepared by the oxidation of naphthalene with chro-
mium trioxide in glacial acetic acid.
1,4-Naphthaquinone is a yellow crystalline solid, nip l25'C. It is volatile with steam.

It is reduced by hydriodic acid and red phosphorous to 1,4-dihydroxynaphtha]ene
OH
Hi
0
OH
I,4 -NAPHTHA
1, 4--D/#tyDRQxyAp/IryAj
Oxidation of 1,4-naphthaquinone with potassium permanganate and dilute sulphuric

acid gives phthalic acid.
11
0
O
cool-f
PMnO4
H?504
(acoc"
o P/-THA/C -4C10
I4.4ITNAQIJ/Nf

Fused Polyrniclear kometic Hydrocarbons 1185
A number of 1,4-naphthaquinone derivatives have been isolated from plant and animal
sources. For example, jug/one (5-hydroxy. 1,4naphthaquinqe) is found in the shells of walnuts.
Plumbagin (2-methyl-5•hydroxy-1,4 . naphthaqujnone) is isolated from the roots of various species
of plumbogo. Lawsone (2hydroxy-1,4. naphthaqujnone) is obtained from the henna plant and is
used in the manufacture of henna hair dyes.
0
0

0 1
OH 0 CHI

Pt (IMDA6/N L A(/5ONE
Ju& ONE
Vitamin K is found in leafy vegetables and is essential for the proper coagulation of
blood. It is a derivative of 2methylL,4.naphthaqUinOfle (meriadione).
CH3
CE4 C43
CH
0
VITAMIN K
1,2.Nsphtlaaquinone (-Naphthnquinone)
12-Naphthaquinone is obtained by the oxidation of 1amino-2-naphthol with ferric
chloride or potassium dichromate and dilute sulphuric acid.
NH? 0
/OH
Fed3
00 HCJ
cl: 0
1.AM!NO-2-NAPHTKOI. 1,2.NAPHTkAQL11NOVE
0 C (with decomposition). It is
1,2. Naphthaquinon e is a red crystalline solid, mp 115
non-volatile with steam. It is reduced by hydriodic acid alone to 1,2.dihydroxynaphthalene.
OH
0 5/OH
HI . c
a --

t, 2 -NAPHr/IAWYQN( I. 2-DiflyoRox )WAPHTML (NE
Oxidation of I,2.naphtbaquinone with potassium rmananate in dilute bicarbonate

59luion gives phthaloflic acid.
Adyancd Organic Chemistry
1186
1,2-A'APHT,YAQU1N0NE
KMnO4
DO NaHC3 0 C—COO4f
COOK
PH THALON/C A CID
2,6-Nspbthuquinone (Amphi-naphlhaquinone)
2,6-Naphthquinone is obtained by oxidising 2,6-dihydroxynaphthalene with activated

lead dioxide in warm benzene,
M CON
HO
2) 6-W/1YAWXYNAPWTHALEJs'E 1,6 .N4PHT#IAQL/'NOM6
2,6-Naphtbaquinone is an orange solid, mp 135 0 C. It is non-volatile with steam.
a-NsphthylEetic Acid
s-Naplithylacetic acid is obtained by the chloromethylation of naphthalene, conversion

to nitrile, and hydrolysis.
CH2CI CH2C00H
1©
NA PH TIIA L Flit
________
HCHO
HO
(1) KCN
(2)H20/H
I-Ci'LOROM( rNyLNAPfiT/IALENE i-NAPHTHyL,q frI( ACID
-Naphthylacetic acid is used as an 'apple set' spray to reduce the premature dropping
of fruit from the tree ; one application near the end of growing season holds the apples on the
tree for one or two weeks -Naph thy ]acetic acid is also used as a spray to delay the flowering
of fruit trees until the danger of frost is past, and as a spray to keep potatoes from sprouting.
When sprayed on tomatoes and cucumbers, it causes the production of seedless fruits.
ANThRACENE
Anthraccne occurs in coal-tar (less than I per cent) and is obtained from the green oil
fraction (bp 270-360C). On cooling this fraction crude anthracene crystallizes out. Crude
anthracenc contains phenanthrene and carbazole as impurities, It is purified by washing it
successively with solvent naphtha (to remove phenanthrene) and pyridine (to remove carbazole).
Finally the solid is sublimed to give pure anthracene
In naming derivatives of anthracene, the numbering system shown below is used. The
numbers selected to denote the position of a substituent on the anthracene rings should be as
small as possible.

Futed Potyncictear Aronwtic Hydrocarbons 1181
SOi
9
to
ANTRRACLN(
.5
9thOMQArJHRAC(NE
C)C
t-A'7HRACEA1(541LPM04'1C
AC/0
STRUCTURE OF ANTHRACENE
All fourteen carbon atoms in anthracerie are s1 2 hybridized. The sp2 hybrid orbit ls
overlap with each other and with s orbitals of the ten hydrogen atoms forming C—C and C - 11
a bonds. Since the bonds result from the overlap of trigonal sp' orbitals, all carbon and hydrogen
atoms in anthracene lie in the same plane. This has been confirmed by X-ray diffraction
studies
Also each carbon atom in arithracene possesses an unhybridi7ed p orbital containing one
electron. These p orbitals are perpendicular to the plane of the a bonds. The lateral overlap of
these p orbitals produces a t molecular orbital containing fourteen electrons (Fig. 463). One
half of this it molecular orbital lies above and the other half lies below the plane of the a bonds.
Anthracene shows aromatic properties because the resulting it molecular orbital satisfies the
Huckel's rule (n=3 in 4n+2).
INHYBRID/ZED
P-'R8/TAtS
MO
- Fig. 463. Forniatian of tr molecular orbital in anthracene.
A common shorthand representation of anthracene is simply three linearly fused hexa-

gons with a circle inside each hexagon. The circles represent the r, molecular orbitals.

00:cd -
MOUCCUIAIR
ORBITA.
According to the resonance theory, anthracene is considered to be a hybrid of the folio-

wing four canonical forms.
0a Yf rY
X-Ray diffraction studies show that, like naphthalene, all carbon-carbon bonds in
anthracene are not of the same length. In particular, the Cl—C2 bond is considerably shorter
(I37A) than the C2—C3 bond (142 A). This difference in bond lengths can be understood if we
examine the four resonance forms given above. Notice that the Cl—C2 bond is double in three
structures (A, B and C) and single in only one (D) ; whereas the C2—C3 bond is single in three
structurres (A, B and C), and double in only one (D). We would, therefore, expect the CI—C2
bond to have more double-bond character (shorter bond length), and the C2—C3 bond to have
more single-bond character (longer bond length).
The resonance energy of anthracene is 84 Kcal/mole. This averages to 28 Kcaljmole per
ring, which is substantially lower, than that of benzene (36 KcalJmole). As a result, anthra-
cene is much less aromatic than benzene and behaves more like an unsaturated aliphatic hydro-
carbon.
SYNTHESIS OF ANTHRACENE
Anthracene may be obtained

(1) By Friedel-Crafts Reactions. Benzyl chloride reacts with itself to form 9,10-dihydro-
anthracene, which readily loses two hydrogen atoms to yield anthracene,
H' n00
Cct MCI -2H
(-2Hc1)
ANTH9JcFN6
BENZYL C/-ll-O//DE 9,10-O/HYDRONTHRACfNE
'(2 MOLES)
Anthracene may also be prepared by the Fricdel.Crafts reaction between beozene and
1,1,2,2-tetrabromoethane (acetylene tetrabromide), or between benzene and dibromomethane.
O
-
I (_4HBr)
'BrCBr
H ANTHR4CENE
ENZ(NE BENZ ENE
ACETYLENE
T6rRMROM,OE
Fused Poiynuciear Aromatic Hydrocarbons 1189
0
HH
ar\)
Br
© Aid3
(._4HBr
0 2H
©+
API THRACENE
BENZENE /C\ 8ENZEN°
H H
9, 10-D/h'YOR0ANTIIR,4(ENE
(2) By Haworth Synthesis. This involves the treatment of benzene with phthalic
anhydride in the presence of aluminium chloride to form o-benzoylbenzoic acid. This is then
heated with concentrated sulphuric acid to give 9,10-anthraquinone. Distillation of the
anthraquinone with zinc dust yields anthracene.
o 0
II II
© A101 H2501
+
'-._-
o 8EMZENE 0
i°HTHAL/CAttIHYDR/O( o-8IWZOY48ENZOIC ACID
0
0 Zn
DISTIL
ANT/IRA CENE
9, iO-ANTHRAQ (J/WONE
(3) By EIbs Reaction. The conversion of a diaryl ketone containing a methyl or

methylene group ortho to the carbonyl function is known as the Elbs Reaction. For example,
when o-methylbenzophenone is heated at 450°C, anthracene is formed.

= + H20
):c

0 /e?11Y8fN10PHE/VONE A NTIiRAC EIVE
(4) By Diets-Alder Reacton. This involves the reaction of l,4-naphthaquinone with

1,3.butadiene. The product of this reaction is oxidised with chromium trioxide in glacial
acetic acid td form 9I0-anthraquinone. Distillation of anthraquinone with zinc dust yields
anthracene.
1190
0
--
CH
0
1,4- NAPIiTHAQUINOME
H2
CH
J', 3-8umoif,
Q0 CH3COOH
D1EL5. pfR ADD(JCT
Zn
0
.INTIIRAC(NE
9, ?O -ANTNRQjj
PROPERTIES OF ANTHRACENE
(Physical). Anthracene is a colourless solid. It melts at 21 8 0C and boils at 340°C.
Anthracene is insoluble in water, but dissolves in benzene. It shows a strong blue fluorescence
when exposed to ultraviolet light. This fluorescent property of anthracene is used in criminal
detection wtrk, since a small amount of finely powdered anthracene on clothing, skin, money,
etc., is not detected under ordinary light but easily noticed when exposed to ultraviolet light.
(Chemical). Anthracene undergoes addition and c]ectrophilic substitution reactions.
These reactions preferentially occur at the C-9 and C.lO positions. This can be under-
stood if we examine the intermediate carbomum ions obtained from attack at C-I, C-2,
and C-9 (all other positions are equivalent to either I or 2 or 9 by symmetry). E+ in the
following equations represents an electrophile.
Attack at C-I
oc:6cd
E
5 10
-I-
Attack at C-2
I Ii I I 4. :r < C-1
Attack at C.9
-
Fused Po1ynuc1eir Aromatic Hydrocarbons H91
Attack at C-9 yields a carbonium ion intermediate in which two benzene rings are
retained whereas attack at C-I or C-2 yields an intermediate in which a naphthalene
system is retained. The former intermediate is more stable and its formation favoured because
the resonance energy of two benzene i ings (2 x 36 = 72 Kcal) exceeds that of naphthalene
(61 Kcal). This carboniurn ion intermediate can lose a proton to give the corresponding
substitution product, or it can react with a nucicophile to form the 9,10-addition product.
Nui in the following equations represents a nucleophile.
.suBsrIIc/r/QN PftOtflJC 1
ADDITION Po'cT
Substitution at C-I or C-2 occurs only when the reaction is reversible (as in the case
of suiphonation).
The main chemical reactions of anthracene are described below.
(I) Reaction with Sodium. Anthracene reacts with metallic sodium in liquid ammonia
to form a deep blue 9,10.disodioanthracenc.
lí ç . NH3
+ 2Na
AMTACEN6
9,I0— 01$ 0D,O.4NTHRACF/VE
(DEEP BLUE)
When the disodio-derivativve is heated with an alklyl halide, it gives the corresponding
9,10-dialkylanthracene.
CHCH
CHCH2Ct
9,0I0010A,Tw'ACEw5 'H1CH
9, 7O-DiET/iY ANTI/RACE//f
(2) Reaction with Halogens. Anthracene reacts with chlorine in carbon tetrachloride
at room temperature to give 9,10.dichloro.9,10 . dihydroanthracene (an addition product). On
heating, this addition product loses a molecule of hydrogen chloride by 14-elimination
to form 9ehIoroanthracene (a substitution product).

H92 Advanced Organic Chemistry
M C1
IN CCI4
+ , -
r__cIJ
CI
AITNRAENC 9<IIWRON1THMCENE
9, 10 -o,cio p - 9,10-
DI'4Y00AWTHRAUN1
9. Chloroanthracene may also be obtained by chlorinating anthracene at 100°C, or by

treating anthracene with cupric chloride in CC],.
Bromine reacts similarly.
(3) Friedel-Crafts Acylallon. Anthracene undergoes acylation with acetyl chloride and
aluminium chloride in benzene to form 9-acetylanthracene,
0=0 + CI'43--CI
/NB(A(ZENE HIC
anthracene 9-acctylanthraccne
(4) Nitration. Anthra'ene undergoes nitration with concentrated nitric acid in acetic
anhydride at room temperature to yield a mixture of 9-nitroanthracene and 9,10-dinitroanthra
cene. The usual nitrating mixture (HNO 2 + HSO4 ) is not used because it leads to the
formation of 9,10-anthraquirione by oxidation.
U.
NO2
X©
ANThAC(N(
+I1NO
(CH3CO)20
S- NITROAWTHRACEN(
+*
NO2
9,T01w1T0AwmRAc4fw5
(5) Sulphonation. Anthracene undergoes sulphonation with concentrated sulphuric
acid to yield a mixture of 1-anthracenesulphonic acid and 2-anthracenesulphonic acid. At
lower temperatures I -anthracenesulphonic acid is the major product ; where as at hi,hcr
temperatures 2-anthracenesuiphonic acid is the major product.
503H
(=S034
NSO4
2 t

NrF1RACNE V-AWTHRACFNE5ILPH0N1C
-Ni1HRACENEWLPmW1C
ACID ACID
(6) Reduction. Anthracene undergoes reduction with sodium and ethyl alcohol to
form 9,10-dihydroanthracenc.

Fused Polynuclear kornatic Hydrocobons 1(93
Ne, C2HSOH
^*D
-
ANTHgACENE
9, IO-D//IYOROAJITHRACfNE
Catalytic reduction using nickel at 225 CC first gives 9,10-hydroanthracene, and on

continued hydrogenation this is converted into 1,2,3,4-tetrahydroanthracenc and 1,2,3,4,
5,6,7,8-octahydroanthracene. Notice that the 9,10-hydrogen atoms migrate to the neighbouring
ring.
501 scss
9,10-0,HYDR04Nn4CENE 1,2,3,4-TE7IVAtQANTH. AC(/lE 1,2,3,4,5,6,8-0CTA-
HYOROANTHRACEJiE
(7) Oxidetion. Anthracenc undergoes oxidation with sodium dichromate and

sulphuric acid to form 9, 1 0-anthraquinone. Other oxidising agents like nitric acid and air in
the presence of V101 also lead to the formation of 9, 10-anthraquinone.
N- ANTSL4RACEWE
NbCr2O7,
H,504
A l'ITHRAQ U/NONE
(9,10-ANTHRAQt1/NOtiE)
(8) Diels-Alder Reaction, Anthracene undergoes a Diels-Alder reaction with maleic

anhyd rideto yield the corresponding adduct.
C\
ANTPRACENE MARC
ANHYD R IDE
II
0
!ELS -ALDER 4DDL/C7
Use. Anthracene is used in the manufacture of anthraquinone.

Organic chemistry - 76

H94 Advanced Organic Chemistry
IMPORTANT DERIVATIVES OF ANTHRACENE

Anthriqulnooe (9,10-An:hraquinone)
Three quinones of anthracene are known. They are the 1,2-, 1,4-, and 9,10-
anthraquinone. 9, IO . Anthraquinone is of considerable industrial importance and is usually
referred to simply as anthraquinone.
Preparation. Anthraquinone may be obtained:
(I) FROM ANTHRACENE. When anthracene is oxidised with sodium dichro-
mate and sulphuric acid; or air in the presence of vanadium pentoxide at about 400°C, anthra-
quinone is formed
FII :: IIIIIIIJ
ANTHRACENE
9,10-ANTkAQtJ1NO'VE
(2) FROM BENZENE AND PHIHALIC ACID. When benzene is treated with
phthalic anhydride in the presence of aluminium chloride, o-benzoylbenoic acid is formed.
Treatment of this with concentrated sulphuric acid yields anthraquinone.
0
5EWZEN(
AICi
H2SO4
(-4420)

P4Tt4C ANkYOPJ1E o-SENZOYL8EMi'CACID ANNRAQUINONE
This process is used commercially, The derivatives of benzene and phthalic alsydride
may be used to produce substituted anthraquinones.
Properties. (Physical). Anthraquinone is a pale yellow solid, mp. 26°C.' It isins'oluble
in water, but dissolves in boiling benzene.
(Chemical). Anthraquinorse shows very little resemblance to p-benzoquinode e.g. it
has no smell, is not volatile, and is resistant to oxidising agents. This is probably because the car-
bonyl double bonds are each part of an aromatic system. It behaves more like an unreaclive
aromatic ketone.
Some of the important chemical properties of anthraquinone are described below.
(I) Redacijois. Anthraquinone undergoes reduction with alkaline sodium hydrosuiph.
ite (Na1S104 ) or zinc and alkali to form 9,10.dihydroxyanthracene. This dissolves in alkali to
yield a disodium salt of 9, 10-dihydroxyanthracene, which is blood-red iii colour. Its formation
may be used as a test for anthrquiaon. When the red solution is exposed to air and shaken,
anthraquinone crystallizes out.
4.
OH
NaOH
0
P
N s25204
NaOH
04.4
*0 ONe
9,JQ 1D/gyDR0xyANTHRAC5 /5OWMSALT0F
ANTHRAQWNONE
.yy44FiK4CENE

Fund PolyncicIe,r Aromatic Hydrocarbons 1195
Reduction of anthraquinone with tin and hydrochloric acid in glacial acetic acid
yields anthrone which tautomerizes to anthrol (9.hydroxyanthracene) with boiling alkali,
OH
000
ANTHRALI/WONE
Sn /HcI
CH3COOH
@ 10
NTHONE
-NaOH
ANTHOI.
Anthraquino'ne is reduced to anthracene by heating with concentrated hydriodic acid at

15OC or distilling with zinc dust.
(2) Nitration. Athraquinone undergoes nitration with concentrated nitric acid in the
presence of sulphuric acid to form I-nitroanthraquinone. Prolonged heating yields a mixture of
1,5. and 1,8 .dinitroanthraquinoncs. When 1-nitroanthraquinone is heated with ammonia,
l-am • noanthraquinone is formed,
NO
0 NH
NH
H2SO4
mTNR.euIONE

1N1 TROmThRAqu/t,O*

016
f- A MAVOAN7HRAQ4v1.VNr
1-Aminoanthraquidone is used in the manufacture of indathrene dyes.
(3) Snlphonatlon. Anthtaquinone undergoes sulphonation with fuming sulphuric acid
at 160°C to give Vanthraquinonesulphonic acid. Prolonged heating yields a mixture of 2,6.
and 2,7 . anthraquinoaedisulphonic acids. If suiphonation is carried in the presence of mercuric
sulphate catalyst at 135°C, l•antliraquinonesulphonic acid is obtained. Prolonged heating in
this case yields a mixture of I, 5. and 1,8•anthraquioonedisulphonic acids.
3H
JAO5H
H:;:*c 1601C 0
0
1ANTHAQ LJ/NC?( ftRUQUaVcWE 2- AW7/RALJ/NoNe.
SUL P/ION/C ACID
5IJLPHO'IIC ACID
When 2-anthraquinonesulphonic acid is fused with sodium hydroxide and sodium
chIrate (NaClOa) at 200°C under pressure, alizarin is formed.
S0H
*/ NeO$1 1/ Na CI 0
200 0C, PR1$S1R(
a&
2-ANT/IflAu,'NON(- Ai/Z4RfN
SLILPHONIC AC41 (1,2.1iiYoRoxI'ANTHR4Qa1NON)

Anthraquinone does not undergo Friedel-Crafts reaction.
Uses. Anthraquinone is used in the manufacture of alizarin and several other dyes.
Alizarin (1,2-dihydroxyanthraquinone)
The structure, preparation, and properties of alizarin are discussed in the chapter on
Colour, Dyes, and Pigments.
PHENANTHRENE
Phenanthrene is an isomer of anthracene. It may be obtained, along with anthracene,

from the green oil fraction of coal-tar. On cooling this fraction we get a solid mass which
contains phenanthrene, anthracene, and carbazole. Treatment of this with solvent naphtha disso-
lves phenanthrene. Evaporation of this, solution yields crude phenanthrene, which may be
purified by recrystallization of the picrate from ethanol.
In naming derivatives of phenanthrene, the numbering system shown below is used. As

before, the numbers selected to denotethe position of a substituent on phenanthrene rings should
be as small as possible.
I
6 9 4 3 8 9
STRUCFURE OF PHENANTHItENE
Like anthracefle, phenanthrene is a planar molecule. All fourteen carbon atoms are sp'
orbitals overlap with each other and with s orbitals of ten hydrogen atoms
hybridized. The sp t
to form C—C and C—H a bonds. Each carbon atom also possesses a p orbital and these are
perpendicular to the plane containing the a bonds. The lateral overlap of these p orbitals produces
a , molecular orbital containing ten electrons. Phenanthrene shows aromatic properties because
(n=3 in 4n+2).
the resulting it molecular orbital satisfies the Huckel's rule
A common shorthand representation of phenanthrene is simply three hexagons fused in

angular fashion with a circle inside each hexagon. The circles represent the it molecular orbital,
AICLECLILAR
ORBITAL
A
0 '0

1197
Fused PoIynuclear Aromatic Hydrocarbons
phenanthrene is considered to be a hybrid of the following five resonance forms:
The resonance energy of phenanthrelie is 92 KcaImotc,

SYNTHESIS OF PHENANTRRENE
Phenanthrene may be obtained from naphthalene and succinIc anhydride by the Haworth
H1
synthesis as follows.
0 CH2 /N
It CH, CH
C^C\ I COOH
IM + H2 AICI, ZrHg)
I MCI
H(
tX!N1C AW/#YD(O(
o Z()
0.
'4210.
- HCI
A,-H,o) .
PROPERTIES OF PIjR4ANT1IR.NP
(Physical). t'henanttircne is a colourless solid, nip tOQ'C. It is insoluble in water, but
dissolves readily in ethanol, benzene, and ether. Phenanthrenc gives blue fluorescence in
benzene solution.
substitution
(Chemical). Phenanthrene undergoes oxidation, addition and electrophilic
reactions. As with anthracene, these reactions preferentially occur at the C-9 and C-tO posi-
tions.
Some of the important reactions of phenanthrene are described below.
(I) Reaction with Halogens. Phenanthrene reacts with chlorine in carbon tetrachloride
at room temperature to give 9,10.dichloro.9,10 .dihydrOPheflaflth r e ne (an addition product). Or
heating this loses a molecule of hydrogen chloride to yield 9-chlorophenaiithrene (a substitutior
product).
Ci Ci Cl
I tO
72
Cl2
IN CCII - HC ij &00
9, 10-D!CHLORO9, 9-CHLOR0P11(MN7I/REME
PHE N1IMTNRENE D -YDOPRENAWTRREN5

1198
9-Chlorophenanthrene may also be obtainea by treatment of phenanth.ene with chlorine

in the presence of FeC!3.
Bromine reacts similarly.
(2) FrIe*lel-rafts Acylatlon. Phenanthrene undergoes acylation with acetyl chloride in

the presence of aluminium chloride at OT to give 9-acetyiphenanthrene.
/ CM3
db
PHNANT/YeEAJE
-I-
MC1 3
. dbo
0-
9-A CETYL PHCAtINTWREN(
(3) Nitration. Phenanthrene undergoes nitration with concentrated nitric acid and
sulphuric acid to yield 9-nitrophenanthrcne.
NO
C%IWENANTHRLN6
HSQ
0
(4) Salphonation. Phenanthrene reacts with concentrated sulphuric acid at 120C to
give a'mixture of 2-phenanthrenesufphonic acid and 3-phenanthrenesulphonic acid. Notice that,
like anthracefle, substitution does not occur at C-9.
-
2 $OH
PHENAN 18eNe 2-PflENA4'Tf*4'f5ULP/10N1C ACID o,ii

3-,Wi'7NRThrSUMvfC ACAP
(5) Reduction. Phenanthrene undergoes reduction with sodium and isopentanol to

form 9,10-dihyd rophCnanthrene,
4H
CAD
PI1t1VAN7*/ljEM5

N C H,1OH
91 10
(6) OxIdation. phenanthrene undergoes oxidation with potassium dichromate and sulph-
uric acid or chromium trioxide in acetic acid to form 9,l0-phenanthraquinone (mp 206' C).
Further oxidation of this with hydrogen peroxide in acetic acid gives diphenic acid.
1)99
Fused PoIynucear Aromat ic Hydrocarbon s
.©11o_ CL
10
C0014
K 2 Cr 2 O7, H20.
3CQOH COOH
içr
pHEA/AIrHREA'E , 10.PHtNAWTNR,4QUINO1VE O/PHEN/CAC/D
Phenanthrene is of little industrial importance but phenanthrerte ring systems are

found widely distributed in natural compounds such as carcinogenic (meaning cancer-producing)
hydrocarbons, bile acids, sex harniones, morphine alkaloids, and cholestrol.
QUESTIONS
(DthruSarh BSc lions, 1994)

1. Discuss ia stiucture cfnaphthalcne.
that of naphihalene?
2, does the structure of diphenyl differfro m
l.Naphthol. (h) 2-Naphthol., and
3. Di...ss the structure of naphthalene. How will you convert it into (al (Gauhaii BSc Hans, 1993)
bthyI*IutiuiC
(c) 2.N i (Mogadh BSc Hoes, 1993)
4, How is naphthalenc obtained from coal-tar
(Maduroi BSc, 1994)
S. how will you synthesit naphthalene?
(Aligarh ASc lions, 1993)
6. Write a note on: Uawoit)i'ssYntheSiS of naphthalene
7. Write a note on Electroçthilic substitution in naphthaleiae.
the clecti'ophiilic substitution in naphthalene takes place at position I
K. How would you explain that (Karnataka BSc. 1994)
(Marathwdda BSc1993)
9. Why does chlorination of naphthalene talccs place at the cu-oositioo?
the cu-position. (Nagpur 1/Sc lii, 1994)
10. Explain Nitration of naplsthalene takes place exclusively in
11. Describe the reactions of naphthalene.
12. Complete the following reactions:
(a) Naphthalene + Conc. H 2S01 at 412°C —*
(Is) Naphthalene Conc. H 2SO4 at 160°C —s
(c) NaphilliaJefle + Na + CHsOU —a
(South Ga)oritl BSc, 1994)
13. What is Bucherer mactins 7 Give two differences between phenols and naphthols. (Delhi 1/Sc Hoes. 1991)

14. What happens when naphthalene is oxidised with chromic acid?
What happens when naphthalene vapours mixed with air is passed over heated vanadium pentoxide'
IS. (Armnamalult 1/Sc, )993)
(Mabus BSc, l993)
16. What is the product of oxidation of naphihalene with potassium permangaitale?
17. flow will you synthesise the following compounds from naphthalcne? .Naphthoic acid.
(d) 3.Naphthylalfline (e) fetralm (f)
(a) a.Naphthol (Is) -Naplsthol (c) ssNspbthylaflsine
(g) Pttthahic acid and (I) Ptithalimide
18. Discuss the structure of anthracenc. (Jwvtsnu .$c. 1993)
19. How is anthracene isolated from coal-tar?
20. Outline the method of preparation and properties of anthracenc
21. Describe the preparation, properties, and .ssnscture of anthracese (BwmdClkhwmd 1/Sc 1-foes. 1993)
22. Explain: lnanthracene, the 9.lQ-Positiom usually attacked ?
1206
23. How will you syntheslic the following compounds from anthroccoc?
(a) Alizarin and (b) Anthinquinone
24. How will you synthesise.
(a) Anthracene; and (is) 9-Mcthylanthraccne
(Saniba1prRScJ1t,,,1 994)
25. Discuss the SIn clure olpisenanthuene
26. Describe Haworths method Inc the sncflbcsis of ptsewusthzenc
(Kerala BSc Ii!. /994)
V. What is the product of oxidation oIpbenanth.rcnc by K2Cr2O7IH2SO4.
Chapter
47
Heterocyclic Compounds
Heterocyclic compounds are those cyclic compounds in which one or more of the ring
carbons arc replaced by another atom. The non-carbon atoms in such rings are referred to as
hetero atoms. The most common hetero atoms are nitrogen, oxygen and sulphur, but other
atoms such as boron, phosphorous, or silicon can also be members of heterocyclic rings
A number of substances which are heterocyclic compounds accoiding to the above

definition have already been discussed in earlier chapters e.g., ethylene oxide, succinic anhydride,
lactones, and cyclic carbohydrates. These compounds are readily formed from open-chafu
substances and are easily converted into open-chain derivatives. -The heterocyclic compounds
which we are about to consider here are much more stable and possess aromatic properties.
variety of such heterocyclic compounds of different ring sizes are known. In this chapter we will
restrict our study to the most important ones which are made of five .
and six-membered rings.
NOMENCLATURE
The simple heterocyclic compounds are called by well established

common 'Tames. How.
ever, the more complex rings which are not within the scope of this book are named more syste-
matically. The common names of some of the most important five , and six-membered hetero-
cyclic ring compounds are given below.
Five-Membered Rinks:
02
PYRCE PURAN TH/OPHEN( INOOLE
Six. Membeted Rings
.4 5 4 4
5
N
PYRIDINE
B Ni
©O 8 I
QUIWOL/NE 150QU1/vVLIN(
Notice that the rings containing nitrogen usually end with -ole if five-membered and with
-me if six-membered. The hetero atom is always numberd as I (isoquinoline is an exception),
and in such a way as to keep the substituent numbers as low as possible.
1201


l22
3.' UETHIZFL1R 28ROP40PYR10th'E
Thecarbon atoms next to the hetero atom are sometimes referred to as the
s-carbon
atoms and those further away as - and i-carbon atoms. This method is used only for naming
simple derivatives or to indicate the equivalence of positions.
CL Q
rHQPFENE P/RIO/NE bflWYLPYR10
FIVE-MEMBERED RINGS
PYRROLE, ()
It is an important five-membered heterocyclic compound because many naturally

occurring substances contain the pyrrole ring e.g., chlorophyll, hemoglobin and some of the
alkaloids. Fyrrole derives its name from the fact that its vapours produce a bright red colour
when brought in contact with a pine splint moistened with concentrated hydrochloric acid (Gr
pyrros, fiery+oleum, oil).
It urs in coal-tar and in bone oil (Dippel's oil). The latter is obtained by the
Pyrrole occ
dry distillation, or pyrolysis, of animal by-products such as horns, hooves, and bones. It may be
isolated from bone oil by first washing it with dilute sulphuric acid to remove the basic subs-
tances, and then with dilute alkali to remove the acidic substances. It is next subjected to frac-
tional distillation. The fraction passing over between 100°C. to 150°C contains pyrrole, which
may be removed by boiling with potassium hydroxide. The potassium salt is formed which on
steam distillation gives pyrrole. This is finally purified by distillation.
Preparation. Pyrrole may be obtained:
vy1in a mixture
H—c r 1
H—C C—H
NH, I.
- pyrrole
_&1Lc&gdjLZW'Q.. At this
N_ By heatingâmmonium mucate with
then undergoes dehydration,
decarboxylation, and rin-closU1e by reaction with ammonia.

Heterocyclic Compounds 1203
H\ /H t.k\ ,,H
C—c ......,. c—c,..,.--.
O4 G1YC(RC o/
\C, 2N3t H/ (\4 41420+2C0
C A ''C c"
OH HOóH H@cx:) 't° 9iP
AhfMONW7'I.UCATE ill VCIC ACID PVROL(
heating succinimide with zinc dust.
HC —CH2 H\C/H
I,
HO—C
\ —OH
2,-s+2Zo0
A
N2
N H
PYRROLE
-4
i/CCiW/M/E
(4) By warming succinic dialdehyde with ammonia.
7 \
H—c C—H
I /\ H
C—H
+Nk3 [) +
I
L
-
SCCINJC DIALDEHY01 I
PYRROE
(5) By passing a mixture of furan, ammonia, and steam over aluminium oxide caly('
at 480-490°C. (Commercial Method)
Cl +NH 3A
n+HZO
4 pyrrole
mi:.inYrroie the nitrogen atom and the four carbon atoms are sp1
hybridized. sp hybrid orbitals overlap with each other . and with s atomic orbitals of the
five hydrogen atoms forming C—C, C—N, C—H, and N—H a bonds as shown in Fig. 471. All
these a bonds lie in one plane.
Also each carbon atom and the nitrogen atom possesses an unhybridized p atomic orbi-
tal and these are perpendicular to the plane of the a bonds. The p orbitals on carbons contain
one electron each and the p orbital on nitrogen contains twpelcctton.s (.the -lone-pair). The lateral
ov p L tebitals p six çkctrons (F72
lit arrlTgnt1 titrequently referred to as an Aromatic Sextet.
aticit because the resultin g 7r molecular orbital sanMs. the ru c
'in 4n+2).
J•

Of
H
5ib-5/a80NO () ( s

- Formation of a bonds in pyrrole.
(JNHY8RID/Z0 -- -
)b-oRD/rAL $
C ñMO(ONTA/N4V6
6 ELECTPON5
H
Pt- H
ZO
Fig. 472. The unhybridizcd p orbitals in pyrrole overlap with each other to form a delocalized
a molecular orbital above and below the plane containing then bonds.
A common -shorthand representation of pyrrole is simply pentagon, a five-membered

ring, with a circle inside (Fig. 473). The circle represents the molecular orbital.
11 MOLECULAR
OR5(TAL
(DELOCAUMD)
Fig. 47-3. Simplified reprSefltaIi0fl of pyrrole,

• lS.&S V1Jr,VtI.rflafl.
,.ording to the resonance theory, pyrrole is considered to be hybrid of the following

canonical forms.,,
I
H
I
H
—
I
H
N
I
H
0 H
Notice that as a result of donation
rrole ring have gained ingIron.
(rhisenb1es pyrrole to participate in eictroptuhIc st1DstttUt1OT7eact15.-
"Iinent&b lengths by X-ray analysis confirms the hybrid character of the
pyrrole molecule. In particular, the C—N bond (138 A), which is shorter than a normal C—N
single bond (148 A), seems to possess significant double bond character.
Properties Physical). Pyrrole is cck' urless liquid, bp 131°C, which rapidly turns brown
on exposure to air. Its odour is like that u tiIoroform. Pyrrole is sparingly soluble in water
but dissolves in ethanol andher.
(Chemical). )1e-in chemical properties of pyrrole are described below.,
(I,) BsjQ-(haiicter. Pyrrole is a weak base (pK1 =3'4). It reacts with dilute' hydro-
chloric acki-t6 give a crystalline hydrochloride. This sdlt is stable in the absence of oxygen
- --- BROWN RESIN

4- HCI -
PYRROLE RESONANCE '

7
OEU.?CALISED • ENER6Y
L011
ci
LONE PAIR PYRROLE HYOR0004O (
&(CTRCN5 (NON- AROMATIC)
otherwise polymerisation rapidly occurs to produce a brown resin. The reason for the weak
basic character of pyrrole is that the lone pair of electrons on nitro
hiation o ize it molecular orbital and is not available or the formation of a new
bond with proton. Furthermore, if a proton is added to the nitrogen atom by reaction with
an acid, the resulting structure ceases to be aromatic and the resonance energy is lost. This
makes the pyrrole cation very unstable in comparison to the free pyrrole and indicates why
pyrrole is a weak base. Also, the pyrrole cation behaves as a typical conjugated diene and
undergoes po1ymejXlefl readily.
(2) sidtCharacter. Pyrrole is not only a weak base but also a very weak acid
(pK 1 =f5) This is shown by its reactions with solid potassium hydroxide and Grignard
reagents.
+
) + (
/
PYP.RV1POTA55'tm
()4- PMBr 10, + RH
Dr Mg
PYRRYLMANF/:/M n'OM(

1206
The reason for the acidic character of pyrrole is that

the electron pair detocalization
from nitrogen makes it
positively charged and increases the possibility of proton abstraction
giving pyrryl anion. Furthermore, the pyrryl anion is stabilized by delocalization of the nega-
tive charge over the ring. The resonance forms of pyrryl anion are given below.
_ —
(3) ectropbllk SuItftutloas. Pyrrole undergoes elecir. philic substitulion reactions
ii iii at C-2. This is understandable if we examine tk intermediate cation. Three
reson cc forms can be written for the intermediate obtained fi.m attack at C-2, whereas only
two such forms are possible for substitution at C-i. E+ in the following equations represents
an electrophile.
Attack at C-2
H
H
ZMØE .51
Attack at C-
rN (t,41-
LESS STABLE
Consequently the former intctrn jate is more ble and the product witb,i'substituent
at C-i predominates. Substitution at C3 only when both the 2 . poslions (that is,
and ') are blocked. The same reasoning is applicable for the electrophilic substitutions in
furan and thiophene.
Electrophilic substitution reactions of pyrwle arc not carried in the presence of strong
acids or reagents which give rise to : ug acids, because under such conditions pyrrole under-
goes polymerisation and resinilication.
(a) Nitration. Pyrrole can be nitrated by a cold solution of nitric acid in acetic anby.
dride to give 2-nitropyrrule.
O.
C
0.0
l
+ HNO5 + CH,—C—O---C—CH,
acetic anhydride
(&^
N
—NOI + 2CH5—C-0}1
0
H
2.nilropyrrole
MECHANiSM, The mechanism oL !his reaction involves the following three steps-
Step I . The electrophile NO, is generated

.0 0 0 0
II K I(P Il -+
- CH3 C0-C—CHI + HNO. CH,C-0N0 + CHs —C—OH
acctic tldddt acetyl nitrate

Hetocydllc Compãunds 1 701
Step 2. The electrophile attacks pyrrole at C2 to form the resonance-stabilised cation
H
NO2
N NO2 C IH A 0
w+cK c)(NO,
Step 3. A hydrogen ion is eliminated to yield 2.ieitropyrroie

0
1+
+ CH3—LOH
+ 0—C—CH3-----
N0
FROM 5T(P1
2-NTROPYRROL(
Similar sequences may be written for other eloctrophilic substitution reactions of pyrrole
(b) Sulpkonatlofl. Pyrrole may be sulphoriated with sulphur trioxide in pyridine at ah"it
100°C to yield pyrrole4-sulphonic acid.
pyridiw
Q+ - ao
H
pyrro1c.2.ulPh0fliC acid
Halogenation reactions of pyrrole proceed with great vigour and
(c) Hslogeiittioa.
require careful control of reaction conditions.
(1) Chlorination is carried out with suiphuryl chloride in ethe r at 0°C.
(ii) Bromination with bromine in ethanol at 0°C.
(ill) lodination with iodine in an aqueous solution of potassium iodide.
In each case the tetrahalogen derivative is obtained.
a C1
CO)
4 SS0202
5ULPIItJR)L
F THtR
-
(-1
0 CI
CHLORIDE H
H
2, 3,4,- r(rRAcJLogOPrnO((
+ 1 2 + K I Oct'
TURAQWME
2,3,45-Tetraiodopyrrole possesses antiseptic properties and is used in medicine under

the name (ado!.
A
(d) Frfrdel-Crafts Acylxiion. Pyrrole may be acetylated with acetic anhydride at 250°C
to give 2-acetylpyrrole. Notice that no catalyst is required in this reaction.
(0
+ CH,—C—O—C—CH,
Qoo
H
acetic anhydride
H
L —CHI + CH,—C—OH
2.acetylpyrrOle
(e) Kolbe-Schmitt Carboiylatlon. Pyrrole reacts with aqueous potassium carbonate
at 100°C to give pyrrole-2-carboxylic acid.
+ aq.K1CO1
H H
pyrrole.2.carbOXYllC acid
(f) Reimer-Tieinann Formylatlou. Pyrrole reacts with chloroform in the presence of

alkali to yield pyrrole-2-aldehyth. (2.formylpYrrole) and 3.chloropyfldine.
0 II
+ dHCl1 + aq.KOH
H
0
H +
3-chtoropyridlne
pyrrole.2-aldehlde
(2.fOrInylPYrrOtC)
Coupling. Pyrroic couples with benzehediazOflium chloride in a weakly

(g) Diazo
acidic solution to give 2.phenyiazopyrrolc.
+ i'a
+ ClNN_)
H
bcnzencdiazoniam chloride 2.phcnytazopyrro!C
(4) Oxidation. Pyrrole is ozidised by chromium trioxide in acetic acid to give the
imide of maleic acid,
Cr2O
+ 3[O] CH3COOH
H
MALE!C—/MlD
(5) Reduction. Mild reduction of pyrrole with zinc and acetic acid yields 3..pyrroline
(2,5 .dhythopyrrole). Catalytic reduction completely hydrogenates the ring system and pro-
duces pyrrolidine.

/••=\
Zn H2, Pt
(..) CH COOH (.) pss
H H H
3.P)ROL,NE PYRR0LF2Nf
(2,5 - 0/#4YDROPYMOLE)
(6) RIng Expansion Reaction. When treated with sodium methoxide and Methylene
iodide, pyrrole undergoes ring expansion forming pyridine.
+ 2Ci.i6a + cH1I, -+ + iai + 2C1'30H

sodium
metho*idc
H Pyridine
(7) Ring Opening Reaction. When treated with hot ethanolic hydroxylamine, pyrrole
undergoes ring opening forming the dioxime of succindialdehyde.
CH—CHI
/f \\ CHOH
. ./ + NH, OH -+ çH çH
hydrozylamine
I NOH NOH
k
succindialdoxime
FURAN AND ITS DERIVATIVES
FURAN,
Furan is the oxygen-containing counterpart of pyrrole. It occurs together with its

methyl homologues in wood-tar. Its vapours produce a green colour when brought in contact
with a pine splint moistened with concentrated hydrochloric acid.
Preparation. Furan may be obtained
(1) By dry-distillation of mucic acid and heating the product, furoic acid (furan-2.
carboxylic acid), at 200-300°C.
•H\
\H!
(cco) Qi°L;H
H'* OH _0H
FL! RU/C 4Ci0 FIIRAiV
/'fLIC/C ACID
(2) By oxidation of furfural with potassium dichromate to give furoic acid and subse.
queot decarboxylation at 200-300°C.
Ornic (hciiiistrv - 77

Ad v anced Organic Chemistry

1210
0
+101 + CO.
H0,/Fi+ K5Cr,
Ft/RAN
lurfuril furolc acid
By decarbonylation ot furfurat in steam in the presence of silver oxide catalyst.
(3)
(Commercial)
C_HsAgiO
-4 + Co
team
furfural - FL/RAN
(4) By dehydration of succinic dialdehyde by heating with P0 5 or ZnCla.
H2C—CH [ HC
\\ + HtO
/ C—H
/ \ H—C
H—C ,.C—H HO / _____

D/ENED10 FL/RAN
UCC/N/C O/ALDEPYDE
furan the oxygen atom and the four carbon atoms are sp' hybri
Structure of Fiwan. In
dized. The sp 2 hybrid orbitals overlap with each other and with s orbitals of four hydrogen atoms
bonds as shown in Fig. 474. Notice that se orbitat of
forming C—C, C—O, and C—H a
oxygen is completely filled. The electrons residing in this orbital make up one of the two
lone pair electrons of oxygen.
Also each carbon atom and the oxygen atom possesses an unhybridized p orbital and these
bonds. The p orbitals on carbons contain one
are perpendicular to the plane containing the a
electron each and p orbitals on oxygen contains an unshared pair of electrons (the other lone
six
pair). The lateral overlap of these p orbitals produces a n molecular orbital containing
electrons (Fig.47 5'). Furan shows aromatic properties because the resulting
is molecular orbital,
like pyrrole, also satisfies the Huckel's rule (n = tin 4n+2).
5p1 -5p 2 0 eowø
/H
OR
/\
5kb'- Sb'a- BOND COSMINING LLWC fr4J

Fig. 474 Formation of a bonds in furan.
Hezerocyclic Compounds
/211
UNHV5RIIZED
i'c —c1__z._1T MO CONTAINING

6 ELECTRONS
-. HC
LONE PAIR.
Fig. 47.5 Forrnaiun of ' molecular orbital in furan,
A common shorthand represe!?.,n of furan is simply pentagon with a circle inside

(Fig. 47-6). The circle repcsects the r molecular orbital.
IT MOL(C(/LAR
ORBITAL
eo
Fig. 476. Simplified representation of furan.
According to the resonance theor y , furan is considered to be hybrid of the following

canonical forms.
• c9 U P \
Measurement of bond lengths by X-ray analysis confirms the hybrid character of the
furanmolecule. In particular, the C—O bond (137 A), which is shorter than a normal C—O
single bond (143 A), possesses significant double bond character.
Properties. (Physical). Furan is a colourless liquid, bp 32CC, with a chloroform

like smelt. It is only slightly soluble in water, but dissolves in most '.acic solvents.
(Chemical). Some of the important chemical reactions of furan are
(I) Basic Character. Furan, like pyrrole, is a wek'b!e. It forms unstable salts with
mineral acids. These salts may either polymerize to produce a bre--i resin or undergo bydroly.
sis to yield succindialdehyde.
Advanced 0goriic Chemistry
12)2
02 -
-- BROWN RESIN
[LVMER1SA TION
+ HCI
FL/RAN HICI
C—CI
FL/RAN I.IvDROC1tORfDE
0c ' c=0
H /
(2) Electrophilic SubstitutlotW Furan, like pyrrole, undergoes electrophilic substitution

reactions mainly at C-2. Substitution at C-3 occurs only when both of the 2-positions (that is,
aic aise.sd> blocked.
L.c.LipI, substitution reactions of furari are not carried in the presence of strong
acids, because under such conditions it undergoes polyrnerisatiOn.
nitrated with a hot so!utionof nitric acid in acetic anhy-
(a) Nitration. Furan can be -
dride to torm 2-nitrofuran.
NOg + 2CH3—C—OH
HNO3 + CH_1-1_O_C—CH3
acetic anhydride °
2-nitrofuran
Suiphonation- Furan may be suiphonated by sulphur trioxide in pyridine at 70 0C to
(b)
Yield furan-2-sulphonic acid.
pyridine
© + so, SO5H
70•
furan-2-sulphonic acid
Halogenatioli. Furan reacts vigorously with chlorine and bromine at room tempera-
(c)
ture to give polyhalogenated products but does not react at all with iodine. Much milder
conditions have to be Used to obtain manochioro or rnonobromo derivatives.
Cl Br1, dioxaji
+ L__CI 4—
—40' OQ— 0'
Bf
2,5-dicblorofuraa 2-'omofuran
-chIorofuran
Fr1edel-r*fts Acylatlon. Furan can be acetylated with acetic anyhy.ride in th
(d) 00 to yield 2-acety1fufri.
pesence of BF 3 (or SnCI4) at
0 0 0 0
II BP II
+ CH2_C-0—C—CH —p —CH1 + CH,- C—OH
0
acetic anhydride 2-acety1furan

(c) Mercuratlon. Furan undergoes mercuration on heating with mercuric chloride in
aqueous sodium icetate to yield 2-chloromercurifUran.

+ HgC
CH1COOt
a Q
HgCl
2-chloronwzcurifuran
2-Chloromercurifuran is useful in synthesis, because the Iflercuri-group is readily replaced
by iodine or bromine and by an acyl group, -
2-Chloromercurifurer 2-I060uror,
+ C3 — l! — C
Cd'^_Hqc:
A etyl chloride
2-Acetylfurn
(1) Reaction with n.Butyl .Iithiuui. Furan reacts with n-butyl-lithium in ether to give
2-furan-lithium.
efher
+ CH3CHCH1CH, Li 1_Li + CHICHICH,CH3
2-furio-lithium
2-Furan-lithium undergoes many of the usual reactions of organolithium compounds. For
example, it combines with carbon dioxide to form furoic acid (furan-2 .carboxylic dCid
Q
a C_OH
0.
2 . furan-lithiurn furoic acid

(g) Dlao Coupling. Furan is not sufficiently eacl,vc to couple with bntc,,tdirwnium
chloride.
(3) Reduction, Furan is reduced by hydrogen Jrt the prcsQne omckel j,r. produce
tetrahydrofuran
Q+L Q
(4) Ring-opening Reaction. When t y eated Wt%h mrthn d oythichlo'ric icid, furan
undergoes ring-opening forming the diagetal of suc,nd*kJthyd
C —
( ) + CH3 01f + MCI —p CH CH
(OCR,), (OCH,),
diacetat of succindiaIde1yde

11' Advanced Organic Chemistry
Hydrolysis of furan with dilute hydrochloric acid also leads to ring-opening

(5) Reaction with Maleic Anhydride (Diels-Alder Reaction). Furan has sufficient diene
character to undergo Diels-Alder reaction with maleic anhyride to form an addition product.
The addition occurs across C-2 and C-S. Pyrrole and thiophene do not give this reaction
o 0
H it II
C
C
FQRAN -4 ii - it
o 0
MAL VC OIEL5-ALDER ADDUCT
MI
Use. Furan is used in the manufacture of tetraJydrofuran.
FURFURAL, Furun-2-aldehyde, 2-Fornry1furan, ç)_C_H
Furfural is the most important derivative of furan. It derives its name from the fact that
it was first obtained by boiling bran with dilute acid (L., Furfur, bran). Furfural produces a
green colour when brought in contact with a pine splint moistened with concentrated hydrochlo-
ric acid. It also produces an intense red colour when heated with aniline and acetic acid.
The group, —CH 3O e.g., , is called fury!.
Preparation. Furfural is obtained commercially by the acid catalysed dehydration of pen-

kises, I c-..1kUuh gs1s, i:d as polymers in oat hulls, corn cobs, bran, and straw, Oat
ikullb jivr LILV LtIgIei cd.
___ /H
C10H':
()__ H ± 3H0
r1-
furfural
H OH
/ \10N
., PENTO5E
Furfural is a colourless oil with a pleasant characteristic odour,
Properties. (Physical).
bp I62C. It is only slightly soluble in water, but it is rn,scible with most organic solvents.
Furan is oxidised by air, the colour changing through shades of yellow and brown to almost
black. These changes can be prevented by storing in the absence of oxygen or by adding ant i-
oxidant like hydroquinofle.
(Chemical). Furfural closely resembles benzaldehydc in cheinic?l behaviour. It
undergoes clectrophilic substitution at the other available 2 (or ) position, that is, at C-S.
Furfural is much more stable than furan towards acidic reagents.
Some of the important reactions of furfural are described below.
(I) Nitration Furfural can be nitrated by a cold solution of nitric acid in acetic anhy-
dnide to yield 5-nitrofurfural.

ii' 5
0 0 0
I
H
QCD_H + HNO 3 ± CH 3—C--0—C---CH1 -
a
acetic anhydride
futfural 5-nitrofurfural
0
+ 2CH,—C—OH
(2) Brotwination. Furfural reacts with bromine in dichioromethane (methylene chloride)

to give 5-brornofurfural.
+ Br1 CHIC],
5.bromorurfurat
(3) Grign&rd Addition. The Grignard reagents add to the carbonyl group of furfural
to form a product which on hydrolysis yields secondary alcohols. For example, with methyl-
magnesium bromide, 2-furylmethylcarbinol is obtained.
H/H2O
CH 3 CK
ADDUCT 2 FUR YLMETHVL CAR8JN01
(4) Bisulphite Addition. Sodium bisuiphite adds to the carbonyl group of furfural to
form a bisuiphite addition product.
0 OH
+ NaHS0 ----
bisulphite SO1Na
a bisuiphule
addition product
(5) Reaction with Hydroxylainiee. Furfural condenses with hydroxylamine to form an

oxime.
o
LO + H IN—OH
hydroxylaminc
QLN—OH
a
0
osime of furfural
(6) Reaction with Acetone (Claisen-Schmidt Condensation). Furfural condenses with
acetone in the presence of a base to give furylidene acetone.
} 0___ H 0
ji NaOH . I ii
C=0 + H 1C—C—CH I - _, C=C—C—CH, + H10
acetone
furylidene acetone
(7) Reaction with etbanolic Potassium Cyanide. Furfural undergoes benzoin type conden-
sation with ethanolic potassium cyanide to form furoin.

11
Q
C_0 1
KCN
'' OH
C .' + I cyt
C2H5OH \/-

FIJRFURAL FLIRO IN
(2 MOLE.S)
(8) Reaction with Sodium Hydroxide (Cannirzaro Reaction). Furfual undergoes self-
oxidation and reduction with aqueous sodium hydroxide to yield a mixture of furfuryl alcohol
and sodium salt of furoic acid.
4.
21 —c_H + NaOH a
QCHOH QC
+ a 1L 6Na
furfuryl alcohol sodium furoate

(9) Oxidation. Furfural may be oxidised by silver oxide or dilute potassium perman-
ganate to give furoic acid. When a stronger oxidising agent like potassium chlorate is used,
furfural undergoes ring opening, forming furnaric acid.
H \ /COOH
5L. {J).__OH
HOOC "H +101
fumaric acid ' furoic acid
(10) Reduction. Furfural may be reduced with (I) hydrogen and CuO-CrO, to give
furfuryl alcohol; and (ii) hydrogen and nickel to form tetrahydrofurfuryl alcohol. Notice that
in the first reaction only the carbonyl gTccp is hydrogenated, but in the second . case both ring
and the carbonyl group are reduced.
()—CHOH -
Ni, A
L ----
CuO—Cr103
k)- CHOH
tetrahydrofurfuryl alcohol F U4N fuduryl alcohol
Uses. Furfural is used : (I) as a wash in poultry houses to kill lice; (2) as a solvent for
refining lubricating oils, and for removing butadiene from its mixture with bulenes and butane;
(3) in the manufacture of resins (phenol-furfural resins) of the Bakelite t y pe; (4) as a solvent for
cellulose esters; (5) as a paint remover; and (6) in the production of furan and many of its
derivatives.
TETRAHYDROFURAN,
Tetrahydrofuran is another important derivative of furan. It is a saturated cyclic ether

and is commonly designated as THE It does not occur in nature.
Preparation. Tetrahydrofuran may be obtained

(I) By catalytic hydrogenation of furan.
(2) By acid catalysed dehydration of I, 4-butanediol. (Commercial)

/H:—c
HPO4
HA CH, - + H10
tctrahydrofijran
I 4-butanediol
1,4-Butanediol used in this reaction is obtained by the condensation of acetylene with

formaldehyde to form 2-but y ne-1,4-diol. This on hydrogenation in the presence of a catalyst
yields 1,4-butanediol,
H 0 CFJOH MOH
I I
C
C II ± 2H—C--H I
-p
H,
Ni,A
cH
I
H L,OH CH1OH
acetylene 2-butyne-I,4-diol I 4-butancdiol
(3) By treatment of 4-chiorobutanol with water. In the presence of water 4-chloro-

butanol undergoes intramolecular S N 2 reaction with ring closure to yield teterahydrofuran.
H 2 — CH 2 C.H—C2
/
H 2 C
N
\
,Cd21—Ci '
'__
. HC

CH2
__
lop
0
TE1RAHYDRQFU4N
4 -CWLORO8iJTANO
Properties. Tetrahodrofuran is a poisonous volatile liquid, bp 66°C. It is miscible with

both water and most organic solvents. Some of its important reactions are given below
(I) Hydrolysis. Tetrahydrofuran undergoes hydrolysis in the presence of dilute sul-

phuric acid to yield 1,4-butanediol.
I
+ H2 O — HO—(CHI),—OH
p
1,4-butanediol
tetrahydrofuran
(2) Reictien with Hydrogen Suiphide. Tetrahydrofuran reacts with h ydrogen sulphid
in the presence of aluminium oxide at 300° to give teirahydrothiopherte
.4,5t982
Advanced C1 ranc Chemistry
r2 Is
Q M1
- HO
ceirahydrothiophene
t3) Reaction with Ammonia. Tetrahydrofuran reacts with ammonia at 300°C to form
let riihydropyrrole.
•j. NH1 + 2 H2O

()
tetjahydropvrolc
(pyrrolidinc)
hydrochloric acid to
(4) Reaction with Hydrochloric Acid Tetrahydrofran reacts with
give 4•chlorobutanol (tetramerhylene chiorohydrin). When the reaction is carried out in the
presence of ZnCI 1 , 1,4-dichiorobutane is obtained.
"Cl HCI
)
CI—(CH 1 5—OH *- -.. Cl -(CH,) 4—CI + H20
4.chlorot'uiaflOI ZQCI1 I 4-dichiorobutanc
Uses, Tetrahydrofuran is used : (I) as a solvent in the preparation of Grignard

reagents and its reactions; and (2) in the manufacture nylon 6-6 and 1,3butadiene.
COMMERCIAL CONVERSION OF TETRAFJYHROFURAN INTO NYLON 6-6
This involves the following five steps.
Step I. Tetrahydrofurall is treated with HCI in the presence of Zn0 1 to form
(I)
4-dichlorobutanc.
+ HCI -
I ,4-dichlorobutane
Step 2. 1,4-Dichlorobutane is heated with potassium cyanide to give adiponitrile.
Cl—(CH,),--Cl + KCN - NC—(CHI),—CN

I, 4-diChlOrObUt&flO adiponitrite
The adiponitrile so obtained is divided into t wo portions.
.\tt'p 1. One portion of adiponitrite is reduced in the presence of a catalyst to form
1.6.diiminohexafle (hexamethyleliediarnirie).
Ni
NC_(CH)_C=N + H 1 -p
adiponiirile I, 6.diaminohexaoe
.
Step 4. The other portion of adiponitrile is hydrolysed in the presence of an acid cata
lyst to give adipic acid.
0 0
NC_(CH,',.—CN + H 1 0 - HO—C—(CHn)t-C—OH
adiponitrilc adipic acid
j '9
Step 5. Adipic acid and 1,6-dianuftohexane are finally condensed at 280°C to yield
Nylon 6-6.
0 9
H0_C_-4CH 3 )-t-0H + HN-(CH-NH
adipic acid I, 6-diaminohcxaiie
0 0
LNH-(CI1,),-NH-C--(CH1)4-C---
[
This variety of nylon is known as Nylon 6-6, be-,iust diamine and the dicarhoxylic acid
contain SLt carbons each.
THIOPHENE, Thiophen, \/
Thiophene is the sulphur containing counterpart of loran. It occurs in the light oil frac-
tion of coat-tar and is usually present as an impurit y in commercial benzene. The boiling points
of thiophene and bcnzeiie are so cloc together that they cannot be separated by distilixtion.
Thiophene may be separated from benzene by shaking the mixture with cold .oncen-
trated sulphuric acid. Thiophenc reacts to form thiophene-2-sulphonic acid, which is soluble
in sulphuric acid. It can also be removed by refluxing the mixture with mercuric acetate which
niercurates thiophene with much greater ease. Thiophene can be regenerated from the organo-
mercury compound by heating with hydrochloric acid. The best method of renlosing thiophene
from ben7ene is by shaking with Raney nickel.
Thiophene gives a blue-green colour when it is added to a solution of isatin in sulphuric

acid.
Preparation. Thiophene may be obtained
(1) By passing a mixture of acetylene and hydrogen sulphide tirough a tube containing
aluminium oxide at 400°C.
H-C C-H AIOa

- Iii III 2 H,
ri-C C-H A S
S
H / "H thiophenc
(2) By heating sodium succinate with phosphorous trisulplside.
CH-- 042
+- / \ i.
P.S3
N.sO—C C—ONa + 2Na}'O,S + S

ihiophne
SODIUM .50CC/NATE

1;20 Advanced Orgaric Chemistry
(3) By distillation of furoic acid with barium sulphide.
dwii
a
Q "ROH ± BaS -+ () + BaCO3
furoic add thiophene
(4) By reaction of sulphur with ri-butane in the gas phase at 650'C. (Commercial)
H IC—CH 650'
± 4S n - 3HIS
H 5C CH,
n.butane
thiophcne
Structure of Thiopliene. The structure of thiophene is similar to that of furan. It

•s considered to be resonance hybrid of the following canonical forms,
9
and can be represented simply by a pentagon with a circle inside. The circle represents the
molecular orbital containing six electrons (Aromatic Sextet).
17 MOLECV1A
7 ORBITAL
Properties (Ph ysical). Thiophene is a colourless liquid, bp 84'C, with an odour very
similar to that of benzene. It is insoluble in water, but miscible with most organic solvents.
(Chemica'). Thiophene does not show any basic properties. It is much more stable
to acids than either pyrrote or furan. Thiophene does not undergo the Diels-Alder reaction.
lowever, some of its important reactions are described below.
(I) Electrophilic Substitutions. Thiophene, like furan and pyrrole, undergoes electro.
philic substitution reactions primarily at C.2. Substitution at C-3 occurs only when both of the
2-positions (that is, s and a) are already occupied.
(a) Nitration, Thiophencan be nitrated by solution of nitric acid in acetic anhydride to

yield 2-nitrothiophene.
r HNO3 ± CH,CO—C—CK, -. + 2C4—C-OH

S
.njothjophe
(b) Suiphonation. Thiophene undergoes suiphonation with concentrated ' uhtric acid
to give thiophene-2-sulphonic acid.

QO + H1SO4 - LSO3H
thiophene.2 .sulphonic acid
(c) Hlogenation. Thiophene reacts vigorously with chlorine and bromine at room
temperature to give polyhalogenated products but does not react at all with iodine. Much milder
conditions have to be used to obtain monosubstituted derivatives.
—30
Chlorination : + SO,C1 1 -.--. Cl
$ ihionyl s
chloride
2_chlorothiopheflc
Brominalio;,
–0 + N—Br
0_ Br + N—F4
THIQPNEN( N-8ROA&7iL/CC/NIMID( 2-BgoIworH/OPHfNE SUCChWM/DE
lodination O
Q+ II HSO P aQI
2-iodothiopliene
(d) Friedel-Crafts Acylatlon. Thiophene may be acetylated with acetic anhydride in the
presence of phosphoric acid, or with acetyl chloride in the presence of SnCI 4 to yield 2-acetyl-
thiophene.
CP + CH,—C—O—C—CH I -..
acelic anhydride
HPO
S
2-acetylthiophene
-f C111—C–OH
acetic acid
(e) Odoromethylation. Thiophenc reacts with formaldehyde and hydrochloric acid to

give 2-chloromethylthiophene.
+ H—C--H + HCI -p
formaldehyde u,(Q CHCl + H10
2-chi i eth; hinpi

Mercustloo. Thiophene undergoes mercura ion with mercuric "orid aqueous
(f)
sodium acetate to produce 2-chloromercurithiophene.
OQ S
+ H 90 1
CHaCOONa
(\ >--HgC
S
2.chloromc OptiCi'

Adancd Orgcnc Ciertistr

(222
(g) Reaction with n-Butyl-llthium. Thiophene reacts with n-butyl-lithium to yield the
2-lithium derivative
ether
gCO + CH3CFICHCH2Li
n-bityl -Iii hwrn
j—Li + CH3C}{ICU1CF{
n-butane
2.thiophene-tithium
2-Thiophene.lithium can he used to prepare various 2-substituted thiophenes. For

example, it reacts with carbon dioxide to form thiophene-2.carboxylic acid
Li I4-OH
2-thiophene-lithium Lhiophenc-2-carboxylic acid
(h) Diazo Coupling. Thiophene does not react with benzenediazoniUtfl chloride.
(2) Reduction. Thiophene may be hydrogeifated by means of sodium amalgam and
ethanol to tetrahydrothiophene.
CAM
tetrahydeothiophene
General Methods for Preparing Five-membered Heterocyclic Compounds
Five-membered heterocyclic compounds may be obtained from I 4-diketones by ring

closure. For example, 25-dimethyl derivatives of pyrrole, furan, and thiophene may be
obtained from 2,5-hexanedione as shown below.
NH ), CO,
HC CHj
H
, 5-OIMF/HV1PY0L(
H 3 C- NC_C t 1
/ CH,
/
CH—\f_CHJ
\ 25
'b
H
OH OH 2,5 -DIME THYI. F/A N

2 5- I4EXAMEDIONE
DIENEDIOL E
(ACETONYLACE TONE) (L'N5 TAB LE)
2,5/METKYLTHI-bVE

1223
INDOLE AND ITS DERIVATIVES
INDOLE a, .BenzoproIe,
Indole consists of a benzene ring fused to the oc, positions of a pyrrole ring. It derives
its name from the fact that it was first obtained by distilling oxindok, a degradation product
of indigo, with zinc dust. Indole occurs in coal-tar and in the oils of jasmine and orange
blossoms. It is also found as a part of the total structure of a number of alkaloids and amino
acids e.g, serotonin, reserpine, and tryptophan. Indole, like pyrrole, produces red colour
with a pine splint moistened with concentrated hydrochloric acid.
Preparation. Indole may be obtained
(1) By the Li;p Synthesis. In this method o-amino-w-chlorostyrer is heated with sodium
ethoxide at l60-170°C,
CH
+ C2HsOH + NaCI
HHO+NOCH6
- - - ----
H S.--...
INDOt.E
O•AM/NO-tJ -ci/wRosrvRrne
(2) By the Fischer Indole S ynthesis. In this method pyruvic acid is first treated with
phenylhydrazine to form the corresponding phenylhydrazone, The hydrazone is heated with
anhydrous zinc chloride or polyphosphoric acid (H1 P05 + P2 05) to give indole-2-carboxylic
acid which on decarboxylation yields indole.
p4 3C 0
©:?
J02
+C20
© II
a t4-NH2 cl^ (,:-0,,
PH(A/YHVDRAZI01E PYRL/V/C A PHEtVV18 ygA70Nf IND&E-Z-CARBOXYUC INDOLE

ACID ACID
(3) By she R1ssert Synthesis. In this method o-nitrotoluenc is condensed with

diethyl oxalate in the presence of a basç to form a 2-keto-ester. This is then reduced with zinc
and glacial acetic acid to give indole-2-carboxylic acid which on decarboxylation gives indole.
CHI 0 0 CHaCC005H&
D
1 C 2HON Zn
± C5HSO—C—C-0C.2H -
diethyl oxalate CH5COOH
05
o-n,trotoluenc 2-keto-ester

1224 Advanced Orginic Chemistry
0
II
• © ':0H -'
iodole-2-carboxylic aLid
Indole
(4)
From o-Tohiidine. This involves treatment of o-toluidine with formic acid to form
N-formyl.o.toluidine. This undergoes dehydration on heating with potassium t-butoxide to yield
indole.
0 CH, CHa
IIt-C4H,0K+
+ C—H -+0
@( .._ II , H10
@^
N—H H
H
formic acid
ololuidine

H20) NH- C — H
Y-formyl-o-ioluidinc indole
(5) From o..Nitropheny/acetaidehyde, This involves reductionof o-nitrophenylacetalde

hyde with iron powder and sodium bjsulpbite to give o-aminophenylacetaldehyde which cyclises
spontaneously to yield indole.
o 0
II It
He—C—H CH,—C—H
ro–'Ir — . g, —
o.nitrophenylacetaldehydc o.aminophenylaceialdehyde indole

(6) From trans-Indigo This involves oxidation of trans-indigo with potassium permang-
anate to form isatin. Isatin on reduction with zinc and glacial acetic acid first gives dioxindole
and finally oxindole. This is next distilled with zinc dust to give indole.
H 0
f II
awC=<::::©3 ©(\c=o (PlriO4
N'"
CHiCOOH ao.. ,
KOH
I II
H 0 H
TRAN.S - INDIGO / A TIN D/OXINDOLE
U
CH
Zn
CHjCOOH
=o p ©f 0H -
H H
OXINOOU INDOLE
Het.r.qcuc Coi'itotv,ds 122S
2
Stritctureor Idole. Like pyrrole, all ring atoms in indole (eight carbons-f-one nitrogen)
are a hybridized. The sp hybrid orbitals overlap with each other and with s orbitals of
hydrogens to form C--C, C—N, C—H, and N—H a bonds. Each ring atom also possesses a p
orbital and these are perpendicular to thE plane containing the a bonds. The p orbitals on
carbons contain on electron each and the p orbital on nitrogen contains two electrons (the lone
pair). The lateral overlap of these p orbitals produces a it molecular orbitial containing Zen
electrons. Indok shows aromatic properties because the resulting n molecular orbital satisfies the
Huckel's rule (n=2 in 4n+2).
Indole is considered to be hybrid of several canoaical lrms, some of which are shown
below.
::
3Q-(::ON ek
C
Properties (Physical). Indole is a colourless, volatile solid, mp 52 C. It is sparingly soluble
in cold water, but dissolves in hot water and most organic solvents. Endole has a powerful
odour which is pleasant and flowery in low concentrations. It is, in fact, used commercially
as a perfume base. In contrast, indole and its 3-methyl derivative (Skalole) are responsible for
the strong offensive odour of faeces.
(Chemical) Some of the important reactions of indole are given below:
(I) Bask and Acidic Character Like pyrrole, indole is a weak base and also a weak
acid. It is polymerised by strong acids and reacts with potassium hydroxide and Grignard
reagents.
.
(2) Electropilic Substitutions. Unlike pyrrole, indole undergoes electrophilic substitu-
.
tion at C 3. This is because two resonance forms can be written for intermediate cation obtained
from attack at C 3 (without disturbing the benzene ring), whereas only one such form is
possible for ubstiLution at C-2.
Attack at C.3
WE WE
'WORE STA$LE 3-5U1S7i TUTION
PRO,O6CT
Altuek at C.2
-W +
-
1tJ-E
H

LESS STABLE
Consetiucntly the former intermediate is time stable

P Qp VC 7
2-sti8STITtiI/O/V
C3 predominates. Substitution t C.2 eccurs onlyand the product with a subetitu-'

when the 3-position is alread
Organic ( liernistry - 78
1226 Adyanced Organic Chemistry
(a) Nlfritloa. Indole may be nitrated at low temperature with ethyl nitrate in the
presence of sodium ethoxide to yield 3-nitroindole.
QINOI
g
IijI[I) +
ethyl nitrate
C1$64a
5'
H H
3-nilroindote
(b) Sulpbonallon. Indole undergoes suiphonalion with sulphur trioxide in pyridine at
110°C to give indole-3.sulphonic acid,
I
pyrldl,,e
-F- SO,
H
indole-3-sulpbonic acid
(c) Bronilnatlan. Indole can be brominated with bromine in dioxan at 0°C to form
-bromoindole.
Br
dioxan
H
3-bromolndae
(d) FrItilel-CmRs Acylitien, Indole may be acetylated with acetyl chloride in the
resence of SnCl to yield 3-acetylindole.
0
C—CH,
SriCl4
©IJ H
+ CH1-C---.CI
acetyl chloride
o
H
3-acetylindole
(e) Alkylation. Indole reacts with methyl iodide in dimethyl suiphoxide (DM1) at about
0°C to give 3-methylindole (skatole).
DMF
+ 5I CHWH,
3-methylindole
(f) Reimer-Tiemann Formylatlon. Indole reacts with chloroform in the presence of
alkali to yield indole-3-aldehyde (3-formylindole) and 3-chioroquinoline.
0
IJIJ + CHCII -+
NaOH
indole.3-aHehyde 3-chloroquinoliic

Heterocyclic Compounds tv
(g) Diazo Coupling. Indole couples with benzenediazonium chloride in a weakly acidic
solution to yield 3.phenylazoindole.
N=N.q'
+ ClN- + HCI
-+
I benzenediawnium

H Chloride H
3•pheiiylazoindiolc
(h) Mannich Reaction. Indole undergoes Mannich reaction with formaldehyde and
dimethylawine to give 3dimethylaminomethylindole (Gramine).
.—+ 1çJ/cRIN(dH)I
+ H-C-H + (CH3)NH
©c° formaldehyde dimetbylamine
N
H
3403etllylamioomeThylindole
(Zramlne)
Gramine also occurs naturally in sprouting barley.
(3) Oxidation. Indole may be oxidised by ozone in formajnjde to give 2-formamido.
benzaldehyde. Notice that this product is obtained by cleavage of the 23-bond in
indole.
H
H
+ o
H_L111
TO- C=0
H
H"
2-forznainldobeozaldehyde
(4) Reduction, Mild reduction of indole with zinc (or tin) and hydrochloric acid yields
2,3 .dihydroindole (Indolirse). Catalytic reduction hydrogenates both rings and produces ocata-
hydroindole.
0 So
Ha 250'
2,3-dihydroindole octahydroindole
tndaxyl. It is an unstable yellow solid, mp 85°C, which is isomeric with 3-hydroxyindole.
WON
H H
INOX YL. 3-HYDR0XV1ND0LF

Indoxyl gives a red colour with ferric chloride and is ressnified by concentrated
hydrochloric acid. It is easily oxidised in alkaline solution by air (autoxidation) to give the
dyestuff indigo. Indoxyl gives indole on distillation with zinc dust.
Oxindole. It is a colourless solid, mp 126-7°C. Oxiodole may be obtained from aniline
and chloroacetyl chloride as shown below.
0 CH 20
Mci3©ç_
1T2d1

AN!L'NE CHLOROACETYL OXINDOLE
C/-II..ORIDE
Dloxindole. It is a colourless solid, mp 180°C, which is tautomeric with 2,3-dihydro.
xyindolc.
OH
OH
DIOX/NDOLE 2,3-DIHY0R0XY1ND04E
(3-HYDRoxvoxINOoLE)
Dioxindole can be obtained by reducing isatin with zinc and hydrochloric acid.
Zn
o
0
HCI
H H
15A TIN
Isatin. It was first obtained by the oxidation with nitric acid. Today isalin is prepared
from aniline by the following two steps.
Step 1. Treatment of solution of aniline in concentrated hydrochloric acid with chlorLj
hydrate and hydroxylamine, produces crystals of oxirninoacetanilide.
©
CH=NOH
HC!
+ CCI3C(OH)1 + NH1OH -,
chloral hydrate hydroxy-
Nfl1 Iammc
WHO
ozimtanitide
Step 2. Treatment oximinoacetanilide crystals with sulphuric acid yields isatin by ring
closure.
H=NO+i l'12504
(D'.'I
H20
0
rcô
14
15 AT/N

Hetocyc1Ic Compounils 1229
Isatin is a red crystalline solid nip 200-201C. It is sparingly soluble in water, but dis-
solves in ethanol. Isatin reacts with phosphorous pentachioride to form isatin chloride, and
with sodium hydroxide to yield isatinic acid as sodium salt.
00
II II _+
CC-ONa
NaOH
0. WARM
(a NH2
CZ H
lcl ^ H
SODIUM SALT OF I5ATIN ISATIN CHLORIDE
ISATINIC ACID
\I,Q ju.i s thninost

SIX-MEMBERED RINGS
imp^d
the heteroc clic nfl systemlt occurs.along with
pyrrole in bone oil and in the ligh ofcoaar.-lt can be isolated
from the latter by tttingit wi ilute
stil removes pyridine and other
bases in the acid la jer as e su p ates. The acid layer is then treated with sodium hydroxide
when a dark brown liquid separates. Pyridine is obtained from this oily liquid by fractional
distillation.
Preparstion, Pyridine may be obtained
(1) By passing a mixture of acetylene and hydrogen cyanide through a red-hot tube.
-
1)
r. Y
R"i
(2) By dehydroenation of pipenidine with concentrated sulphuric acid at 300°C or with

nitrobenzene at 260°C.
) Conc. H9SO4
+3Hz
N
pyridine
pipeildioc
(3) By heating pyrrole with dichtoromethane in the presence of sodium ethoxide.
+ ci1a5 + 2C1H56a + 2N,CI + 2C1H10H

() N
1230 Advancei Organic Chemisty
(4) From .Plcoline (3-Me:hylpyrldL',e). This involves oxidation of -picoIine with

potassium dichromate and sulphuric acid to give nicotinic acid (pyridine-3-carboxylic acid).
Nicotinic acid on decarboxylation with calcium oxide yields pyridine.
(),,CH 11 4. C—OH
KCrO,/H
+

-plcolie nicotinic acid pyridine

(5) By beating glutaconic aldehyde with ammonia.
ZN +NH,
+ 211,0
HC CH A
HC \ CH
" O HO"
o Pyridine
GLUTACONIC
ALDEHYDE
(6) By heating tetrahydrofurfuryl alcohol with ammonia in the presence of aluminium

oxide at 500°C. (Commercial Method)
()- AI305
CHOH + NH3 -4. I + 2H10 + 2H,
A
erahydrofurfuryl alcohol pyridine

(7) By reaction of acetylene with ammonia and formaldehyde dimethylacetal in the
presence of aluminium oxide at 500°C. (Commercial Method)
CH(OCH1)1
H—C C—H M03

+ III ---+
H—C C—H N
NH3
Pyridine
Structure of Pyridine. In pyridine all ring atoms (five carbons + one nitrogen), are spt
hybridized. Two of the sp orbitals on each atom overlap with each other to form the C—C
and C—N a bonds. The third sp2 orbital on each carbon atom overlaps with an s orbital
from hydrogen to form the C—H a bonds ; the third sp5 orbital on nitrogen is occupied
by the nitrogen lone pair electrons (Fig, 477). AU a bonds in pyridine lie in one plane and
all bond angles are approximately equal to 120°C.
Also each ring atom in pyridine possesses an unhybridized p orbital (containing one
electron) and these are perpendicular to the plane containing the a bonds. The lateral overlap
of the p orbitals produces a delocalired n molecular orbital containing six electrons (Aromatic
Sextet). One half of this n molecular orbital lies above and the other half below the plane of a
bonds (Fig. 47-8). Pyridine shows some aromatic properties because the resulting molecular
orbital satisfies the Huckels rule (n=1 in 4n+2).
*terocycIJc Compounds 1231
SA.5 Or BONO
s/,2r8ONo
OR EMU
7RITAL
I/N/MG
3L
PAIR
Pig. 477. Formation of a bonds in pyridine.

71 MO CON MINING
- ELEC7RONS
- 0R81741S
H^ , ------ i__ _/ H
Pig. 471. The unhybridized p orbitals in pyridine overlap with each other
to form a deloealieed n molecular orbital above and below the plane of o
bonds. The nitrogen lone pair electrons being in rp t hybrid orbital do not
interact with x molecular orbital.
A common shorthanu presentation of pyridine is simply hexagon, a six-membered
ring, with a circle inside (Fig. 479). The circle again represents the n molecular orbital.
K MOLECULAR
QA 8/TA L
CONTAINING
SIX EL (C TRONJ
d
Fig. 479. Simplified representation of pyridioe
According to the resonance theory, pyridine is considered to be hybrid of the following
five contributing structures.
Measurement of bond lengths by X-ray analysis confirms thehybrid nature of the

pyridine molecule. The C—C and C—N bond lengths of 139 A and l37 A are intermediate
between those corresponding to a single and a double bond.
Properties (Physical). Pyridine is a colourless liquid, bp I l5C°. It has a very characteristic
pungent and disgusting odour. Pyridine is miscible with water and most organic solvents. it
is very hygroscopic. Pyridine reacts with sodium and so should be dried over solid potassium
hydroxide or barium oxide. The presence of water in pyridine can be detected easily by
adding pure benzoyl chloride. If water is present, a precipitate of beazoic anhydride will be
formed immediately.
Almost all classes of organic compounds are soluble in pyridine, even many of the
high melting solids which scarcely dissolve in solvents such as ethanol and benzene. It is conse-
quently used as a solvent.
Pyridine forms an azeotrope with water, which boils at 92-93°C.
(Chemical). The main chemical reactions of pyridine are dcstribed below.
(I) Basic Character. Pyridine behaves as a base (pK. 52). It reacts with acids to
form fairly stable salts.
. HQ
PYRIDINE
P YRID IN! UM
CHLORIDE
The reason for the basic character of pyridine is that the nitrogen lone pair being in
cp' hybrid orbital is not involved in the formation of the delocalized Tc molecular orbital.
It is readily available for the formation of a newFN—fl bond with proton. Pyridine is a
stronger base than pyrrote (or aniline) in which the'bascity is reduced by delocalization of the
nitrogen lone pair. On the other hand, pyridine is a considerably weaker base than trimethyl-
amine (a typical aliphatic tertiary amine).
LOA/( PAIR W LOwI PAIR IN

3j.2 OA'B/TAL 5,6 ORBI7AL
H3C
/
coil 17
H3C
PYRIDINE JkIM(T#IYLAMINf
(LEss 8A.5I) (nOt Ms/c)

Hetsrocyclic C ompounds '233
This is probably due to the difference in the nature of hybrid orbitals containing the
nitrogen lone pair in the two molecules. In pyridine it is an sp' orbital; in trimethylamine it
Is an sp5 orbital. Recall that sjft orbitals are smaller (due to more s character) than the
spa orbitals. This means that the lone pair of electrons on nitrogen in pyridine is more closely
associated with the nitrogen nucleus. It is, therefore, less available for the formation of a
bond with proton and consequently the relative bascity is reduced.
(2) Eleclrophilic Sithstltutloa,. Pyridine is considerably less reactive than benzene towards
elect rophilic substitution. This is so as (1) the nitrogen atom in pyridine, because of its
electronegativity lowers the elctron density around the ring carbons ; and (Ii) the vual
electrophiles can coordinate with the lone pair of electrons on nitrogen to form resonance
stabilized pyridinium salts.
0Q --.
0 + E
QO
pYRIDINWM
CATION
Pyridine, however, does undergo electrophilic substitution reactions when extremely

vigorous reaction conditions are used. Substitution occurs almost exclusively at C-3 (13-Posi-
tion). This can be understood if we follow our guide of examining the intermediate cation.
Attack at C.3
: O2-{d4i-(J 40X MORE 5 TABLE 3-50571TUTIOft

PRODXT
Attack at C-i
H.
J (N:Ê N E N
- -.
2-505TITUTR.4'
LESS STABtE A PRODW
Attack at C-4
O '-
78 (45.521I9)
*i -d4kO LESS STABLE
4.3UajTlTU
The contributing forms (4) and (B) which result from attack at C-2 and C-4
respec-
tively are energetically unfavourable and may be ignored. This is because the nitrogen atom in
these forms has only six electrons. Thus, the intermediates arising from attack at
C-2 and C-4
have two resonance forms each. Consequently the product with a sustituent at C.3 predo-
minates. if C.3 is already blocked, substitution will occur at the other available .position,
that is, at C-S.
(a) Nlfritlon. Pyridine undergoes nitration (in poor yield) with potassium nitrate in the
presence of sulphuric acid at 300°C to yield 3-nitropyridine.
Q^rNO,
+ KNO3
341ropyridine
(b) Sulphonation. Pyridine undergoes suiphonation with fuming sulphuric acid in the
presence of mercuric sulphate at 230°C to give pyridine-3-sulphonic acid.
SOH
+ a
Q
pyridine.3.gutPhOfliC ada
(c) Broiniuiatlon. Pyridine may he brominated by passing the vapours of pyridine and
bromine over charcoal catalyst at 300C to yield 3.bromopyridirie and 3,5-dibromopyndine.
B1 + B Br
charcoal
± Br, -0
LçI)
3-bromopyridinc 3, 5-dibromopYridifl
When temperature of 500°C is used, a mixture of 2.bromopyridine and 2,6-dibromo-
pyridine is obtained. At this temperature substitution probably occurs by a free radical mecha-
nism, the active agent being bromine atom obtained by homolysis of bromine molecule.
(d) Frledel-Crafts Acylatlon and Alkylation. Pyridine does not undergo Friedel-Crafts
acylation and alkylation. This is because the Lewis acids (e.g., Aids) which are used as cata-
lysts in these reactions coordinate with the lone pair of electrons on nitrogen.
©+1iCI -
CA—CI
CI
PYRIDINE-ALUM/N1UM
COMPLEX
(3) Nuwleopbilk Substitutions Unlike benzene and pyrrole, pyridine undergoes nucleo-
philic substitution reactions. The same clectronegativity that makes pyridine unreactive toward
clectrophilic substitution makes it highly reactive toward nucleophitic substitution. Substitution
occurs mainly at C.2 (or at C-4 if C-2 is blocked) Preference of attack at C-2 or C-4 over C-i '
again rationalised on the basis of stabilities of intermediates. Nu: in the following equations
represents a nucleophile.

Heterocyclic Conipound 1235
Attack at C.2
:Q::i ;
+I If4

-':c: ''Nu Nu
2sti8sTI TO 1/aN
MORE STABLE PDflfWT
Attack at C.4
NU
NU
4-SUBSTITUTION
PROOUCT
MORE .STA&E
Attack at C.3
14 H H NU
fc
LESS 5T48LE 3-SUBSTI7'117I0N
PRODI,Q
Notice that attack at C.2 and C.4 in pyridine involves intermediates (A and B) in which the
negative charge is spread over nitrogen (more electronegative than carbon) as well as carbons.
This leads to the enhanced stability of these intermediates. Consequently the products with
substituents at C-2 and C-4 predominate.
(a) Reaction with Sodamide (Chiclitbabin Reaction). Pyridine reacts with sodamide in
liquid ammonia at about lOO'C to form 2-aminopyridine.
liq. NI1
1J I -4-
+ taNH
aQ N NI-12
2-aminopyridine
steps. MECHANISM. The mechanism of the above reaction involves the following
three
Step I. The nucleophile (:NH) attacks the C-2 position in pyridine.

I + N:i
- -
Na
Step 2. Hydride ion (:1-I) is eliminated as sodium hydride to yield 2-aminopyridine.
NaH
H —01112+
No
Step 3. Sodium hydride is removed by reaction with liquid ammonia to give back
sodamide.
NaH ± NH, -p NaNH1 + H1
(b) Reaction with Sodium Hydroxide. Pyridine reacts with sodium hydroxide at 300C to
yield an equilibrium mixture of 2-hydroxypyridine and 2-pyridone. The reaction is carried out
in the presence of oxygen (or air).
() + NaOH
a0H
2-hydrox)pyrldine
(:ô
(pyridof)
2-pyridone
Infra-red studies indicate that 2-hydroxypyridine is present only in small amount, and
2-pyridone is the major product.
(c) Reaction with n-Butyl-lithium. Pyridine reacts with n-Butyl .lithium at 100°C to give
2-n-butyipyridine.
0
QO
N
+ CR3CFI1CH,CH,—Li
-+ N HICHICHICH,
+ [jH
2-n-butylpyridinc
MECHANISM. Two steps are involved.
Step 1, The nucleophile (CH2C1{6H1C}{1 :) attacks the C-2 position in pyridine.
CH3 CH2 CH2 CH2 L .-

.. - 0420I2CH2CH3
Li4

Step 2. Hydride ion (:H) is eliminated as lithium hydride to yield 2-n-butylpyridine.
/.; ------
4.
•LH

LLP ,1 CHCH2CH2CH3
• W.m"',a CaC41CI42CH,
4
Li
2-n-butylpyridioc
(4) Oxidation. Like benzene, pyridine is quite stable towards mild oxidising agents. It
does not i-pact with chromic acid or nitric acid. However, it may be oxidised by peracetic acid
to give pyrid inc-N-oxide.
OQ + [o]
PYRIDINE-N-OXIDE
(PYR!DINE+ OXIDE)
(5) Reduction. Pyrrole undergoes reduction with lithium aluminium hydride (LIAIH4),
or hydrogen in the preSence of nickel catalyst to form piperidine.
Ni
200
N
H
piperidioe
(6) ReactIon with Alkyl Halides. Pyridine reacts with alky, halides to form N-alky
pyridinium halides. For example, with methyl bromide it yields crystalline N-methylpyridiniui:.
bromide.
(Q, ) 3 U OQ
.
Cu 3 Br
N-PTHYtPTRmIMsR MOM
(I- sethylpyridw,im brild.)
Uses. Pyridine is used: (I) in organic synthesis as a basic solvent, whereby it not only
exerts a catalytic action but also can combine with acids produced in reactions. For example,
acylation and benzoylation takes place smoothly in pyridine solution; () to denature ethyl
Alcohol; and (3) as s starting material in the preparation of suiphapyridine, Zelan, and niacin.
Suiphapyridine sad Coramine. Suiphapyridine is a colourless crystalline solid, mp
191-1934 C. Although it is known to have severe cde-effects, suiphapyridine has been used in the
treatment of pneumonia, genorrhoea and other infectious diseases.

1238 Advanced Orgonc Chemistry
a
9NHSOj`@
suphapyndine coramine
Coramine is widely used as a respiratoy stimulant.

Picolin. The monomethyl derivatives of pyridine are called picolines. They occur in
bone oil and in coal-tar, and are obtained from the latter source. There are three isomeric
picolines, known as the e-, -, and y-picolines, oc Lhe 2-, 3-, and 4-mcthylpyridines.
CH,
6Q,
.-picoline -picol1ne TPIColinC
(2-me1hylpyridine) (3-methylpyridine) (4-n..e(hypyrüfine)
bp 1294' bp 143'5 bp 1430'
Picolines undergo oxidation with potassium permanganate to yield carboxy derivatives
of pyridine. For example, -picoline gives nicotinic acid.
CH, C—OH
KMnO
+ 10] -+
-pico1ine nicotinic acid

(py,iduw-3-carboxylic acrd)
2-Ylnylpyridine. It may be obtained from a-picolinc (2-methylpyridine) by the following
two steps.
Step I. e-Picoline is condensed with formaldehyde to form 2--hydroxyethylpyridine.
0
(TJ + H—C—H --
Cli, formaldehyde - aQCH,—CH1OH
pico11ne 24-bydroxyethylpyridlfle
Step 2. Dehydration of 2frhydroxyethylpyridine yields 2-vinylpyridine.
OH
(91+
. CH=CH1
2-vinylpyridine
Z..hydroxyethylpyridine
2-Viny]pyridine undergoes polymerization in the same way as styrene, The copolymeri-
zation of 2-vinylpyridine and butadiene yields elastomers which adhere well to nylon fibres and
are used in the manufacture of automobile tyres. Incorporation of 2-vinylpvridine during the
polymerization of acrylonitrile produces polyacrylonitrile (PAN) fibres which have basic proper.
ties, and thus are easily dyed with acid dyes.
PJPERIIMNE,
0
Piperidine derives its name from the fact that it was first obtained by the hydrolysis of
piperine, one of the alkaloids of pepper.
Prepsration. Piperidine may be obtained:
(I) By the hydrogenation of pyridine over nickel at about 200°C.
(2) From pentamethylcnediamine hydrochloride by the following steps.
/CH2
H 2C
I
H7 C
CIN143 ?1 31
-
CH2
I
CH2
—(a'*tci)
0/\
H
cl -
H
NaOH
H20
I
H
FfNTI1 METH YLEN(CIM MIN E PIPER/DINE 9PER/L3/fE

HYDROCKLORIX HYDROCHLORIDE
Structure of Piperidine. In piperidine all ring atoms (flue carbons+one nitrogen) are
sp5 hybridized, and all bond angles are approximately equal to 109°28'. It is a non-planar
molecule and preferably adopts a conformation analogous to the cb4ir form of cyclohexane
(Fig. 4710).
LONE PAIR /A(
sp3 ORBITAL
F1i4710. Chair form of piperidine.

Properties. Piperidine is a colourless liquid, bp 106°C, which has an amine-like smell. It
is miscible with water, and most organic solvents. Piperidine is a much stronger base than
pyridine or ammonia (pK=112). It forms salts with acids.
Piperidine behaves like a typical secondary amine in its chemical behaviour. It reacts
with acetyl chloride, benzoyl chloride, alkyl halides, and nitrous acid in the same manner as
secondary aliphatic an'Jnes do. On heating with concentrated sulphuric acid to 300°C, it is oxi-
dised to pyridine.
Uses. Piperidine is used : (I) as a catalyst for a number of reactions, for example, the
condensation of aldehydes with malonic acid; and (2) as an accelerator in the vulcanization of
rubber.

1240 Adianced Organic Chen stry
Methods of Opening HetocycI1c Rings. A number of methods (in whch piperidinc is

taken as an example) are described below for opening of heterocyclic rings. They are of great
value in the determination of the structure of heterocyclic compounds.
(1) By Oxidation. This involves treatment with hydrogen peroxide.
0
( H2O
I .-o E]1N—CHI—CHI—CH2--CH1—C—H
tN ..,)a r P
N
-aminovaIciaIdehyde
N
piperidinc
(2) By Reduction. This involves treatment with hydriodic acid at about 300°C.
Cm N
-* CH,CH,—CH,—CH,—CH 3 ± NH3
,l-pentane
H
piperidine
(3) By Hofmann's Method of Exhaustive Meihylation. This is based on the observatiol
that mary q uaternary ammonium hydroxides on heating lose water to give an unsaturated hy
drocarbon and a tertiar y amine.
(4) By Von Brauns Me11id. This involves treatment with benzoyl chloride to form the
N-benzoyl derivative, which is subsequently treated with phosphorous pentabnmide
CN_L©
PIPER/DINE BENZOYL CHLORIDE N-BEMZOYL PIPER WINE
PBr,
Or
Lc}l 4_ r H 2_ CH 2_ t!.H, i- ic__.)

[KII—.-]
Br
,5 0I8ROMOPEN1ANE 8ENZONITRILE
(./N.5TA8LE
(5tLQi./ NT" 11.çN
H H3C CH HC CH H3C
H
CH • / H.
L.. CH (2) A90140 '!9 L. - -+ CH3CHCHCHCH
C33 H) CH
j i,3-pti$TAQIENE
N IC'CH H3C CH
3 1I( CH2
UNSTABlE

Heczerocyc tic Compounds 124!
QUINOLINE, a, -Benzopyridine, co
Quinolinc consists of a benzene ring fused to the a, 0 positions of a pyridine ring. It

derives its name from the fact that it was first obtained by heating the famouc antimalarial alka-
loid quinine, with alkali. Quinoline occurs in coal-tar, bone oil, and in angostura bark.
Preparation. Quinoline maybe obtained
(1) By Skraup Synthesis, In this reaction, a mixture of aniline and glycerol is heated
in the presence of sulphuric acid and a mild oxidising agent, usually nitrobenzene or arsenic
pentoxide. The reaction is exothermic and tends to become very violent. Ferrous silphate or
boric acid is generally added to make the reaction less violent.
ONNHC:H
aniline glycerol quinolinc
MECHANISM. The mechanism of this reaction is not completely understood. How-

ever, it is believed that it proceeds by the following steps.
Step 1, Glycerol undergoes dehydration with sulphuric acid to give acrolein.
CH2OH
CHO
rose, HSO4
CHOR -.-, CH + 2l1O
I A 11
H2OH
CH,
glycerol acrolcin
Step 2. Aniline adds to acrolein (1,4-addition) to give (A).
I-I
H
o=c
HO—CA
—%H
©N +H—'
(A)
Step 3. (A) Undergoes ring closure in the presence of sulphuric acid to form
.2- ydroquinoline.
I
H
a HSO
- + 14:0
(A)
1,2-dibydroqu1oHne
Orginic ( liemistry - 79

Adisnced Organic Chemistry

1242
Step 4. 1 ,2-Dihydroquinolirle undergoes oxidation with nitrobenzene to finally yield

quinoline. Nitrobenzene itself is reduced to aniline which is reused in step (2).
+H10
(rCH2
I-
quinotiiic
H
1, 2-dihydroquinolifle
This synthesis is used for the commercial preparation of quinoline. It is also impor-
tant bacause by starting with substituted anilines, substituted quinolines can be made.
This involves the condensation of o.aminobenzalde

(2) By she Friedlander Synthesis.
hyde with acetaldehyde in the presence of an alkali.
C=)o H211.4
2H0.
- quinolinc
O.AM/NOfNZAL - ACETAL QEHYL'E
OEHYDE
Structure of Quinoline. All ring atoms in quinoline are sp' hybridized. As in the case
of pyridine, the nitrogen We pair electrons reside in an sp2 orbital, and are not involved in the
formation of the delocalized t molecular orbital. It shows aromatic properties because its n
orbital contains lea electrons and satisfies the Huckel's rule (n=2 in 4n+2).
Quinoline is considered to be the hybrid of the following canonical forms.
0
9N N - - -
(1) (2) .. (3)
+
(4) (51
CiI vi?
(6) 47) -
The first three structures are similar to the Kekuk structures written for naphthalene.
The last four, which are polar structures, show the effect of the electron-attracting nitrogen atom
on the molecule. .. -
Properties (Physical). Quinoline is a colourless liquid, bp 231°C. It turns yellow on

s(snding, and has pyridine-like smell. Quinoline is miscible with most organic solvents, and
dissolves in water to about 07 per ce'it at room temperature.
(Chemical). The main chemical properties of qulnoline are described below.
(1) Bask Character, Quinoline is a slightly weaker base (pK.r=4'94) than pyridine
(pKa=5'2). It reacts with acids to yield salts which are sparingly soluble in water.
II5J + HCI ._+
Quinotioe c
QU!NQL(NIUMCHORlD(
(2) Electrophilic Substitutions. Quinoiine undergoes electrophilic substitution reactions

only under vigorous conditions, as was the case with pyridine. Substitution occurs at C.8 and
C-5.
(a) Nitration. Quinoline undergoes nitration with fuming nitric acid in the presence of
fuming sulphuric acid tto give a mixture 'f S-nitroquinoline and 5.nitroquinoiine.
NO
'N
+ HNO, + H1SO -
(fuming) (ftnthig)
NO
+
60
5-nitroquininole
- 8-nitroquinolinc
(b) Suiphonation. Quinohne may be sulphonated with fuming sulphuric acid at 220°C to
yield a mixture of quinoline-8-sulphonic acid and quinoiine-5-sulphonjc acid,
SO3H
)+HISO4 -
SO3H quinoline-5-sulphonic
quiooiine4-sujphosijc acid
• acid
(3) Nucleophilic Substitutions. Like pyridine, quinoline undergoes nucleophilic substitu-

tion reactions. Substitution occurs at C-2 (or at C4 if C-2 is blocked).
(a) Reaction with Sodamide. Quinohne reacts with sodainide in liquid ammonia at about
100°C to form 2-aminoquinoline.
11g. NH,
+ aNH I
MN H.
2-aminoquinolinc
(b) Reaction with Potassium Hydroxide. Quinoline reacts with potassium hydroxide at
220°C to give 2.hydroxyquinoline.
1244
+ KOH -

COO aQOH
2.hydz11yqulfl0line
lfthlum. Quinoline reacts with n-butyl-lithium to yield

(c) Reiction with n.Butyi.
2.n.butylquinOlifle.
+ CHsCHiCHsCHrL

- 1I aQCH,CH,CH,CH, + LiH
2.n-butyIquiDOIifle
Quinoline is oxidised by peracetiC acic' 'o give quinoline-N-oxide

(4) Oxldttlon.
-f (O CH.COOH
Q,LltVEtlFOXIOE
Oxidation with alkaline potassium permanganate yields pyridine-2, 3.dicarboxylic acid.
orl
+ KMnOa -
aQc 0"
PYRILwN&2 3-01CAR8OP'IJC
ACID
(QU1NOL Ill/C ACID)
The above reaction provides a major clue to the structure of quinoline because it
shows the position of ring fusion relative to the nitrogen atom
Mild reduction of quinoline with tin and hydrochloric acid gives
(5) Rediictloia.
1, 3,4..tetrahydroquinolinC Reduction . with hydrogen and platinum catalyst produces
decabydroqilifloline.
XJ
1.2,3,4 —TETPAHYDR7- / DECAIIYOROQUINO1IN(
QUINOL/NI
. aIk y
Alkyl HiUde. Quinoline reacts with alkyl halides to give N
(6) Ractib with
-quinolrahdes.Fxmpl,withyodelsN-mthyquinofrde.
HerocycIk Compounds 1245
rono
cHdI
N-METHYLaU,NOL,c/M /O/X
(-AlErnYQuwQL/uM IODIDE)
Uses. Quinolinc is used (I) in organic synthesis as a high-boiling basic solvent,

whereby it not only exerts a catalytic action but also can combine with acids produced in
reactions; (2) in the manufacture of pharmaceuticals, dyes and insecticides.
tSOQUINOLINE, p,y-Benzopyrldlne,
(ÔN:
Isoquinoline consists of a benzene ring fused to the P,? positions of a pyridine ring.
It is isomeric with quinolinc. Isoquinoline occurs in coal-tar and in bone oil. It is isolated
from coal-tar in the forth of a sparingly soluble sulphate. Isoquinoline is also found as part of
the total structure of a number of alkaloids e.g., papaverine and morphine.
Isoquinoline is one of the very few heterocyclic compounds in which numbering of the
ring atoms does not start on the hetero atom. As in the case of naphthalene, the numbering
starts adjacent to the benzene ring.
Preparation. Isoquinoline can be prepared:
(1) Ftom Cinnamaidehyde. This involves condensation of cinnamaldehyde with hydro-

xylaniine to form the corresponding oxime, The oxisne is then heated with phosphuus pent-
oxide to yield isoquinoline. It is believed that the oxime first undergoes rearrangement which
is then followed by ring closure.
OH CH CH
-
. (0", H'C
C
C/t.WAMALDEIIYDE HYLROXYC - CINNA MAt DOXIME
AMINE (UNSTABLE)
H2000
(2) By the Btschier.Napieraiskr Synthesis. In this reaction, 2-phenylethylamine is first
treated with formyl chloride in the presence of a base to form N.formyl-2-phenylethylamine.
This amide is next heated with phosphorous pcntoxide in pyridine to give 3,4-dihydroisoquino-
line which on oxidation (dehydrogenation) with palladium or selenium yields isoquinoline

(YCH2 - CH CM2
OH CH2
-low I
(-HO) NH
V
2-PkEWYLETKYL- FORMAL H C
AMINE CHLORIDE NT0RMY1-2-FWE1VYL-
ETHYL-AMINE
cM2
Psos se, A
&(-H20) 0;N -
(01 ISO Q(J?NOLINE

3,4 -01H YDRO I5Ot1/s'OL INE
Properties. lsquinotineis a colourless solid (mp 26°C; bp 243°C) with a smell like that
of benzaldehyde. It is volatile in steam, sparingly soluble in water, and is soluble in many
organic solvents. It turns yellow on normal storage.
Isoquinoline (pK 1 =514) is a stronger base than quinoline. It forms stable salts with
acids.
Isoquinoline resembles quinoline in most of its chemical properties. Like quinoline, it
undergoes electrophilic substitution at C5 and C-S. It is oxidised by alkaline potassium
permanganate to give pyridinc-3,4-dicarboxylic acid (Cinchomeronic acid).
c—OH
K MnO4
N
(N
PYRIDINE-3,4 -D/CARBOXYLIC
ACID
(CNCHOMERONIC AC/O)
Oxidation with peracetic acid gives the N-oxide. Mild reduction of isoquinoline with tin
4tetrahydroisoquinOIine. Reduction with hydrogen and
and hydrochloric acid yields , 2 , 3 ,
platinium catalyst produces decahydroisoquinolifle.
QUESTIONS
1. Write the structural formulas of pyrrole, pyridine, and thiopheno. How is thiophene separated
from benzene and how do you test for thiophene in beazene? Mention the properties of ihiophene.
2. How would you prepare pyrrote I What arc its chief uses?
3. How is pyridine obtained ? Discuss its structure and mention its uses.
4. Discuss briefly the structures and comparative chemistry of pyridine and benzene.
3. How is pyridine prepared ? How can it be converted into:
(a) Pyridine .2 . sulphoniC acid (b) piperidise; (c) 2.aminopyridine and (d) pyridinium
.,ii 1nride
6. Discuss briefly
the chemistry of furan and pyrrole. How can a compound belonging to each of
these ring systems be synthesised?
7 Draw the Molecular Obital Picture of pyrrole (or pyridine), labe lling each of the orbitals
involved, and showing all bond angles.

8 Explain: (s) Electrophilic substitution in the case of lasso takes place preferentially as 2 or 5 positions
(ii) Pyrrole is weakly acidic whereas pyridine is weakly basic. (Lidaipur BSc 111, 1980)
.9 (a) Iii addition to electrophilic substitution reaction, what other types of reactions are given by
(tiran ? Give suitable examples.
(Ii) Explain why luran is more reactive at position 2 than at position 3.
(c) Compare the bascicity and reactivity of pyrrole and pyridinc. (.Banara.i .BSc III, 1980)
10. Give any two reactions in which pynole resembles phenol. (CalicuiBSc 111, 1980)
11 Discuss the Ml) s t ruct ure Pyrrole. (Punjab BSc Chem Engg 1980)
12 (a) Give one method for the preparation of Pyrrole, Furan and Thiopheec.
(b) How are these classified as aromatic compounds?
(c) How will you synthcsisc the following compounds
(1) 2-Aminopyridirse (ii) 3-Aininopyridine (Punjab BSc 111, 1980)
13 Describe one method of preparation and one property of any No of the following
(i) Furan (ii) Thiophene (iii) Pyrrole.
(Bombay BSc, 1980)
14. Discuss she elecirophilic substitution in Pyridine. (Himachal BSc Jj/, 1980)
15. Explain Electrophilic and Nucleophilic substitution in Pyridine with the help of one example in each
case.
(Kuridaiie,ra BSc 111, 1980)
16. Pyrrole is weaker base than Pyridine.- Explain. (Guru Nonak DeBSr 111, 1980)
17. (a) Show the steps in y ohcd in the preparation of lucas from slcioputose. Gie structural
formulae.
(8) Indicate the steps in any one method of preparation of ixoqaiuolinc. (Kerala BSc III, 1980)
18.
react with: What are he:eri.acycjic compounds ? How is pyridisie isolated from coal tar ? How does pyridine
(ii hot cone. H 5 SO 4 (ii) Na1C2F{aOH (iii) Bra?
1. Give methods of synthesis and discuss aroarsauvity and orientation in:— nh1ti BSc 111.1980)
(i) Pyridine (II) Isoquinoline. (Earr4aJSc 111, 1980)
20. Give one method of synthesis of pyridine and isoquinolime.
(Banj'alortBSc 111, 1980)
Il. (a) Describe important properties of pyrrole and pyridine.
(b) On she basis of Huckcl's Rule account for the arornaticity in thiophene and beitrenc.
(Gorakhpur BSc 11, 1981)
22. What are heterocyclic compounds? Describe she important reactions of Pyridine and establish
its structure. (Al(garhB$c Hoer, 1980)
23. (a) Give the synthesis of: Forest, Pyrroic and Thioph from 1,4-diketone.
(b) Starting with pynole, how will you get the following:
(I) 1-Nitropyrrole (ii) 2-Acetylpyrrole (iii) Pyrrole-2-sulphonic acid.
(c) Why is pyridine more basic than pyrrole? (Punjabi BSc 11, 1981)
24, (a) What ire hcterocyclic compounds? Why are some of them classified as aromatic compounds?
(b) Give resonance foams of Funan. (Osmanic BSc lii, 1981)
25. Justify the statement that Pyrrole, Thiophenc and Fumn are superaromatic compounds. How are
these synthesised 1 (Rajosthan 8Sc III, 1981)
26. How does pyridine react with:—
(1) HI at 300.0 (ii) Sodamidc I (Sav.garBSc II!, 1981)
27. (a) Predict the products of reaction with pyrTole of the following reagents:
(I) Nitric add in Acetic anhydride at —10..
(II) Sulphur tnoxide in Pyridine.
(iii) Benencdiazoniutsrs chloride.
(iv) Bromine in alcohol.
(b) Give reason to justify pyridine is more basic thin pyrrole. (Maharishi Dayaiimd8Sc 111, 1981)
21. (a) Illustrate the reactions which could be used to chacidale the structure of Pyridine.
(b) In what respects does the .-poaition of pyridine resemble closely the who or pare position
in nitrubcnne7. (Ls,skji,era BSc Ill, 1981)
1. (a) Diacus the nucicophilic substitution reactions of pyridInc.
(6) How will you explain:
(1) Electrc,sbiljc nubtitution in pysidloe occurs cbiey in position 3 wbaua it takes place
in position 2 in pyreole.
(U) Grow basicity of pyridine is conspired to that of pyTrole. (P,Jab &c 114 1981)
31. (a) Explain the following:—
(I) Eleciropiubc subaftudw its Pynolc takes place at 2-pion, whereas in Pytiditte it I

1248 Advonced Organic Chemistry
at 3-position.
(ii) Pyridine is more basic than pyrrole. (J1i,nachafRSc ii!, 1981)
(iii) Discuss the oribital picture of Pyridinc.
What are heterocyclic compounds? DesciThe the resonance hybrid in pyrrole.
31 (JIirnacholBSc 111, 1982)
32. (a) Give principal products of reaction of Pyrrole with the following reagents:
(i) Nitric acid in acetic anh)dridc at —10C.
(ii) Chromium trioxide in solphuric acid.
(iii) Potassium iodide-iodine solution.
(Guru Naak Des BSc /11,1982)
(is) Phenyldiazonium chloride.
33. Describe the preparation of furors. Discuss its aromatic character. How would you prepare the following compounds
li-sin furan:
(a)Tetrahydrofuran
(b)2-NitrofuTan (l3ibrugorl 1/Sc/Ions, 1994)
34. Explain the aromaticityofpyrrole. (Cochin 1/Sc. 1993)
35. Explain Pyridine is a much strongerbuse than pyrrolc. (Bangalore 1/Sc W. 1993)
36. Explain: Piperidineisastrongerbasethairpyridiue. (Dalhi 1/Sc lions, 1994)
37. Explain with the help of orbital diagram that nonbonding electron pair at nitrogen in pyridine is not involved in
delocalisation. (Sntxholpur 1/Sc i/ross. 1994)
3$. Describe the synthesis of:
(a) Pyridine : (b) Pyrsote (c) Paean (d) Quinoline ; and (e) lsoquiooline
39. How will you synthesise 3-aminopyridinc frons .picoline. (Madras BSc, 1 994)
Hint, Use the following steps: (0 KMn04 ; (/i) SDCl2 (iii) NI-I3; and (iv) NaOBr.
40. How will you synthesise 8-ethylqninolirse from benzene ? ( Luicbsow 1/Sc, ) 993)
Hint. Use the following steps : (i) CFI5CH2CVAICI3 ; (ii) Hr403/}12SO4; (iii) H2/Ni or Sn/HCI; and (iv) glycerol (Skranp
synthesis) -
41. Writes note on: Molecular orbital structure ofpyrrote. (Karnataka Mc, 1993)
Chapter 48
Alkaloids
The term alkaloid, meaning 'alkali-like' has been used to designate

The compounds of plant origin having one or more basic nitrogen atoms in heterocyclic
ring systems, which induce pronounced physiological activity in animals and man.
The above definition of the alkaloids is by no means perfect and does not cover all
compounds classed as alkaloids.
(1) Piperine, the alkaloid of pepper, is not basic and has practically no physiological
activity.
(2) Purities such as caffeine (in coffee and tea) and theobromine (in cocoa bears),
which stimulate the nervous system, and are heterocycles containing nitrogens, conform to the
definition of alkaloids but are frequently not included in this class,
(3) Opium (containing the alkaloid morphine) and hashish or Mang, are both habit-
forming drugs, yet the active principle of the latter does not contain nitrogen.
(4) Ephedrine is a straight-chain alkaloid that is produced by animal glands, and has
marked physiological activity.
4HHNHCH,
© ephedrine
In fact, no precise definition of the term 'alkaloid' is possible but in general it designates
compounds ha y ing the following common features:
(a) They are found in plants, although a few are of animal origin
(b) They are basic in character and show marked physiological activity
(c) They have heterocyclic rings containing nitrogen as a part of their structures.
As stated above, most of the alkaloids induce physiological responses when administered
to man and animals. Thus the active principles of some of the oldest drugs and medicines
known to man were alkaloids. This made the study of alkaloids particularly fascinating for
thousands of years. By now over 2,500 alkaloids have been isolated, and their structures
elucidated. The search for new and useful ones continues even today.
OCCURRENCE AND ISOLATION

Alkaloids occur chiefly in plants of the dicotyledons families and are localised in seeds,
leaves, bark, or root of the plant. Each site may contain several closely related alkaloids. They
occur largely as salts of common plant acids such as acetic acid, oxalic acid, lactic acid, malic
acid, tartaric acid, citric acid or of certain special organic acids.
1249
79 (45.5/9)

For extraction of alkaloids, the plant material is macerated. If the material is rich in
fat (seeds) it is first extracted with ligroin or petroleum ether for their removal. The plant
residue is then extracted with methanol and the cellulosic material separated by filtration
The filtrate is evaporated to give the crude plant extract. 'This is then dissolved in dilute acid
and extracted with ether. The acid soiutiçn of the alkaloid salts is then basilled and extracted
with ether, Evaporation of ether solution gives a solid mixture of crude alkaloids. It is ther
subjected to fractional crystallisation for separation into individual pure alkaloids. In moderr
practice the isolation is effected by column chromatography, gas chromatography and b)
counter current distribution. The general scheme for the extraction of alkaloids is illustratec
in Fig. 481.
MACERATED PLANT
1. Extract with ligroin
Step! I 2. Filter
I
I Filtrate
Evaporate
FATS
PLANT RESIDUE
1. Extract with CH30H

Step 11
2. Filter out cellulosic material
3: Evaporate filtrate
CRUDE PLANT EXTRACT
I. Dissolve in dii. inorganic acid

Step Ill
2. Extract with ether
Evaporate
Ether solution NON-BASIC MATERIAL
ACID SOLUTION OF ALKALOID SALTS
I. NaOH solution
Step IV - .., -
2. Extract wun enter
' AQUEOUS RESIDUE
ETHER SOLUTION
Step V 'Evaporate
ALKALOIDS
Pig. 481 Procedure for the hoJalion Alkaloids from Plants.
The bit Exchange Method. Recently an entirely new technique based on the ion
exchange principle for the isolation of alkaloids has been developed. The alkaloids ract with
FI ion to form a covalent bond by exchange with a positive ion, and are adsoibed srnoothlon
a hydrogen ion exchanger. . They are then removed from the exchanger by regeneration with
a'kali together with a suitable solvent as ethanol or acetone -
Alkaloids
GENERAL PROPERTIES
(1) Alkaloids are usually colourless, crystalline, non-volatile solids, while a few of
them (conline, nicotine) are liquids.
(2) Except the liquid alkaloids which are soluble in water, the rest are insoluble in
water but dissolve readily in ethanol, ether, chloroform and benzene.
(3) They are optically active, the majority being laevorotatory.

(4) They are basic with a bitter taste, and dissolve in mineral acids to form salts.
(5) PhysiologIcal Activity. Most of them possess marked physiological activity who
orally administered coniine is a violet poison ; quinine is an antimalarial ; cocaine acts as local
anaesthetic ; morphine relieves pain ; alcophine dialates pu'l of the eye ; and so on.
(6) Basic CharaclerThc molecule of an alkaloid contains one or more basic nitrogen at-
oms. Most alkaloids are tertiary monoacid bases, while a few are secondary bases. Thus they
form well defined cr y stalline salts with mineral acids, the hydrochloride and nitrate being
generally readily soluble in water.
Alkaloidal Reagents. The solutions of alkaloids in dilute mirerals acids when treated
with certain reagents form insoluble precipitates, often having characteristic colours and
melting points Such reagents as are usea for identification of alkaloids are frequenti) spo-
ken of as Alkaloidal reagents. The common ones are
Chloroplatinic acid, H 2PCI6 Phosphomolybdic acid; Phosphotutiestic iacid; Picric acid,
Tannic acid Potassium mercuric iodide, HgCI -K) (Mayers reagen t ); Potassium bismuth
iodide, KBil 4 iDragendroff '.1 reagent, Potassium cadmium iodide. KCdI 1
(Marine's reagent)
Potassium iodide solution in iodine, K13.
The same alkaliodal reagents may be used for the precipitation of proteins and other
complex substances of basic nature.
CLASSIFICATION ; A BRIEF SURVEY
Alkaloids are so numerous and involve such a variety of molecular structure that their
rational classification is difficult. However, the best approach to the problem is to group
them into families, depending on the type of heterocyclic ring system present in the molecule.
Very often a number of alkaloids having similar structure are found in the same plant and also
show resemblance in the properties. Alkaloids are also named as a group after the name of the
plant from which they are isolated.
For historical reasons as also because of their structural complexities, the nomenclature
of alkaloids has not been systematised. The names ofindividual members are, therefore, gete-
tally derived from the name of the plant in which they occur, or from their characteristic
physiological activity.
The various classes of alkaloids according to the heterocyclic ring system they contain
are listed below.
(1) Pyrrolidine alkaloids; (v) Quinoline alkaloids

(ii) Piperidine alkaloids; (vi) isoquinoline alkaloids
(iii) Pyridine-Pyrrolidine alkaloids ; (vii) Indole alkaloids.
(iv) Pyridine-Piperidine alkaloids
In the following treatment we will discuss the above classes taking examples of the
familiar members. In most of these cases we will also give concisely the structure, the source
and the characteristic physiological activity. The detailed study of the important alkaloids
however, will be taken up separately at a later stage.
(1) Pyrrolidine Alkaloids. They contain the pyrrolidine (tetrahydropyrrole) ring system
e.g., Jlygrine and Cuscohygrine.

252 Advanced Organic Chernstry
I,
0
CH
CH3
H

PROL/OfNE HY6R/NE C USCOIIY6RINE
Hygrme is isolated from the leaves of the Peruvian Coca shrub. Cuscohygrine is found
in 'cusco leaves'.
(2) Piperldhie A21olds. They have piperidinc (hexahydropyridiiie) as the heterocyclic

structural unit e.g., Contine, Jsopelletiertne, Lobellne, and Piperine.
0
CN)aCM7 — CH2—CH 3 CH 7 —C —CH)
H H H
P/frf DINE COWINC 150FELI ET/EA'I"/(
0 C
II
CH?—C — CeH5 CMCH HCH J- Nfl
I
CH3
LO8ELIN( PIPER/NE
Conline ocurs in the oil of hemlock and is poison to humans. Isopellelierine is isolated
from bark of pomegranate tree. Lobeline, obtained from the seeds of Indian tobacco
is used in medicine as a respiratory stimulant and as a tobacco substitute.
(3) PyTrolldlne- yMlne Alkaloids. Th. h5terocyciic ring system prent in thrr
alkaloids is pyrrolidine-pyridine. Examples are nicotine or myo.sinine-
C H]
P y,cRo/IDIN(-p yR/U/NE ,v1C071NE
Nicotine is isolated from tobacco leaf. It is highly toxic which in very small doses causes
respiratory stimulation and in large doses causes respiratory failure and de h. Mysomine also
occurs in tobacco and aroma of tobacco smoke is due to it.
(4) Pyridine.Piperldioe Alkaloids. This family of alkaloids contains a pyridine ring

system joined to a piperidine ring system. The implest metber is Anabasine, the chief
alkaloid isolated from the poisonous Asiatic plant, i nabasis aj.hyllan. Another alkaloid of this
class is Anatabine.
1253
Alkaloids
0QO _nC;-4
N
ANA8ASIWE ANAT48(WE
Alkaloids. These have the basic heterocyclic ring system quinoline e.g.,
(5) Quiaolhse
quinine and prim.aquinine.
140
'ICH
CHI CHI CHCHC2
CHI 042
HCO HC
CON
QUINOLINE QUININE
HC-C- CH2CH2CH2NH2
H
PR/4QjJINtNf
Quinine occurs in the bark of Cinchona tree. It has been used for centuries for treat-
ment of malaria. Synthetic drugs such as prilnaquinine have largely replaced quinine as an
antimalarial.
A recently isolated alkaloid of this group is cainptothecin found in chinese tree Campho.
This is known to possess antileukernic and antitumor activity in
theca acwninaf a Nyssacae.
animals.
CAPTOTHECIN
CH2I42C
Alkaloids. They contain the heterocyclic ring system isoquinoline e.g.,

(6) lsoquhsollne
panaverine and morphine.
Papaverine is isolated from the unripe seed capsule of the opium poppy. It finds use as
medicine in the treatment of spasms of the stomach or intestines.
Morphine is isolated from opium. It is used in medine as hypnotic (sleep producing)

and (paiii releiving). Unfortunately, prolonged intake of morphine leads to addiction and hence
it use is sharply restricted.
1254 Advanced Oganic chemistry
HO
gN
0
OR c]
NH HO
MORPHINE
OCH3
OCH3
ISO QU1NOtINE
PAPA V(R/N6
(7) Indole Alkaloids. Alkaloids based upon the indole skeleton are widely distributed
in nature. The physiological action of these substances may rest in the fact that derivatives
of indole play important roles in the chemistry of the brain
HO--C""&\
INOOLt
(&4JIc 5/CELETO/f) STRYChNINE
L YSFRGIC ACID
Lysergic acid, isolated from the fungus Claviceps purpurea, is the best known alkaloid of
this class. In small regulated amounts, it is. used in the treatment of migrane headaches as also
for the induction of uterine contraction in childbirth. The dimetbylamide of lysergic acid
(LSD) is the most potent psychotomi'iietic substance known. It has varied effects on humans,
producing colour halliciinations an .ychotic states similar to those of schizophrenia.
Another indole alkaloid is strychnine which is isolated from the seed of s:rychnos
nuxvomica. It is extremely poisonous and is used for exterminating vermin. Its structure
was elucidated in 1948 and this was followed by its total synthesis by R.B. Woodward.
DETERMINATION OF STRUCTURE
Alkaloids mostly have complex molecular stucture the determination of which is both
tedious and challenging. This needs a careful and systematic approach. The usual procedure
is as follows,
(I) Determination of Molecular Formula. The molecular formula of the given unkown
alkaloid is first determined by suitable methods described before.
(2) Detectloa of Groups The presence of various functional groups in the molecule
is ascertained by applying specific tests.

Alkaloids 1255
A. NATURE OF OXYGEN FUNCTIONS

Oxygen is usually present as alcoholic, phenolic, carbonyl, carboxyl, mcthoxy or
ester group.
(a) Hydroxyl group OH. The alkaloid is treated with acetic anhydride, acetyl chloride
or benzoyl chloride to detect the presence of hydroxyl group (Note that —NH 1 group also
reacts with these reagents). The —OH group may be phenolic or alcoholic. It is phenolic if
the alkaloid—
(1) gives a colouration with ferric chloride.
(ii) is soluble in sodium hydroxide and is reprecipitated by carbon dioxide.
If the above tests are given in negative, the —OH group is alcoholic. Primary alcoholic
group, CH 2OH, forms esters and on oxidation yields aldchydes. The secondary alcoholic group,
>CHOH, forms esters and on oxidation gives a ketone.
(b) Carhoxyl group CO011. The presence of carboxyl group is indicated by the
formation of salts and esters, and the evolution of carbon dioxide with sodium bicarbonate
solution.
(c) Methoxy group, —0CH1. This group produces methyl iodide on heating with hydrio.
dic acid.
—OCR, + HI -+ —OH 4 CHI
(d) Carbonyl group, >CO. The presence of carbonyl group is detected by the
formation of oxitne and hydrazone.
(e) Ester group, —CO—OR. The alkaloid containing the ester group gives an acid and
an alcohol on hydrolysis.
B. NATURE OF NITROGEN FUNCTIONS
(a) Amino group, —NH5. The alkaloids containing an amino group form salts with
acids. The nature of (be amino group is decided on the basis of the sollowing reactions.
(1) Aliphatic —NEI1 group reacts with nitrous acid to give a primary alcohol with the
evolution of nitrogen.
(u ) Aromatic —NH1 group forms diazonic salts and dyes by coupling reactions.
(iii) Secondary amino group, —NH—, reacts with nitrous acid to form nitrosoamines.
(iv) Tertiary amino group, >N—, reacts with methyl iodide to form quaternary-salts,
(b) Amide group, —CONH5 . Upon hydrolysis, the alkaloids containing an amide
group yield the corresponding carboxylic acid and ammonia.
C. PRESENCE OF MATURATION
The presence of unsaturation in alkaloids is indicated by treatment with bromine water
or dilute alkaline potassium permanganate. Reduction with sodium amalgam, sodium and
ethanol, hydriodic acid, or tin and hydrochloric acid also shows the presence of unsafuration.
(3) Estimation of Groups. The estimation of various groups detected as above, is carried
as follows.
(a) Hydroxyl groups, The number of hydroxyl groups is determined by acetylating the
alkaloid and hydrolysing the acetyl derivative with a known volume of IN —NaOH.
CHCOCt NaOH
K—OH -p. R—COCH1 -+ R—OH + CH1COONa
The excess of alkali is estimated by titration witha standard solution of hoydrochlorjc
acid. The number of acetyl groups or hydroxyl groups can be calculated from the volume
of alkali used for hydrolysis.
(b) Carboxyl groups. The number of carboxyl groups may be determined volumetri.
caily by titration against a standard barium hydroxide solution using phenolphthalein as
indicator or gravimetrically by 'Silver salt method'.
256
Adiwiced Organic Chemistry
(c) Methoxy groups (Zeisel's method). The number of methoxy groups is estimated
by heating the alkaloid with conccntated hydriodic acid. The methyl iodide evolved is absorb-
ed in ethanolic silver nitrate when silver iodide is precipitated.
R(OCH1)n + nHl -k R(OH)n + nCH3I
nCH1I + nAgNO1 -+ nAg! + nCH3NO5
The precipitate of silver iodide is boiled with nitric acid, filtered, washed, dried and
weighed. From the weight of the pricipitate formed, the number of methoxy groups can be
calculated.
(d) —NH1 >NH and —N< groups. These can be estimated: (1) by forming the
hydrochloride and titrating its aqueous solution against N/lO KOH using phenolphthalein as
indicator ; and (ii) by the platinichioride method described before.
(4) Degradation. The alkaloid is decomposed by treating with suitable reagents to
give simpler compounds which can be identified easily.
Hydrolysis. An alkaloid containing an ester or amide group gives simpler products on
hydrolysis. For example, piperine gives piperidine and piperic acid on hydrolysis.
- C11H,02—CO--NH1 + HO —s CH 2O—CO—OH + C5HSO—NH
piperine pipede acid piperidiac
From this we infer that pipeline is an amide of piperic acid.
(ii) Oxidation. Oxidation of alkaliod with potassium permanganate, potassium dichromate,
or with hydrogen peroxide can bring about several changes, Thus with potassium permanga-
nate the molecule may be oxidised away leaving a COOH group at the root.
(lil)- Distillation with Zinc dust. When distilled with zinc dust, many alkaloids yield
the parent compound, or are dehydrogenated. Thus morphine on distillation with zinc dust gives
phenanthrene, indicating the presence of the latter as the basic skeleton in the molecule. Coniine
yields conyrine by the loss of a molecule of hydrogen.
(iv) Exhaustive Methylalion. This is an important method used to find a recognisable
moiety in an unknown alkaloid. This is acomplished by degradation of the alkaloid by the
following step3.
(a) The heterocyclic ring of the alkaloid is reduced if unsaturated,
(b) The alkaloid (or the reduced alkaloid) is treated with excess of methyl iodide when
the >NH of the ring system is methylated and then converted to the respective quaternary
ammonium iodide.
CH3I 4 CH 5 1 +
---+ >N—CH -* >N( I
merhylatton ' ' CHJ
- imino group methyl derivative 4' amm Iodide
(C) The quatenary ammonium iodide is changed to the corresponding hydroxide by
reaction with moist silver oxide (AgOH).
+ CH 31 . A5OH + ,CH 3 1' -
>N<' 11 . > N( OH+AgI
'-CH5.J 'CH.J
4' amm hydroxide
(d) The quaternary ammonium hydroxide on pyrolysis splits out a molecule of water
the OH group extracting a H atom from the p.position with respect to N atom. As a result,
the C—N bond on the side of the p-hydrogen concerned ruptures to give an open chain
unsaturated amine.
(e) The above sequence of reaction listed in steps a, b, c, d are repeated with excess
of CH1 I when rupture of the second C—N bond occurs and N atom is eliminated as (CHN.
The unsaturated hydrocarbon left behind, which often isomerises to a conjugated dieie, is
identified 'by the usual analytical methods.
Alkaloids 1257
Th'e overall process mentioned in the steps above involving repeated methylation to get the
degradation end-products is called Exhaustive Methylation. The nature of these products helps
in arriving at the structure of the parent alkaloid. This may be illustrated by taking example
of pyridine ring system.
I, H, H,
,CN
HC""CH HN. H2C CH, 1.01,1 H2 0 CHj. HK CH
i 2. AO H H
nC 01 H J 2 Cal,
CN, "'\
N
N.
PIPERID/NE
113 H, H
I H,CNCH CHI
______ A ,.-' OOMFRISfS C
Il N—01 + '
2. AgOil w2c CHI —14,0 \ KIC H,C I
O2 (H,
/ I ,4-PENrAD((Nf
Ht CM) (PIpfeyem)
Thus the mode of linking in the ring system is established. The-method has been best
exploited in the elucidation of structure of ccnhine.
Hofmann's exhaustive methylation method is applicable as long as (i-hydrogen is available
for elimination of H 20, otherwise it fails. Thus it does not apply in case of quinoline and
isoquinolinc derivatives.
(5) Newer Physical Methods, In conjunction with the chemical methods mentioned
earlier more recent and sophisticated techniques are now frequently used to elucidate the
structure of alkaloids. In fact, in some cases the structure of alkaloid has been given even
without carrying out any chemiral work.
(i) infrared Spectra are used to detect the presence of many functional groups
(ii) Ultraviolet Spectra are employed so as to project the possible type of structures
present in the molecule.
(iii) X-Ray Analysis has provided a means to fit in the various strucLural units indicat-
ed to be present in the molecule, thus givining a sure procedure to give the final structure of
the alkaloid accurately.
(iv) NMR Spectroscopy. It is a more recent and sophisticated method for detecting
many functional groups such as 'lken. protons, N—., 0—, and C—methyl groups. The pre-
sence of heterocyclic ring systems e.g., pyrrole, pyridine, quinoline, isoquinoline indole etc, is
clearly proved by NMR spectroscopic method.
(6) Syatbesls.. The analytical procedure discussed above will project the tentative struc-
ture for the alkaloid under investigation. Because of the aforesaid physical methods, which are
sure and accurate, the confirmation of the structure by synthesis of the alkaloid is no longer that
important. Nevertheless, synthesis will ever remain a fruitful method for confirming the
proposed structure as it might as well provide a newer way of obtaining an alkaloid rather than
depending only on a natural source.
CONUNE
It is the principal toxic substance present in the hemlock herb (Con flint maculaluin)
and is now of historical interest only. The extract of hemlock containing contine was used
as official state poison by Greeks for the execution of criminals. The famous philosopher
Socrates was put to death in 400 B.C. by being required to drink hemlock extract.
Organic ('lieniistry - 80

Isolation, The seeds of hemlock are powdered and distilled with sodium hydroxide
solution. Conilne is then recovered from the distillate by on extraction with ether. The
ethereal extract on evaporation leaves behind the alkaloid.
Properties. Conhioeisa colourless, stronglyalkal Inc liquid, bp 167°C. It has an unpleasant

odour recalling a mouse, and has a burning taste. It is sparingly soluble in water but dissolves
readily in ethanol. Both coniine and its salts are exceedingly poisonous to humans, causing a
gradual paralysis of the nervous system that ends in convulsions and death. The natural alka-
loid is dextrorotatory, []D= 1570.
Structire. (I) The molecular formula of coniine as deduced from its analytical data
and the molecular weight determination is CH15N.
(2) When distilled with zinc dust coniine loses six hydrogens giving a new base cony-
rifle, C,U 2N. The conyrine on oxidation with MO, yields pyridine-2-carboxylic acid
(a-picolinic acid).
C 8H, 7 N
ZINC DUST
CONIfN( PUTIL COOVYRM

-w C0H,1N
kMnO4
(D"COOH
PYRIDINE-2—CARBOXYLIC ACID
These changes indicate that conyrine is probably pyridine derivative with a side-chain
in 2-position which upon oxidation would be capable of producing pyridine-2-carboxylic acid.
Again, since conyrine is obtained from coniine by loss of six hydrogens the latter compound
ouId be the corresponding piperidinc derivative. Thus we can depict the above reactions as
—6H[0)
(N (C 3H7) (C3H7) R
N COOH 10
CON!! WE CONYR/NE PYRIDINE-Z-CARBOX...h ,C/D
The side-chain (— 05H7) in coniine can be represente' in two ways.

I
-CHr-CHr---CHs or _C4( ca.
C14
Therefore, the two possible structures for c'.diine are
OR
.
(3) On heating with hydriodic acid and phosphorus, confine is reduced to give n-octane.
This shows that the side-chain is n-propyl and not isopropyl.
HI/P
N. CH'I"CH2—CHI—CH3
H
2_CH—CH,
17-OCTAME

1259
Alkaloids
Had the chain been isopropyl, the expected product would have been isooctane.
HI/P
(143
(+4H) CHj + NH)
CH'
IN, CH3
H
2-60PROPYL PIPIRIDINE ISOOCTANE
Therefore, it stands to reason that confine has the structure
aCH2—CH2—CH3
(4) An additional evidence for the above structurc of conline is afforded by the exhaus-
tive methylation of the alkaloid which gives an alkene, coeylene (CH14) with the elimination of
nitrogen as (CH) IN. The conykne can be reduced to form n-octane.
(5) The structure of confine was finally confirmed by Landenburg's Synthesis (1886). The
condensation of .picóline (2-inethylpyridinc) with acetaldehyde at 25OC forms 2.propenyl-
pyridine, which on reduction with sodium and ethanol yields (±).coniine.
OHC —CM3
C1.CHa_CH;_CH
QNCH==C H--043 —:--
a
d - pROP(NYLPYRIDII H
-P,COL/NE
(±) CONII4I'f
(±)- Coniine so obtained is resolved by forming salts with (+)-t artaric acid and frac.
tional crystallisation. The salt of (-f-)-Coniinc being less soluble crystallises out first. This
on treatment with alkali gave free (+)-coniine which was found to be identical with the
natural alkaloid.
The structure of cohiine has also been confirmed by another synthesis effected by Berg-
mann in 1932.
C,HU
0"3 a
g C^ z j .AM rj4 C'CN,O43CH$

.(- PlC tIC/Nt CDWiR1A
The product is a racemate which is resolved to give (+)-conhinC&S described before.

PIPERINE
This alkaloid occurs in the ripe fruit (white pepper) and in the unripe fruit4bJack
pepper) of fqvr nigrum. It occurs in the kernel of the black pepper to the extent'If 5 to 10
per cent and was isolated from this source by Oerstedt (1819).
Exlmctloa. Piperine is obtained by extracting the powdered black peppcti with ethanol.
The extract is evaporated and the solvent free residue is treated with NaOH solution to remove
teem. The insoluble residue is again dissol v ed in warm ethanol (or ether). From the solution,
piperine crystallises out on cooling.

Properties. Piperine froms beautiful colourless crystals, mp 128-129'5C. It is neutral

to litmus and has the characteristic sharp flavour and taste of black pepper. It is difficultly
soluble in water but dissolves readily in ethanol and ether. Its toxicity is much feeble as com-
pared to other alkaloids. It is optically inactive.
Structarç. (I) By elementary analysis and molecular weight determination, piperine
has been assigned the molecular composition CI,HJ.03N.
(2) On hydrolysis with alkali it gives piperic acid and a base piperidine.
NaOH
CI,HJIOIN + I{O -+ CI1 H,02—COOH + CI11,NH
pipcnnc boil pipaic acid piperidjoc
Obviously, piperine is the piperidine amide of piperic acid. The structure of piperidinc
is already known and hence we could represent the alkaloid as
CiIH902__co_NEI
(P/PEP/DINE AM/DC)
Thus to have a complete picture of the structure of piperine, we should know the structure of
piperic acid.
(3) Structure of Piperic acid. (a) Piperic acid on oxidation with potassium permanga-
nate first gives piperonal and then piperonylic acid.
(01 (O
CU H 2 O l .COOH -+ C 7 HOa.CHO -+ C7HO2.COOH
pipenc acid piperona) piperonylic acid
Since piperonylic acid has C 4 H 4 less than piperic acid (C 1I H,0 2 .COOH . CH 5O,.COOH =
CA), this proves that the aromatic moiety C,HO 1 in the molecule, has a single side chain and
the fragment C4H4 is knocked out during oxidation. Thus piperic acid could be written as
C7 H5O1—CIJ—COOH and the above reaction yielding piperonylic acid explained as follows.
(0)
C,F!O—CH4—COOH-p CH5O5—COOH
piperic acid - (CaH) piperonylic acid
(b) The structure of piperonylic acid follows from the fact that on heating with hydro
chloric acid at 200°C under pressure forms proto r atechuic acid and formaldehyde.
HO
•
20°, pR(55t/RE C) 0011
C7H0f COOH -f H0
PIPERQ#/)tK ACVHO
HCj
4- CHO
PRQTOCATECHUIC AC/C)
Since one carbon has been eliminated as CH IO and as a result two free OH groups appeared
in protocatechuic acid, it follows that piperonylic acid is 3. 4-me(hylenedioxybenzojc acid. The
above reaction can be visualised to have proceeded as follows.
HO
+ H20
h2< J- H7cQ +
COOH
A00H
BENZOIC Acir
3,4 . f4U/IVLlWtD/0XY•

Alkaloids 1261
(c) As indicated in step (a) above, the structure of piperic acid may now be written as.

112C /
C4114---000H
(d) The structure of the side-chain in piperic acid becomes clear from the fact that
(i) it takes up readily four bromine atoms showing the presence of two double bonds; (ii) on
careful oxidation with KMnO it decomposes to form a mo!ecule of tartaric acid and oxalic acid
each, indicating the presence of two bonds in alternate positions.
CH(OH)COOH
—4=_c+L COON
+'I 01 (OH)COOi-i
310E CHAIN 0'4Lf .'C'D 74RT4N/CAC/i
Hence the complete structure of piperi' acid cip be written as

0
H2c(0
H=CHC00i
P/PERf ACID
(4) Knowing the molecular structure of piperic acid arij pipaidint tile Structural for-
mula of piperine can be derived by joining the two as amide (See step 3c)
0 CH-CI1=_CH-_C -N.
P/PER/NE
(P/P,D/NE AMIDE or P/PER/c ACID)
(5) The synthetic evidence for the structure of piperine was afforded by firl synihccicin
piperic acid and then preparing from it the alkaloid.
(a) The Synthesis of Piperic acid (Landenburg and Scholtz, 1894).
(1) Piperonal is obtained from catechol by Reimer-Tiemann reaction.
Ho
NaOH
) c'2" /::ac
Q + CHC 3 -J.-
H
ED NaOH
CATEC/L P/PEROi'v.4

1262
of sodium hydroxide
(ii) Pipernal is condensed with acetaldehyde in the presence
Claisen Condensation) to give cinnasnaldehyde derivative. This is then heated with acetic anhy.
presence of sodium acetate (Perkin Reaction) to yield piperic acid
dude in the
- NOW °<J :
Q4CHO40
M CM^CM—CH = L W —CO04
0
C,A,tjAMALOC/IVD(DWVATP/t PIPE nic 4C10
PIP RJIA
(b) prepara t ion ofPiperinefroin Piperic acid. This is done by first reacting piperic acid
with phosphorus pentachloride so as to get piperoyl chloride. This is heated with piperidinc
in benzene solution when the product is found to be identical with natural piperine.
PCk CH(
- 1—
OOH
PIPERO YL CHLOR/OE
PIPER/C ACID
\0^ a CHCH_cCHC_C NQ -
- Hs
.',PIROYL CHLORIDE
P/PERID/NE
(:c1..CHCH_CH = CR-C - "o

PIPER/NE
QUININE
It occurs along with more than two dozen alkaloids in the hark of cinchona tree.
Quinine, the most important of these has bsen used as antimalarial for centuries. In fact, the
successfully
name Cinchona' was given to the tree because the material obtained from it was
employed in treating the wife of Count Cinchona, Spanish viceroy of Peru (1869). In recent times
the main source of quiniqe has been plantations in the Dutch East Indies, chiefly Java,
Alkaloids 1263
isolation. The finely powdered cinchona bark is extracted with benzene or toluene in
the presence of alkali. It is present in the bark as ester of quinmic qunitannic acids and passes
into the solvent extract after being liberated by alkali. The mixture of alkaloids is then extracted
from the solvent layer by dilute sulphuric acid. When the acid extract so obtained is neutralised
with alkali, the sparingly soluble quinine sulphate precipitates out. The other minor alkaloids
present left behind are precipitated from the filtrate with excess of alkali.
Quinine was synthesised by Woodward and Doering (USA) in 1944, but a commercially
feasible process has never been realised,
PropertIes. Quinine is a white solid, mp 171°C, which crystallises with three molecules
of water to form the trihydrate, mp 57C. It has an intensely bitter taste. The alkaloid is very
sparingly soluble in water but dissolves in organic solvents such as benzene, toluene, chloroform,
ether etc. The natural quinine is leavorotatory, [J= — 158°. It is very weakly dibasic but
forms well-defined salts with acids e.g., quinine sulphate and quinine hydrochloride.
(C2 HHN,)1H2SOg. 8H 20 CFT14ON2HCl. 2HO

quinine sulphate quinine hydrochloride
Quinine has a specific property of fighing down malarial parasites in the human body.
The drug is suppriive but not curative. Quinine and its salts were used for long as antimala-
rials. The al!' ',oid is also an anlipyretic, that is, it Lowers the body temperature in high fever.
Quinine has now been replaced by more effective and less toxic medicines as aiebriz, plamochin.
Sfructure. (I) The molecular formula of quinine is C,0H14N202.
(2) It adds two molecules of Cl!1 ! to form di-quaternary salt which suggests that both
the N atoms present in the molecule are tertiary.
CsHngNsOn + 2CH,I - CIHI4NIO2.2CH$I

quinine di-quaternary salt
(3) Quinine readily forms the acetyl derivative and chloro compound on treatment with
acetic anhydride and phosphorus pentachloride respectively. Therefore, it cOntains one —OH
group.
(4) On mild oxidation the alkaloid is converted into a ketone, quissinone, without loss
of any carbon. This shows that the —OH group is present as secondary alcohol group.
101
[C10H11N,Oi >CHOH [CH55N50] >CO -- H10
quinine quininone
(5) On heating with hydrochloric acid, quinine loses one carbon atom as CH 3CI, mdi
eating that the second oxygen in the molecule is present as methoxy (—OCH,) group.
HCI
[CeH,,NsO]>N—OH
1CjjHsiNsO]>C__OCHs —+ + CH5CI
quinine cinchonirse
(6) It adds one molecule of Br1 or halogen acids, showing the presence of a double
bond in the molecule. Also, quinine on oxidation with KMnO4 yields a monocarboxylic acid
and formic acid; which confirms the presence of double bond in a vinyl group (—CH=CH1).
Hr
[C 15 H11 N1051—CH=CH1 + Br5 -+' (C5 , Hsi N2O,]—(H—CH5

quinine dibromide
• [CHN 50,j—CH 'CH1 L

KMnO4
(C11 H11 N 20 2 j-.COOH + HCOOH
monocarboxylic acid formic acid
(7) Quinine on vigorous oxidation with chromic acid yields quininic acid and 3-vinyl-
quinuclidute-

COCH
C00
()J__CH=CH2
9N)
QUINIMIC ACID 3-VINYL-Ul WCI. ID/NE
(8) The above reactions supplemented by more evidence of complex nature have shown
that quinine has the structure.
40N
3CON
ON
QUININE
NICOTINE
Nicotine is the chief alkaloid of tobacco plant (Nicotina tabam). It occurs in the plant
leaves as salts of malic acid and citric acid to the extent of 4 to 5 per cent. The alkaloid was
named after the Frenchman Nicol who introduced tobacco in France in 1560.
Isolation. (I) Waste parts of the tobacco plant are finely powdered and extracted with
dilute acid. The water-soluble salts of alkaloids are thus removed in solution, leaving the
soluble cellulose, chlorophyll etc behind.
(2) The acid extract is then made basic with lime or sodium hydroxide, and steam-dis-
tilled. Steam-distillation separates the nicotine from water-soluble nonvolatile materials (sugars,
inorganic salts etc).
(3) The distillate is acidified to about pH3 with solid oxalic acid and concentrated to a
syrup. On cooling, the crystalline salt of nicotine and oxalic acid separates. Other alkaloids
not forming slightly soluble oxalates are left in the solution.
(4) The crystalline nicotine oxalate is then transferred to a separating funnel and treated
with excess of aqueous KOH. The nicotine thus set free rises to the surface as a brown oil, and
separated by extraction with ether.
(5) The ethereal solution of the alkaloid is dried over solid anhydrous KOH, and the
ether evaporated. For further purification, the residue is fra...tiooally distilled under vacuum.
Properties. (1) Nicotine is one of the few alkaloids known to exist in a liquid form;
colourless, bp 246°C.
(2) It has a tobacco-like smell and a burning 'alkaline' taste.
(3) It is soluble in water and also in organic solvents such as ethanol, ether and benzene.
(4) The natural alkaloid is laevorotatory, [aJ0=-169.
(5) It is a deadly poison to animals and is used commercially as an insecticidal spray for
plants and animals.
(6) In small quantities, nicotine stimulates the nervous system for a while, which is
followed by depression. A low nicotine-content tobacco is used for smoking purposes even-
though it is definitely injurious to health, causing diseases like asthma and lung cancer.
Structure. (I) Elemental analysis and molecular weight determination leads to the
molecular formula C I# H,*Nl for nicotine.
Alkaloids 1265
(2) It absorbs two molecules of CH 1I, suggesting the tertiary nature of both the nitro-
gen atoms.
(3)on ozidation with chromic acid, nicotine yields nicotinic acid (pyridine-3-carboxylic
acid).
-p
[OJ (O
C10H14N1 '),COOH or CsH4N1COOH
nicotine
nicotinic acid
This shows that the alkaloid contains a pyridine nucleus with a side-chain at the 3-posi-
tion. That is, the side-chain has the composition (C 1,H1 N—05 H4N) = CH10N. Therefore'
the formula for nicotine may be written as
CH10N
F,
From the above formula it is evident that the side-chain must be saturated.
4) Nature and Position of the side-chain. (i) The alkaloid forms an addition com-
pound with zinc chloride, C10H14N1.ZnCI1 , which when heated with lime yields pyridine, pyrrole,
and methylamine.
lime
C10H4N1.ZnCl -.. + OQ+ CH, —NH,

pyridine H
pyrrole
This suggests that the side-chain, CH 10N, is a pyrrole derivative.

(ii) When heated with concentrated hydriodic acid at 200-300°C (Herzig and Meyer),
nicotine yields CH3 I, showing that methyl group is attached to N-atom. Therefore, it appears
that the side-chain could be N-methylpyrrolidine.
— CH
N/
La OR II
L tH3
However, the point of attachment of the side-chain to the pyridine nucleus could be C1
or C as shown above.
(iii) Nicotine hydriodide when treated with CII,!, forms nicotine isomethiodide which
on oxidation with potassium ferricyanide yields nicotone. This on further oxidation with
chromium trioxide produces hygrMic acid.
80 (45-5211982)

012 - CHa
1. HI K5Fe(CN)1 Cr03
C L, H 1 N1 -_, C II H 4N.CH1 -+ CI,H1.N10,CH3 CH7
nicotine 2. CHa! nicotine NaOH nico)onc CH
isometbiodide
HOOC/N/
Ck
hygrinic acid
The formation of hygrinic acid as above proves beyond doubt that the side-chain,
V-methylpyrrolidine, is attached to the pyridine nucleus through C1.
(5) From the foregoing considerations the structural formula of nicotine may be written
Ci.1 2_ CH2
U CH 2
OR
04j
L)
(N-/.IETMYLPYRROL/DlP/E-2-PYR /0/NE)
(6) The above structure of nicotine is further confirmed as it explains the following
reactions of the alkaloid admirably.
(i) Nicotine when treated with bromine in acetic acid followed by aqueous sulphurous
acid gives dibromonjcorjne, C10 H 1 ON1 Br,. This upon oxidation with a mixture of sulphurous
acid and sulphuric acid at 130-140°, yields 3 . ace(ylpyrjdiue, oxalic acid and methylamine
(Pinner, 1892).
__________
ii B.fAc' L (01 • cooi, r°" +
c , .043
(3) '' © °'/
COO"
O4
WCOINE Ol*AW,ilcOm
(ii) Nicotine on reaction with bromine in hydrobromic acid gives

which when heated with barium hydroxide solution at IOOC, yields nicotinic acid, malonic acid
and methymine.
co_ r __
r -0¼ Ira h b0th
S J-OH +
i-kL
—. Co
©cc,P41
OCØOM
C$1
#.(or.wfc4clo
N1CT!N(
WOQTW1
(7) Finally, the structure of nicotine was confirmed by the foliowmg synthesis axom-
$ished by Spath (1928).

1267
Alkaloids
CH2—CH2
-- CH2
AfVWLATION
ELECTROLYTIC -
H, O
cc CO REDUCTION CO
p4 Ii
SUCCINIMIDE 2-PYRROL Ilk.WE
CJ CMC'
I
J,
C2HONa
(ii) + (_CHS OH) CO CH
CO CH
Q
N a
(rHYL N/COT/NATE CH3

043
tr2
CO — CH —CM2 CO CH,
- 1300 [( J 100H 1:H 2

IlH
Of NH
I
CM3
,8-KE70W/C ACID
TABLE)
CHk7
CM Ct-I2 CH CH,
Q
KOM
'
iOO°
Ct-I3 N CM3
(±) —NICOTiNE
(iii) The racemic alkaloid obtained is resolved by means of (-I-)-tartaric acid to get
(—).nicotine which is found to be identical with the natural alkaloid.
ATROPINE
(the
This alkaloid is present in the stems and roots of the plant Atrapa belladonna
"deadly night shade") in traces. It is believed that the original alkaloid Is (_)-hyocyarnine,
which is usually racemised to the optically acitive form, atropine, during isolation.
Atropine is obtained by treating the plant juice with alkali, followed by ex-
IsoI*tios.
traction with ether. The crude alkaloid is purified through oxalate formation, fractional recrys-
tallisatic,n, and treatment o f the salt with alkali.
Atrophic is invariably prepared in the laboratory as well as commercially by the recemi-
sation of (-).-hyocyamine by heat or alkali.
1268
Properties. Atropine is a white crystalline solid, mp 116-117°C. It is optically inactive,

basic in character, and having bitter taste This alkaloid has a specific action when dropped
into eye. It dilates the eye pupil and paralyses the accomodation muscles of the eye temporarily.
Therefore, i t finds extensive use in ophthalmic practice.
Ati opine is also used in medicine as an antispasmodic, a substance which relieves muscle
spasms such as those of intestines.
Structure. (I) The molecular formula of Atropine has been determined to be
C,7I-I,NO3.
(2) The alkaloid on hydrolysis with HCI at 130C or with alkali at 60°C, yields
(±)- tropi c acid and tropine.
Hf
C17 H,3 NO3 + H 20 -.+ C.H J0O, + CaHiNO
atropine 10 (±)-tropic tropinc
acid
Therefore, atropine is an ester of tropic acid and tropine (tropine tropate). If we can
elucidate the structure of tropic acid and tropine, we can easily construct the structural formula
for atropine.
(3) STRUCTURE OF TROPIC ACID
(i) It has the molecular formula CIHJOO.
(ii) As shown by the usual tests, tropic acid molecule has one —OH and one —COOH
group.
(iii) When heated with barium hydroxide, it dehydrates to form atropic acid, which
upon oxidation with chromic acid yields benzoic acid, C 6l-15 C001-i. This shows that a benzene
nucleus is present in tropic acid as also in atropic acid. Therefore, the above reactions can be
represented as
—H10 [0]
C,115—CIFI3OH--COOH -.+ C 1 H5—C2H2_cOOU
tropic acid airopic acid
-b CIH6—COOFI
benzoic acid
The two possible structures for atropie acid are
QIZ
C 0I6—C--COOH CIHS—CH=,CH—COOH
1 11
We know that structure 11 is cinnamic acid and hence atropic acid has structure I.
Theoretically we can get the formula of tropic acid by adding a molecule of water to
CH,
unit in structure I. Since it can be done in two ways, tropic acid can be assigned the
structure Ill or IV.
5HOH
CH1—C—COOH C,H5—C—COOH
'OH H
HI IV
The structure IV represents tropic acid since structure HI is known to represent afro/ac-
tic acid. -
(iv) The structure of tropic acid has been confirmed by the following syDthe$i$
(Mackenzie, Wood, 1919).
CHr.. HCN CH, "Cf ,CN H0 CH, JCOOH
-.
CH( C6H5/ OH Hf CH, / "OH redaced
acetophenonc cyanobydrm presore

Alkaloids
1269
CH,
CHOH
Ha H,. 1
,CH CI K1CO1
C—C—COOH
1-I -+ >C -. C,H—C--cOOH
ether S
CaH ' 'COOH .1
H
tropic acid
The product is found to be identical with the tropic acid obtained by the hydrolysis of
natural alkaloid
(4) STRUCTURE OF TROPINE

(1) The molecular formula of tropinc has been found to be C4H15N0.
(ii) As shown by the usual tests, it contains one —OH group.
(iii) On oxidation with chromic acid, Iropine gives a ketone tropinone, indicating the
presence of secondary alcoholic —OH group.
-' -'
CIHUN ' >CHOH -
(ropipe .J'
101 C7H1N J ')co
tropinone '
(iv) Tropine takes one molecule of methyl iodide, demonstrating the presence of a
tertiary N-atom.
CH15ON + CHI -_ CaHuON.C}IaI
tropinc meth iodide
(v) Wilistalter observed that tropinone (obtained by oxidation of tropine) reacts with
benzaldehydc to form dibenzylidene derivative, suggesting that the kèto group is flanked by two
methylene groups, —CH,-_CO—CH,.--. Therefore, tropinone can be written as 11 and trepine
as I which explains the reaction as below.
—CH H
c=CH—C,H
[01 ,H1CHO
I.
6HIN CHOH - HN cS co -. c8HN
[—CCH, C—H,
[—O
—C=CH-CH,
I (tropine) U (tropinonc)
III (dibcczyljdenc derivative)
(vi) Tropinone on chromic acid oxidation gives (±)
4ropinic acid containing the
same number of carbon atoms. This shows that tropinone is a cyclic ketone.
CS H vN OC,H,N j :
100H
L
tropiccee (trvpinlc acid
(vii) Tropinic acid upon further ozidation yielda N.
methylsuccjnjniide, idicating the
presence of N-mcthylpyrroljdjnc ring ayltan.
r.qop/M(ci4c/D
tol,, I.
N-M(TIYLS11CCIN1MD(
(viii) Tropinic acid on exhaustive methylation (EM), leads to the formation of an

unsaturated dicarboxylic acid which on hydrogenation gives primelic acid.

A4vonced Organic Chemistry

1270
CH,—CH,—COOH
EM H1
TROPINIC ACID —p UNSATURATED ACID —* CH,
cat. .
CH,— CH — COOH
pimclic acid
Hence tropinic acid must contain a straight chain of seven carbon atoms and tropinone
a seven-carbon ring. The presence of seven-carbon ring is further supported by the fact that
Iropine when subjected to exhaustive methylation yields tropilidene (cyclohepttriene).
r—cH.=cH
EM I
TROF1NE —p CH
CH=CH—CH
-c
(cyclohcp(tflcOC)
From the reactions discussed above it follows that tropine, tropinone and tropinic
(ix)
acid may be represented as
H'CH_?HaCH1H—, 1Hs_?H_COOH
N.CHa CHOH 14.CH3 CON.CH 3 COOH
I I I I
TH.—C CHa CH1—C11
tropinonc tropnsic acid
tropine
The structure of tropinc was confirmed by numerous syntheses given from time to
(x)
time. Robinson synthesised tropine as follows.
CH,—CH—CH, çHI_CH_—CHI
CH. —CHOHHCH5 I .cH1 cHOH
I
E I .cHa O —+ ZnJHI
+ N—CH5 + CO
HCH1 CHICH H5 CH,—CH— i
1H,,H0 H
tropine
(5) Finally the structure of atropine is established by combining tropinc with tropic
acid in presence of HCI.
,H5 CH5_CHcH2 CA
CH,—CH—CH,
I I l.lCl I
- N.CHS CH_O—CO--CH
.CH3 CHOH + FIOOC—CH I
II I CH1OH
CH5 CHCH 5 CH 1OH CH1—CH—Ct1a
atrophic
tropine tropic acid
Tte product obtaind is identical with the natural alkaloid.
QUESilONS
1. Give a precise definition of the term 'alkaloid'. Could you say if this definition is'perfect'?
Discuss the occurrence of alkaloids as natural products. How are they isolated from plant
2.
material in which they are found 7
Give the physical characteristics of alkaloids in general, elaborating their physiological activity
3.
and basic character.
Give the modern classification of alkaloids based on the nature of the heterocyclic ring system
4. thcir molecular structure. Give at least one example of eah type, also mentioning its source and
present in
specific physiological activity.
Write a brief note on the following alkaloids: primaquinine, campioihcein, papaverint.
5.
morphine, and LSD.
Mkalolds liii
6. Give an outline of the procedures followed for the determination of the structure if alLaloicis.
Make a special mention of the more sophisticated physical methods introduced recently for the elucidation
of structure of aikaloidi.
7. Write a note on'Exhaustive Methylation Degradation method' as auplied to find out the hetero-
cyclic moiety present in the molecule of an unknown alkaloid,
I Describe the occurrence, isolation and properties of conilne. How was its structure determined?
9. What a,e aaIoide 7 How as da isolated huts nainesi faoducts? (Worth Eastern Hill BSc Hone, 1993)
10. Ibscuss thee traction olalkaloide huts plaits and their grsrnl properties. (Bazoda BS, 1993)
II. What as alkaloids 7 How aedayclaasthcd 7 Wnte thestrachual frmaslaofcoenne. (Ka iagata BSc III, 1993)
12. What are alkaloids ? What are the geseeai methods for the thcirheion o(t*niclure of lkaloidc?
(Sanrbalprr, BSc FIrms, 1994)
13 What ace alkal 'Write the slrscsure of atropine. how is tnspic acid detained (ruin atropine ? Give evidence For the
51flJcuI5 of tiopic add. (Kerala BSc. 1993; &snrby BSc.
1994)
14. Write a note on: Exhaustive isathyblion. . (Andhra 1/k, 1994)
15. Watc a note on: Ajkiloidel tcts. (South çi9aiw BSc 111, 1993)
16. Give de synthesis of the following cu,puswxls:
(a)Oiuisw ; (10 Pipthc acid; and (c) Nicotine (Madras 1/Sc. 1994)
17. Describe bow the structure of tdcoiine was cstAthshrA (Bez*wspur BSc, 1992)
II' Describe how the structure of qoirino was established. (Andhra BSc, 1993)
19. Describe how the structure of connos was established. (Madiueu BSc, 1994)
20. Describe how the structure of piperine was established, (North Bengal 1/Sc Hoes. 1994)
._.L•:... ............
Chapter 49
Terpenes
Many of the fragrant components of plants are volatile with steam and may be isolated
by steam distillation, solvent extraction, or other treatment of the plant. These components
are called the Essential oils. They are widely used in the perfumery, food flavourings, and
medicines- The essential oils are not pure single compounds. They usually consist of mix-
tures of hydrocarbons containing 10, 15, 20, 30 or 40 carbon atoms or their oxygenated
derivatives. These individual compoents of essential oils are called the Trpeaes or Tpoids.
THE ISOPRENE RULE
The structure of terpenes is based on a basic "building block" of five carbon atoms.
Their .a-bon skeletons can be constructed by linking together of C 5 units branched at the second
cah,n atom. The Isoperene Rile states that terpene skeletons are formed by linking together
I I 4
C—C--C--C units (Isoprene taiUs) through carbon atoms 1 and 4 (head-lo-!ail), carbon atoms
I and I (head-to-head), carbon atoms 4 and 4 (lit-b-tail) or combination thereof. The

head-to-tail arrangement is most common. This isoprene rule has proved to be of great value in
deriving the structure of terpenes.
CH, C c c
I (1)
/C\/C (TAIL) /C/\/\/C
CI (READ)
ISOPRENE /SOPRENF UNIT ISOPRENE 11N115 UNK rP HEAD TO 7AJL

Examples of some common terpenes are shown in Fig. 49-1. Dashed lines are used to
indicate how the formulas can be divided into isoprene units.
Ob COM
Aimo
G.,
t-
\1/
flO4, (T) 4..
-al
N x
DIPINTEkE 6W.IIOL
C,,
PM/INK
Fig. 491 Some common terpenes and their division into Isoprene units.
1272
Teipefles 1273
ISOLATION OF TERPEN!S
Terpenes are isolated from essential oils present in plants. The essential oil is extract-
ed from the plant tissues by four methods (1) Steam distillation ; (2) Digestion with solvents;
(3) Expression; and (4) Adsorption in purified fats. Method (1) is the one most widely used.
The p!ant tissue is mascerated and then steam distilled. If a particular terpene is decomposed
under these conditions, it may be removed by extraction with light petrol at 50°C and the solvent
distilled under reduced pressure. Alternatively, the method of adsorption in fats may be
employed. For example, the f'ower petals are spread over molten fat until the latter is saturated
with essential oil. The fat is then digested with ethanol to remove the essential oil from it.
Essential oils obtained from plants as above usually contain a number of terpenes which
are separated by fractional distillation or chromatography. Gas chromatography has been
particularly useful.
PROPERTJFS OF TERPENFS
(Physical). Most of the terpenes are colourless fragrant liquids having a boiling point
between 150°and 200° C. They are lighter than water and are readily volatile in steam. They
dissolve in organic solvents, but usually not in water. Most of them are optically active
although their is no prevailing direction of rotation; some are dextro, others are loevo.
(Chemical). Most of the terpenes being unsaturated hydrocarbons, are highly reactive.
They undergo addition reactions with hydrogen bromide, bromine, hydrogen, nitrosyl chloride,
and ozone. They also form characteristic addition compounds with NO, and NOBr, which are
used in their identification. Most terpenes are oxidised easily and tend to resinify upon exposure
to air.
CLASSIFICATION OF TERPENES
Terpenes are classified according to the number of isoprene units they contain. The
classes found in nature are listed in Table 41,
Table 491. Classes of Terpenes
Number of Number of
Class Ca.rbon Atoms Isoprene U,ilg:
Monoterpenes 10
Sesquitcrpenes 13
Dfterpenes 20
TritetpeDeS 10
Tetraterpenes 40
Polyterpcces 5i
A. MONOTERPENES (Ca)
The mcrnoterpenes contain ten carbon atoms (two isoprene units). They may occur as
open-chain (acyclic), monocyclic or bicyclic compounds. Some of the important members of this
class are described below.
MYRCENE, 2.MethyI4-methyleee.2,7-octadiene, CH1
Myrcene is an open-chain monoterpene hydrocarbon. It is found in verbena and bay oils.
CH
N2C
II
CH2
L
H2&
CH

H3C / Cj-q3
MvRCeVe
Organic Chemistry - 81
1274 Advinced Organic Chemistry
For simplicity, the structures of rerpenes are frequently written with line formulas. A
corner is meant to repreit nt a carbon atom with appropriate number of hydrogen:. A line branch-
ing off the structure represents a methyl group, not a hydrogen Thus the above structure of
myrcene may be written as
1"\
---
MYRCEN(
Myrcene is a liquid, bp 166-81
C. It undergoes catalytic hydrogenation to form decane,
C 0 H,,. It reacts with maleic anhydride to yield the corresponding Dials-Alder adduct.
Myrcene undergoes ozono]yis to give a mixture of formaldehyde, acetone, and a ketodialdehyde.
CH1 0
4-
H2CV CNCN 0 1
h2 C0
I
M01
+ (2)Zr-i-HO
II
24—C—H + CH3 - LCH 3 -f
H2C c H2CN
rOp MAtDE/jytE ACETOIVE
N
CH
0
+.
C X(TOO/ALD(AIVDF
HC CH,
CITMAL, 3, 7.Dimethyl.2,6-octadlen-l-al, C50H0

Citral is widely distributed and occurs to the extent of 70 to 80 per cent in lemongrass
oil. It is also found in oil of orange, oil of lemon (6 to 7 per cent) and in citronella oil.
Isolation.
The essential oil containing citral is treated with sodium bisulphite solution, when
crystalline citral bisulphite derivative is obtgined. This derivative is then hydrolysed with
sodium carbdnate to give pure citral.
Structure o f a
The structure of citral has been deduced from the consideration of facts and conclu-
sions such as the following
(1) Elemental analysis and molecular weight determinations show that the molecular
formula of citral is C1,H1.O.
(2) Citral reacts with bromine (2 molecules) to form a tetrabromide derivative. This
indicates the presence of two carbon-carbon dodble bonds in the citral molecule.
(3) Citral reacts with hydroxylamine to form an oxime, It also adds sodium bisulphite.
These reactions indicate the presence of an aldehyde (—CHO) or a ketone (—CO—) group..

m'penes 1275
(4) Citral undergoes reduction with sodium amalgam and water to give a primary alco-
hol geraiiiol, CL,H 2O. It undergoes oxidation with the silver oxide to yield geranic acid, C,H14O,,
containing the same number of carbons. These reactions indicate the presence of an aldehyde
group.
0 0 0
I 2H to] II
—C—H - —CH1OH; —C—H -p —C—OH
UV Studies indi Fate that the aldehyde group in citral is present as a part of an
, -unsaturuted carbonyl system.
(5) When citral is heated with potassium bisulphate, it is converted to p-cymene. This
indicates the relative positicns of methyl and isopropyl groups in the citral molecule.
tjH3
KHSO4 HC CH
C10H6O H I
HC/CH
CITRAL
H3C\CH3
db-CYMINE
(6) Citral undergoes hydrolysis with potassium carbonate to give 2-methyl-2-hepten-
6-one (methylheptenone) and acetaldehyde.
iI.1
C10H160 -
UrRAL
112 0
H7C
I + CH3—C--H
. ACErMop?yo
NH
H 3 C CH,
ME TH YLHEPTENON'E
The above evidence indicates that citral has the following structural formula:
r3
H2C7CH
H2 C. .HO
/C\
I.1 3 c CH
CJTR4L

1276 Advanced Organic Chemrstr•p
This structure of citral has been confirmed by its ozonolysis and synthesis from
2-methyl.2-hcpten-6-one.
Ozonolysis of Citral. Citral undergoes ozonolysis to give acetone, glyoxal, and levulinic
aldehyde. This reaction clearly establishes she positions of the two carbon-carbon double bonds
in the citral molecule.
CH,
H H 0 0 0 H2C'
ICH, L-0. — C — CH3 H—C—C—H
(2)Zn+ H20 +i
H 2 C Cl-tO HC
N CH
ACETONE CLYOXAL
H
+ C 0
LEYIIL /ti'/C 4L40(H4)(
CH.
CITR4L
Synthesis of CitTal. Citral can be synthesized from 2-methyl-2-hepten-6-onc (methyl-

heptenone) by the following three steps.
Step 1. Methylheptenone is subjected tp Reformatsky reaction and hydrolysis to give

a -hydroxy acid.
CH3
CH3
C—OH
/ N
COOH
H2C7 ()Zn -I- 5CH2COC2H5
(2) t-lO H3CN
H2CN
CH
C
/\ H3C / \CH
l-4C CH3
d8HYDR0XYO
41E!WVL#EPTEtiONf
Step 2. Dehydration of -hydroxy acid with acet i c anhydride gives geranic acid.
CH3
Va
0 0
H?C , CFI2COOH CH —O—CCH CH
HC b.0) H,C COOH

NH CH
/C \
l-43C
g -HYORQXY ACID GERANIC AC/C)

Terpeaes 1277
Step 3. Distillation of a mixture containing the calcium salt of geranic acid and
calcium formatç yields citral,
CR3 \ 043
( H 2( CH \
0 H2CH
H2C coo Ice + (H.J0)2c0 H0 2CeCO3
Hi:
CH I CALCIUM
FORMAT(
C
HC\CH3 H3 C "CR7
CA4(/014 SALT OF CI TR AL
C, ERA ACID
Georira Isomerism in Citral
Citrl exists i n two geometrical forms, known as citral-a (ge,'anial) and citral-b
(nera 1).
lxC
NCR
C\
H
=
(HC H2C
CK
0
fl
In geraiuI the methyl and the aldchyd j-oups are cis to each other and in neral they
are it. ,u, Both ftese forms occur together ii, vaiying amounts in natural oils. The unqualified
term citial us.ially refers to the mixture, The configurations of these two isomers have been
determined from a consideration of the rate of cyclisation of their correspondina alcohols.
Proper" of cwd
(Physicat). Geranial and neral are yellow fiquids with the same boiling point, 118C4
20 mm.
(Chemical). Geranial and neral give the same chemical reactions, that is, the reactions of
alkenes and aldehydes. Some of the important reactions of these isomers are listedw Pig. 492.

CH=Nc4-1
NHzOH
GERANIAL OXrniE
CH2OH
2 [o
Na—Hg
GERAN/OL
COON
. [0)
AçQ
CHO
GERANIC AC/C
0 0
ij O II CHO
/N CH 3 — C — CH3 + CH3CH2CN2O
(ERA N/AL ACETONE H0
LEW/UNIC
6LYOXAL ALOEHYE
CH3
CR 3 -----CH ' -- H20
A
b– CYM('JE
K2C0
CH3 — C — H + CH 3 CCH,CH 2 CH C (CH I )2
ACETA4OEA1YtAE ,31E/WYUIEPT(NQNE
Fig. 492 Some Important reactions of geranial. These reactions

are also given by octal.
Terpenes 1279
Uses of CftraI
Geranial and neral are used for scenting cosmetics, perfumes, soaps and in lemon
flavours. Geranial is also used in the manufacture of geraniol.
GERANIOL, 3,7.Dimethyl-2,6-oc!adien-1-ol, C10H180

Geraniol is the alcohol corresponding to geranial. It is found in the oils of rose (40 to
50 per cent), palmarosa (70 to 80 per cent), geranium, eucalyptus, and citronella.
Isolation
Geraniol is obtained from the cheap oil of palmarosa. The oil is treated with anhy-
drous calcium chloride with which geraniol forms a crystalline addition product. This crystalline
addition product is then decomposed with water to give pure geraniol.
Structure of Geraniol
The structure of geraniol has been deduced as follows
(1) Elemental analysis and molecular weight determinations show that the molecular
formula of geraniol is CiOH,aO.
(2) Geraniol reacts with bromine (2 molecules) to form the tetrabromo derivative
(2,3,6,7 .tetrabromo-3,7-dimethyl.l-octanol). This indicates the presence of two carboi.carbon
double bonds in the geraniol molecule,
(3) Geraniol does not form an ovime with hydroxylamine. This indicates the absence
of an aldehyde (—CHO) or a ketone (—CO—) group.
(4) Geraniol can be obtained by the reduction of citral . a (geranial) with sodium
amalgam or with ethyl or isopropyl alcohol in the presence of an aluminium alkoxide catalyst
(Meerwein.Ponndorf-Verley reduction). Geraniol also undergoes oxidation to give citral-a.
These reactions indicate the presence of a primary alcohol group in geraniol and its relationship
with citral-a.
The above facts clearly show that gcranio[ has the following structure. Notice that the
methyl and the —CH2 OH groups are cis to each other.
(H3'
'.4--I
H2C /C72OR
7CFt2OH
/CN
H3C
&(/ANIOL
Properties of Geraniol
(Physical). Geraniol is colourless liquid with a sweet rosy odour. It boils at 23OC.
1.
Geraniol is insoluble in water but dissolves in ethanol.
(Chemical). Geraniol gives the reactions of alkenes and primary alcohols. Some of its
important reactions are listed in Fig. 493.
94, çH,
29r, I I
CH3 C14,CH—cHCH2OH
11,
2,3,6,7 TE7RA8ROfO
3, 7-ornT/iYL --007N.(04
çH,
2H, I I
cH3CH142cI2o'3cH CH2Cfr420H
—N1
3,7- £)/MET/1YL-1-XTANO
CHO
(0I
-
(Cr0])
GtRAN!AL
&ERANIOL ±)- CH,--CH3 + CH3LH2CH2C00H

KMnO4
ACETONE PCRfrI/C UVL/UNf C
ACID ACID
Oil H1SO4
c(- TER P/MEOL
PBr
GERANYL 8RW/DE
Pig. 493. Some important reactions of geranloL
1281
Tpenes
Uses of Gesimol
Geraniol is used in the manufacture of artificial rose scents. It is widely used in perfume,
cosmetic, and flavour industries. it is also used as an agent for luring insects into traps.
NEROL, 3,7-D1me1hy1-2,6-OctO4len-1-01, CoHilO
Nerol is the alcohol corresponding to neral. It is found in neroli oil (orange blossom oil)
and oil of bergamot.
C
H2C
CH20H
= 1 CH20H
R2C
H ' C'/ CH3
NEROL
Notice that nerol is the geometric isomer of geraniol. In nerol the methyl and
the —CH 80H groups are trans to each other and in geraniol they are cis.
Nerol is a colourless liquid, bp 225°C. It has a rose-like odour. Its chemical properties
are similar to those of geraniol.
Nerol is used in the preparation of artificial rose scents.,
Determination of the Configurations of Nerol and Geraniol

The configurations of nerol and geraniol have been determined from a consideration of
their reaction with dilute (5 per cent) sulphuric acid. Both isomers undergo cyclization with this
reagent to give a.terpineol.
CH2O
DtlHsSO 4 i HSO4
FAST SLOW
OH
NEROL a-TERPINEOL GERAAiIOL
Nerol undergoes cyclization nine times faster than geraniol. This indicates that the
—CHOH group in nerol must be nearer to the carbon () which is involved in ring formation.
p-MENTHANE, 4.1sopropyl-1-methylcyclohexane, CwH1
p-Menthane is a monocyclic monoterpene. For naming other such terpenes, p.men
thane is used as the parent substance. The positions of the substituents and double bonds are
indicated by numbers, the conventional method of numbering being shown below.
ii (45-5211982)

'CR3
H2C6 2CR2
H2CS 3CR,
NH/
8CM
H,/ NH,
fr-/dENT/lANE
p-MenUiane does not occur in nature. It is obtained by the catalytic hydrogenation

of p-cymene or limortene.
CH, CH,
I II + 3H1
Y CH CH
H,C/\cH3 H3C
1b -CYMENE
4ENTHOL, 3-p-Menthanol, 3-Hydroxy-4-isopropyl-J .methylcyc!ohexane, CHO

Menthol occurs in the oil of peppermint to the extent of 80 per cent. When this oil is
cooled, crystals of menthol are obtained.
M2C
L CR2
OH
H, CH—OH
CH
MENrHOL
Syials. Menthol is prepared by catalytic hydrogenation of thymol.

1283
Terpenes
043
Ni
LOH +3H2
C CH
H3C / H 3C / "013
MENTHOL
r'1V4iOL
Properties (Phync,(J. Menthol found in the oil of peppermint is laevorotatory. It is a

colourless solid with a strong minty odour and cooling taste. It melts at 42 CC and boils at 216C.
Synthetic menthol is s (±)-mbiU(e
(Chemical)- Menthol vves the reactions of a cyclic secondary alcohol.
(I) It undergoes oxidation with chromic acid to give the corresponding ketone menthone
(3.p.menthanOfle; bp 20TC.
101
OH (Cr03)
MENTHOL MENTHONE
(2) It undergoes dehydration with potassium bisulphate to form 3-merithene (3-p-men-

thene; bp 168'C) by removal of the —OH group from C-3 and the hydrogen atom from C-4.
A
+ H20
Ai(NTHOI. 3-MEN THEME
(3) It undergoes reduction with hydriodic acid to yield p-menthane.

Uses. Menthol is used in pharmaceutical preparations because of its anaesthetic and
antiseptic action. When used in inhalers (Vicks Inhaler:), its vapours have a cooling and mildly
anaesthetic action upon inflamed nasal tissue. Menthol is used in face creams, shaving creams,
tooth pastes, and ointments because of the cooling sensation that it imparts to the skin It is
also used in candles, chewing gums, and certain brands of cigarettes.
L1MONEN 1,8-p-Menthadiene, CH,,
Limonene is an important monoterpene hydrocarbon. It is opt&cally active
(4)-Limonene occurs in the oils of orange, lemon, caraway, and lemongrass. (_)-LUflOflCne is
found in pine needles and in peppermint oil. (±)-Limonene, also known as dipentene, occurs
in turpentine oil Of these three optical isomers dipentcne is the most important
Structure. The structure of dipentene (or limonene) has been derived as follows.
(I) Elemental analysis and molecular weight determinations show that the molecular
formula of dipentene is CH11.
(2 Dipentene reacts with bromine (2 molecules) to form a crystalline tetrabromide
(mp 105C). It also reacts with hydrogen bromide (2 molecules) to give the corresponding
dihydrobromide. These reactions indicate the presence of two carbon-carbon double bonds in
the dipentene molecule.
(3) Dipentene undergoes dehydrogenation over heated sulphur to yield pcymenc. It also
undergoes catalytic hydrogenation to give p-menthane. These reactions tell us about the nature
of the carbon framework of dipentene.
cl-i3 CH3
H2
A
y
DiP EN TENE
CH (H
NCH,
HC/ NCH,
-CY/4ENE 1' -M(NTHA,vE
(4) Dipentene can be obtained by dehydration of a-terpineol with potassium bisulphate
or oxalic acid. The elimination of water molecule can take place in two ways, giving (A) or (B).
CH CH3 . Cl-i3
KHSO
OR
/CN
H H3CcH2
(A) (B)
-TERp/NEOL
Structure (A) can show optical activity because it contains an asymmetric carbon atom
(). (B) cannot be optically active because it is a symmetrical molecule. Therefore (A) repre-
sents optically active lisnonene or its racemic modification dipentene.
The above facts clearly show that dipentene has the following structure.
(H3
H
=
)H
/C A
ft3 C (t1
DIPE/1TE'IE

Terpeies 1285
Sy*tes. Dipentete may be obtained:
ii) By heating -terpineol with potassium bisulphate.
IHIII 41
A + H20
a- U P PINE 01 0IPENTEHE
(2) By heating isoprene in a seated tube at 2800 C.

210C N

ISOPRENE QIPENTENE
(2 .ott(iit,$)
(3) By heating geraniol with dilute phosphoric acid.
7CH20R
dII.H)P0
GERANIOI aiPENItNE
PmpertW (Physical). Dipentene is a liquid, bp 1703°C1695 mm. It has a lemon-like

odour. It is insoluble in water but dissolves in ethyl alcob 1 and diethyl ether.
(Chemical). Dipentene gives the reaction nf aIkaIeres. Some of its important reactions
are listed in Fig. 49•4.

Advanced Orgonk Chemistry
1286
CH
frCYMENE
CH3

28d'C 2 CH=C-_-CHCH3
,sopRm(
2B2
T(rRASROP4'OE
OIP(NT(NE
DIN YOROBROMIDE
2H2
-Ni,
p-M(NT/WJt
NO
P400
1p
N
N,TRO5OCN(O0JD(
Fi& 49•4 Somc inipoiiit rctioi of dp.rnene. These rsacoes are
ahosiwàby1im00CU
Terpenes 1287
Uses. Dipentenc is used as a flavour in foods, beverages, and pharmaceutical prepara-

tions. It is also used in the manufacture of resins, isoprene, p-cymene, and p-menthane.
r-PINENE, C01111
-Pinene is a bicyclic monoterpene. It is present in nearly all essential oils. The most
common source of a-pinene is turpentine in which it occurs in both (+)- and (—)-forms.
cH3
j li^c^
_ _CH31r
H2
11-11'
c( -PINE/YE
s-Pinene is a liquid, bp 154-6° C. It gives the reactions of alkenes. e-Pincne reacts
with dry hydrogen chloride to form colourless crystalline pinene chloride, C, 1HC1 (mp 131°C.)
This crystalline compound has a faint camphor-like odour and is known as artificial camphor.
Turpentine oil which is mostly pinene is used as a solvent for resins, as a thinner for
paints and varnishes, and in the commercial synthesis of camphor.
CAMPHOR, CH,.O
Camphor is obtaind by steam distillation of wood, leaves, or bark of the camphor tree.
This tree grows mainly in Japan and Formosa.
r
HC—C-_<H3
,,,CH2
CAMPHOR
Commercially, camphor is obtained from a-pinene by the series of reactions shown in
Fig. 49.5.
,o
0.
(PfN(Nt
-.-.-c
5ORV

I5050ON'L !J0fMfO
_L (
tr
C4MPH
AC(UT(
Pig. 495. Commercial synthesis or camphor.
Camphor is a colourless, crystalline solid. It has a characteristic strong odour. It
melts at 179°C and boils at 207°C. Despite its high melting point, camphor sublimes at room
temperature. -It occurs in both the (+)- and ( —)- forms.
Cmphor is a ketone and shows the properties ' characteristic of the carbonyl group.
For examaple, it forms an oxime with hydroxylajnjne. It is reduced by sodium and alcohol to a
secondary alcohol borneo! (mp 209°C; bp 213°C).
1288
Camphor is used as a plastisizer for cellulose nitrate (smokeless powder). It is used in

pharmaceutical preparations because of its analgesic, stimulant expectorant, antiseptic, and
carminative effects. In the chemical laboratories, it is a convenient solvent for the determination
of molecular weights, since its cryoscopic constant of 40 is unusually high. It is also used as a
moth repellent, in embalming fluids, and as a preservative in cosmetics.
B. SESQU1TERPENES (C6)
The sesquiterperes contain fifteen carbons (three terpene units). Like the monotcrpenes,
they can he found either a open -chain, such as farneso!, an oil found in flowers, or
as cyclic compounds, such as eudesmol, found in eucalyptus oil.
OH
iio
4RNE50L E(JDE5MOL
C. DITERPENES (Ce)
The diterpenes contain twenty carbons (four isoprene units). Vitamin A, found in fish
liver oils, is a monocyclic diterpene. It is required for the production in ow eyes of visual pur-
ple (rhodupsin), which is necessary for sight. Visual purple is composed of a protein complex
and prosthetic group retinene, the aldehyde of vitamin A.
6c VITA 11N A
RE. TINEN E
Abietic acid is a tricyclic diterpene. It is the chief constituent of pine resin.
COOl-I
AB If TIC ACID
D. TRITERPENES (C..)
The triterpenes contain thirty carbons (six isoprene units). Examples of triterpenes are
These compounds are important intermediates in the biosynthesis of
squalene and lanosterol.
steroids. Squalenee-is also found in shark liver oil and lanosterol in lanolin (wool fat), which
of
is used extensively in hair dressing formulations.

rpen. 89
5QUA LE'VE LANOS TEROL

E. TETRATERPENES (C40)
The tetraterpenes contain forty carbons (eight isoprene Units). They are responsible
for colouring of many food stuffs, such as tomatoes, carrots, corn, egg yolk, watermelon, and so
on. The colour is caused by long conjugated polyene chains in these terpenes. Examples of
tetraterpenes are lycopene and ç3-carotene. Lycopene is responsible for the red colour of ripe
tomatoes and watermelon. p-Carotene imparts orange colour to carrots.
LYCOPENE
- CA,QOT(N(
F. POLYTERPENES (C,,)
The two most important polyterpenes are natural rubber and gutta-percha. In nat rat
rubber, the double bonds of the repeating isoprene units are cis; the molecules are able to b id
back and forth a little so that the rubber can stretch. Gutta-percha has the trans structure. Jt
is hard and non-rubbery. Gutta-percha is extensively used in electrical insulation and dentistry.
CHI C
)\ccC}=\:i
< - / - \
CHI
H
'5
:>''\\\CHI
La
GiTTA-pfrJ
NATURAL QU88E
QUESTIONS
I. What are terPenes? How are they classified? Write the formulas for several terpenes of both
open-chain and cyclic types and by means of dotted lines show the relation of each compound to isoprene
2. What are essential oils? How are they isolated from natural sources?
3. Three Constituents of essential oils have Uie common molecular formula, C 10H14
tion they take up respectively six, four, or two 3 tins of hydrogen per molecule, Name some 0. Upon reduc
compound
correspondIng to these

1290
4. Tell how the structure of c iiral has been established.

5. How can citral be synthesized from 2-methyl-2-beptec4-ono?
. Predict the major product(s), if any, of the reaction of citrol with each of the following reagents
(a) NH5OH
(b) (i) O; (11) Zn + fJO
(c) Ag2O
(d) K2CO3 + l-i50
(e) KHSO4, heat.
7. Tell how the structure of geran (a! has been established.
8. How can geraniol be obtained from citral?
the following
9. Predict the major product(s), if any, of the reaction of geraniol with each of
reagents
(a) Dii. H5S05
(b) H2fNi
(c) Fir5
(d) KMnO4
(e) PCl
tO. Geraniol and nerol are geometric isomers, How will you determine their configurations
11. Describe how the structure oldipen:ene has been established.
12. How can dipentene be prepared from a.terpiseol or isoprene?
13. Predict she major product(s), if any, of the reaction of dipenlefle with each of the following
reagents
(a) S heat
(b) H5JNi
(c) NOCI
(d) HBr
(o) Heat at 280C
14. Show how the following compounds could be synthesized from the indicated starting materials.
(a) Geraniol from citral.a
(b) Citral from 2-methyl-2.beptefl-6'One
(e) n-Terpineol from geraniot
(d) Menthol from thymol
(e) Camphor from n-pinene
15. Writes note on Isoprene rule. (Bombay USc, 1993)

16, What sic Lerpenes ? How sit dy classified. (Anna BSc, 1993; Maclaces BSc, 1994)
17. Outline the synthesis of (a) a .Terpineol and (b) Camphor
is, Describe how the ssniccwe of citesi was established. (South Gujarat USc 111, 1994)
19. Describe tw the structure of geratuol was established.
20. Describe bow the structure of dipentene was eutablishesi (Bombay USc, 199()
21. How will you establish that
(a) Dipenienc contains two double bor.
(b)CitraJ contains an aldehyde gioup (Madwes BSc. 1993)
Eim (a) How are terpenes classified.
(b) Show that citral isan a, n-unsaturated aldehyde.
(c)Write structures of dii 1eret geometrical isomers oIcstsal. (Delhi BSc Hons, 1994)

Chapter 50
Synthetic Polymers
The development of modern technology has brought tremendous changes to our life-styles in
the last 30 years. One of the most significant changes has been the gradual replacement of natural
materials, such as wood, wool and cotton with man-made synthetic polymers. For better or worse,
we are becoming a 'plastic' society. In this chapter we will study how polymers are made and how
they are used.
Polymers are high molecular weight compounds, whose structures are composed of a
large number of simple repeating units. The repeating units are usually obtained from low
molecular weight, simple compounds, referred to as monomers. The conversion process,
monomer to polymer, is known as 'polymerisation'. The formation of polyethylene is an example
of this process.
REPEATING UNITS
•_
CH2=CH —'CH2—CH—CH--l2CH2---
ETHYLENE POLYETHYLENE
(MONOMER) (POLYMER)
The equations for polymerisation are represented as shown below, where n stands for a large
number.
n CH=CH2 11 +H,-,CH,
ETHYLENE POLYETHYLENE
Frequently, the end-groups of polymers are unknown - they may arise from impurities in
the reaction mixture. In some cases, the end-groups can be controlled. The properties of a polymer
are governed almost entirely by the bulk of the polymer molecule rather than the end-groups. To
emphasise the basic structure of the polymer, it is customary not to include the end-groups in the
formul&
Polymers are said to be linear, if the repeating units are joined together like links in a chain.
The chains may be branched, or joined together by cross-links, or both (Fig. 50.1). More exten-
sive cross-linking may lead to the formation of a three dimensional cross-linked oL net-
wort-polymer.
There are two main types of polymerisation processes addition polymerisation anL
condensation polymerisation. In addition polymerisation, all atoms in the monomer are present in
the polymer, but condensation polymerisation is characterised by the elimination of small molecules,
such as water, methyl alcohol, carbon dioxide, etc.
ii(iIl

1292 Advaicsi OW OwnWry
LINEAR POLYMER
(ROSS-LINKED POLYMER
BRANCHED POLYMER
Fu. 50.1 Linear, branched and cross-linked polymers
ADDITION POLYMERS
Addition polymers are formed by combination of alkene monomers to produce a single
huge molecule only. Examples are:
(I) Polyethylene (Polythene). it is obtained by polymerising ethylene. The reaction is carried
at 200°C and 1000 atm. pressure, with small amount of oxygen as a catalyst. At this temperature,
the oxygen reacts with ethylene to form peroxides, which initiate the polymerisation reaction.
PclymtS6tQfl
0. HCHz
ri CFIa'=CHa
ETHYLENE POLYECH.rD'.E
End-use. Polyethylene is used in packaging, houseware, such as buckets and dustbins, carpet
backing, cable insulation and flexible bottles.
(2) Polypropylene. It is obtained by polymerising propylene. The reaction is carried at

50-120°C and 3 atm. pressure, in the presence of aluminiwntrialkyl-titariium tetrachloride
(Ziegler catalyst).
CHI
p.Iyiriitia
nCH)—CH=CH2
PROPYLENE
POLYPROPYLENE
End-use. Polypropylene is used in making houseware, medical equipment (can be sterilised),

toys, electronic components. tubing and pipes, fibres and filaments, coating.
(3) Polyvinyl Chloride (PVC). It is obtained by polymerising vinyl chloride. The reaction is
carried at 80°C and 10 atm, pressure, with small amount of benzoyl peroxide (or lauroyl peroxide)
as a free-radical catalyst.
Cl Ct
PeIynwIlC'Ofl
n CHH -CH--CH
vWfl. C}&OIOE
Vinyl chloride is prepared from acetylene by treatment with HO in the presence of HgCl2.
HqCl2
HCCH + HCL-0 CH2=CHCI
End-use. PVC is widely used in imitation leathers, floor coverings, corrugated roofing
material, and gramophone records. With the addition of a plasticiam, the polymer
has a rubber-like texture. This is used in squeeze bottles, pipes, etc.

SynthefkFners
(4) Orion (Acrilan). It is obtained by polymerising vinyl cyanide. The reaction is carried at
40°C and atmospheric pressure with small amount of benzoyl peroxide (or potassium persulphate)
as a free-radical catalyst.
N CN
PoIyrflISOfl
n CH2=CW CH2—CH-]--
VINYL CYANIDE ORLON
Vinyl cyanide was once prepared by treating acetylene with HCN in the-presence of Ba(CN)2.
Oat (N
HCCH + HCN CH2=CHCN + 6H20
Now it is prepared by a cheaper process which involves catalytic oxidation of propene in the
presence of ammonia.
,
2CH 3 CH=CH 2 + 302 + 2NF13 2CH2 =CHCN + 6H10
End—use. Orlon is used as a synthetic textile fibre in clothing and carpeting.
(5) Teflon (PI'EF or Fluon). It is obtained by polymerising tetrafluoroethylene. The reaction

is carried at 30-40°C and under pressure with benzoyl peroxide (or potassium persulphate) as a
free-radical catalyst.
PoIr..ftaho
IF Fl
f
n CF=CF2
T(TRAFIUONOtTHYLtHE [F F1
T(FLON
Tetrafluoroethylene is prepared by treating chlorodifluoromethane with HCl at 900°C.
2CHCIF tP CF2 =CF2 + 211CI
End—use. Teflon is familiar because of its use as non-stick coating, particularly for cooking
utensils. Nirlep non-stick frying pans kIve teflon coating. Because of its low
chemical reactivity, excellent toughness, electrical and heat resistance, teflon is used
as insulation for electrical items and in the manufacture of gaskets and valves.
(6)Polystyrene. It is obtained by heating styrene alone at 132°C or in the presence of dibenzoyl

peroxide catalyst at 50°C.
yUEIsatA
n ^^CH=CH2
STYRENE POLYSTYRENE

1294 Actvamd 09aw C1ienii'iy
Styrene is prepared from benzene by the following reactions
6 6
CH2CH 3 CHCH2
© CH =CI4? F.Z03/Ct?03
____________
+
AtCt3 650%
BENZENE ETHYIBtNZENE STYRENE
End-use. Polystyrene is used in the manufacture of food containers, cosmetic bottles,

television cabinets, plastic cups, packaging and toys.
MECHANISM OF ADDITION POLYMERLSATION

Addition polymerisation takes place either by a free-radical or ionic mechanism depending uxin
the reagents employed.
Free-Radical Polymerisation
Free-radical polymerisation is catalysed by organic peroxides or other reagents which decompose
to give free radicals. Following steps are invnlved
(I) Chain Initiation. Organic peroxides undergo homiilytic fission to give free radicals.
Ti.ii bond
brook a
0 7a o
R—C-0-fO — C--R —4 2R—C-0 -'-+ 2R• + c021
p ( p QxIoF ubstsatt
(2) Chain Propagation Free radical produced in the above step adds to an alkene molecule to
form a new Irec radical.
---p R—CH2—Cl-12
ETHYLENE
This free radical can attack another alkene molecule and so on.
RCH2C'\CH2 —. RCH2CH2CH2CH2
RCH2 C1l 2 + nCH2CH2 R(CH2CH2)CHCH2
(3) Chain Termination, The chain can be interrupted when two free radical chains combine,
or by disproportiojtation.
COMBINATION:
2R(CH2CH2)nCH2CH2 -. R(CH 2 H2 )CH2 CH2 CH2CH2(CH2CH)R
DISPROPORTIONATION
R(CH 2 CH 2)CH2 CH 2 + R(CH2CH2)_CH42
R(CH2 CH2 )CH 2 CH3 + R(CH2CH2),CH=Cl

Note. Benzoyl or :-butyl peroxides are conmon reagents for free-radical polymerisaions.

1295
Synthef!cPVlv7nefs
it —-*_-, 2 + co,
(Cl-lhC-O_O — C(CH lJ —+ 2(CK1CO —+ CU3)C=o + 16H3

Phenyl or methyl free radicals will then initiate free-radical polymerisatioR.
- Polyinerisation of unsaturated monomers is complicated in practice by several factors that greatly
affect the properties of the product. One such problem is that free-radical polymerisation yields a
product that is not linear, but has numerous branches in It. Branches arise when the free-radical end
of a growing chain abstracts a hydrogen atom from the middle of a chain to yield an internal radical
site that continues the polymerisation.
Ionic Polymerisation
Ionic polymerisation is initiated by acids such as H 2SO4 , HF, or BF, with trace of water (BF, +
HO = HOBFW). Following steps are involved:
(1) Chain Initiation. Proton adds to the carbon-carbon double bond of alkene to give a stable
carbonium ion.
—, CH3CH2
H +
(2) Chain Propagation The car'bonium ion adds to another molecule of alkene to produce a
new carbonium ion, which can similarly add to another molecule of alkenc and so on
+ 4
CI-1CH 2 + Ci-t=CH2 -- CHCHCHCH
+ .4:
CK 3 CH 2 CH 2 CH 2 + nCH 2 CR —5 CFI3CH2(CH2CH2)nCH2CH2
(3) Chain Termination. The chain reaction can he interrupted by combination with an anion
(negative ions) or by loss of a proton.
(H
CH 3CH(CHCH)nCHCH —* C CH(CHzCR2)rCHChl + H2SO

poLy eThyLeNE (POLYMER)
For simplicity, ethylene has been used to illustrate the free-radical and ionic mechanisms of
addition polymerisation. The reactions require pressures of about 1000 atmospheres at 200C. Much
lower pressures and temperatures can be used with Ziegler catalysts which consist of a rialkyl
aluminium and titanium tetrachloride in an inert solvent. TE polyethylene produced by Ziegler
polymerisation has higher density than polyethylene obtained from high pressure free-radical
polymerisation and has the important advantage that it will withstand boiling water without softening.
COPOLYMERS
Copolymers are produced by polymerising two or more different monomers. Consider the
polymerisation of monomers A and B. When allowed to reactseparately,each gives a homopolymer.
When A and B are polymerised together, a copolymer is formed.
n —b -[-A-]- IOPIOPOIYM(R is FOONtO FROM ONE
r%A + nB —. -f-A--B-]- coPol-rM(R is FORM(O FROM TWO OR MORE
Copolymer structure my be either alternating, in which a definite structural pattern may be

observed, or random. -
Advanced Orgamic C?tecnstiy
ALTERNATING COPOLYMER:
nA + nB —4 _A_a_A_e_A_e_A_e_A—B_A—A-
RANDOM COPOLYMER:
nA + nB —k —A--A—B—A-8—B---A—B—A—A—B—A--8—A—A-9—B-
Saran is an important copolymer. It is obtained by treatment of vinyl chloride with vinylidene

chloride in the presence of benzoyl peroxide or lauroyl peroxide catalyst. Saran is used to make
tough food wrap that is very effective moisture barrier. Automobile upholstery can also be fabricated
from saran.
ci
n CH2 CHCI + nCH2=CCl2

polymerisation
P
I
tCH2C H—CH2—
cii
I
VINYL CHLORIDE VINYtEDEWE I
CHLORIDE LIn
SARAN
CONDENSATION POLYMERS
Condensation polymers are formed by combination of monomers with the elimination of
simple molecules such as H20 or 171-1 301-1. There are two main types of condensation polymers
polyesters or polyamides.
(a) Terylene (Dacron or Teron) is the most importarg polyester. It is prepared by heating
ethylene glycol with dimethyl terephthalale at 270-285°C in the presence of metal oxides.
HOCH2CHO[__+cH3oJ0c--coocH3
HOCH,CH 2 00C—)—COOCH 3 + Ctt,OH
'tact
at tech end
tOACRONI
The polymer melt can be spun into fibres and combined with such naturally occuthr.g
The combination of cotton and polyester yields a fabric (e.g., 60/40 cloth), that dries quiAy
wrinkling, yet still retains the coolness and comfort nfl 00% cotton. Polyesters have revolutionised
the cloth industry.
Ethylene glycol is manufactured by catalytic oxidation of ethylene to ethylene oxide which is
then treated with dilute acid.
0,1040
AS H/IlO
______
CH,—CH2 HOCH5CH20H
300'C
ETHYLLft ITHYLENr o&sca
S)nlUleLo PoiymefS 1297
Dimethyl terepbthalate is obtained by catalytic oxidation of p-xylenp followed by cs*erificaiion
of the resultant acid.
0. 0 0
CH 3 COOH
0
CH 3 COOH
p-XYUNE
0
TER€PHTHALIC ACiO
CH2O
0
COOCH3
COOCH
DIMfYHYL
TEREPHTNALATO
(b) Nylon-6,6 is the most Important polyainide. It is obtained by heating adipic acid with
hexamethylene under nitrogen at 180-220T. Nylon-6,6 derives its name from its starting materials,
adipic acid and hexamethylene, both of which have six carbons.
HOOC(CF4).CO 1OH +
I-
HOOC(CH 2 ).CONH(CH,)aNH, + HO
!•SC!Ofl
at •aCh •fld
+ COlCH2JCONH(CH)oNH-]_
NYLON-6, 6
Both starting materials can be prepared from 1,3-butadiene.
CH2==CH— CN=CH2
ctz,J,( tA -Addition)
CICI(2CH=CHCH2CI
I NGO
NC CH2CH=CHCH2CN
NCC H2 C I42CH2CH2CN
H2O/Hj
L IN
HOOC(CH2)COOH4— HZN(CH2)5NH2
ADIPIC ACID ItXAMETHYLEN(
0 IA PUNt
Nylon-6,6 was developed as a synthetic fibre for the production of stockings and other wearing
apparel. It was introduced to the public at the New York Worlds Fair in 1939. It is used to make
fibres for clothing and carpeting, filaments for fishing lines and ropes, bristles for brushes, and

molded objects such as gears and bearings. For the better application no lubrication is required,
because nylon surfaces are inherently slippery.
A similar polyaxnide, Nylon-6, is obtained by heating arninocaproic acid under nitrogen at
220-260°C. Nylon-6 fibres are widely used in carpets and, more recently, in water desalination units
0
N—H
poly merisation
1
II
H2P1—(CH2)5----C—OH (CH2)
A .tIC_NH(CHl)s.j_
E—AIffIOCAPROIC ACID C =0
CAPROt.A(IUM NYLON—
(on ivittr.,diotn)
Because of their ability to form hydrogen-bonds between the polymer chai g s (Fig. 502), nylons
show unusually high strength and make excellent fibres.
POLYMER CHAINS
/---------------------------/
CH2 CH2 Cl-1
/ 1
C=0---H —N C=0
K K
H—N C=O ---- H—^CH2
/
C
/CH2 CI
) CHZ Ct2
CI /'CH2 CH
CH 2 Cz
OC
N—H---- o=C"
CH /CH? C
, ,CH2 C J,CH2
CH 2 CH2 CH2
Fig 50.2. Slrucinre of hydrogen-bonding in Nylon
THERMOPLASTIC AND THERMOSETTING POLYMERS

A thermoplastic polymer is one which softens on heating and becomes rigid again on
polymer molecules and
cooling. This is because there are weak attractive forces between the long
these are readily disrupted on heating. Most addition polymers and some condensation polymers are
thermoplastic. Examples are : Nylon, Polythene and Polystyrene.
A thermosetting polymer is one which becomes hard on heating. It cannot be softened
by heating. Polymers of this type are often prepared in two stages. The first stage is the formation
of long chain molecules which are capable of further reaction with each other. These intermediate
polymers usually flow and can be placed in moulds. Colouring is often added at this stage.

Syn11iet Po(yrne.'s 1299
The second stage is the application of heat which cause a reaction to occur between the chains, thus
producing acomplex-network polymer. Exnmplesare: Phenolic resins, Epoxy resins, Polyurethanes
and Alkyd resins.
(a) Phenolic Resins. These polymers are made by condensation of phenols with formald hydc.
For examples when phenol is treated with excess formaldehyde and alkali catalyst, short chain
polymers are first formed. On heating, these chains increase in length which finally cross-link to
give a hard, insoluble thermosetting plastic Bakelite.
OH OH
OH
©JCH2OH
HCHO+O
PHENOL CH
HaO
+
HOCHjCH 2 0H etc.
OH
OH H OH CH2—..,-
VCYCv YH
CHz CH, etc.
AA
OH OH CH OH
BAKEUTE
Bakelite is widely used for making molded products such as handles on elecuical and cooking
utensils electrical plates and switches, appliances ; and as a bonding adhesive in plywood.
(b) Epoxy Resins. These polymers, which are known for their bonding properties. are used in
adhesives such as A raldite. Epoxy resins are prepared by condensation of excess chloroepoxyalkancs
with dih y ric phenols in the presence of NaOH catalyst at 50-60°C. For example,
0 CH3
nC' 2— C H—CHCl + nHO
CD— C _^DOH
CH3
OH CH3
OCH2CHCH2O(0)t
The polymer produced is cross-linked by heating with certain amines, when terminal epoxy
groups of the chains react with the amine, cross-linking the chains.
Epoxy resins are extensively used to bind glass, porcelain, metal and wood. These resins, because
of their inertness, hardness andflexibility make excellent protective coatings. Fibreglass boat hulls,
for example, have a metal frame coated with a thick layer of spun glass trapped in a set of epoxy
resin.
(c) Polyurethanes. These polymers are prepared by reaction of diisocyanates and diols in the
presence of stannic chloride or stannous octoate at 50-100°C.
A*ancdOrgwc Qeitastiy
nHO(CHOH + nOCN ) CHX NCO —'
-[ CONH )CHNHCOO(C H2O in
If triols and di- or triisocyanates are used, cross-linking can take place to give a thermosetting
polymer,
Polyurethanes can be spun into elastic fibres such as Spandex. If they are formed in the presence
of a low-boiling liquid that will readily vaporise as the reactants are heated, a semirigid polyurethane
foam results. Polyurethane foams are used in construction and interior decoration of buildings.
(d) Alkyd Resins. These are polymers derived from alcohols and acids/anhydrides. Glyptal
resin (a typical alkyd resin) is obtained by heating phthalic anhydride and glycerol at 180°C.
OH
b Co
+ nHOCH2 CHCH20H
HOOC
I.
OH
-
COOCH21_HCHz0_fH + nH2O
This can be dissolved iii a suitable solvent and applied as a surface coating. On heating, the
solvent evaporates and a hard, smooth, protective surface results, owing to cross-linking of the chains.
Ulyptals are mainly used as bonding resins and in alkyd paints.
NATURAL AND SYNTHETIC RUBBERS
(I) Natural Rubber

With the expansion of motor-car industry the demand for rubber increased enormously. Organic
chemists found that rubber is a hydrocarbon polymer built up from the monomer isoprene. Natural
rubber is polyisoprene.
CH3 CH3
II poty.n,t
H2C=—CH=CH2
IsoparN(
CHCHC
KATURAL RUBBER
(po101.p4M)
I
Raw rubber obtained from latex tapped from the rubber tree, particularly Hevea brasiliensLs,
does not possess the characteristic of the rubber with which we are familiar. In order to give it
strength and elasticity, it is vulcanised. In the vulcanisation process, raw rubber is mixed with small
amounts of sulphur and heated. The sulphur reacts with the polymer molecules forming across-linked
network.

UNVULCAINSED Rtm&R VULCM$SFO RUe&R
This cross-linking gives mechanical strength to the rubber. In addition, fillers such as carbon black
and zinc oxide are usually added to the crude rubber before vulcanisation in order to improve its
wearing characteristics.
The recurring double bonds in isoprene and butadiene polymers make it possible to have
polymers with specific spatial orientation as a result of cis-trans isomerism. Recall that two carbon
atoms joined by a double bond are not free to rotate and thus give rise to cis-trans isomerism. An
isoprene polymer can have all cis, all trans, or a random distribution of cis and trans configurations
about the double bonds.
Natural rubber is cis-polyisoprene with an all cis configuration about the carbon-carbon double
bonds. Gutta-pèrcha, also obtained from plants, is an all trans-polyisoprene. Although these two
polymers have the same composition,their properties are radically different The cis natural rubber
is a soft, elastic material whereas the trans gutta-percha is a tough, nonelastic, hornlike substance.
Gutta-percha is used for electrical insulation, and in dentistry.
—c C H 1-
H2\.\c=c/CH2 CH2\C=C/ CH
CH( H CH( H CH( H

All cis CONFIGURATION OF NATURAL RUBBER
_CHi\C_.c/H CHI\ C_c/2cc/H

_
c'/ \CH2_CHç_
Hj H CH( -
All trans CONFIGURATION OF GUTTA-PERCHA
Only random or nonstereospecific polymers are obtained by free radical polymerisation.

Synthetic polyisopreacs made by free radical polymerisation are much inferior to natural rubber,
since they contain both cis and trans isomers. But Ziegler-Natta catalysts Var example,
(C1HA1fliCl4) allow polymerisation to proceed by an ionic mechanism, producing
stereochemically controlled polymers. Ziegler-Natta catalysts made possible the synthesis of
polyisoprene with all cis configuration and with properties fully comparable to thosef natural rubber.
(2) SynthetIc Rubber -
(a) Neoprene (Pulychioroptene). It was the first synthetic rubber manufactured on a large
scale. Neoprene is obtained from chloroprenein the presence of benzoyl peroxide catalyst at 60-80°C.
The monomer, chkwoçxene, is prepared from acetylene. Neoprene is particularly resistant to
chemical action. It is used in the manufacture of containers for corrosive chemicals and hoses for
petrol and oil.
1302
Cu7C12
2HCCH wct'
CHCH—CCH
VIIYLA(ETYLEN(
Cl __________ - CL
I I
CH2=CH—C=°CH 2 C12—CH==C—CH
n
(HLOROP(I NEOPRENE RUSER
(b)Styrene-Butadiene Rubber (also called SBR or Bunna S). It is a copolymer made

from styrene and 1,3-butadiene in emulsion at about 47°C, using potassium persulphate as the initia-
tor.
—CH=CH2 + CH2CH—CH=CH2
STYRENE 1,3-UTAOIEN(
JPOt1Iti1t10fl
I CH_CH2—CHa—CHCH_CH24
6 STYRENE - BUTADIENE (SBR)
SBR has its major use in making tires, shoe soles and inside wall of buildings.
(c)Butyl Rubber. It is a copolymer made from isobutylene and isoprene. The polyinerisation
is crricd out at —1$0 to - 100°C in methyl chloride as solvent and with anhydrous aluminium chloride
as catalyst. Butyl rubber is used for making inner tubes fortires, motorand for other vibratin-dampn
applications.
CH3 Cl-I3
CH 3—C=CH + CH3=C—CH==CH2
ISOBUT1LENI ISOPRENE
poly IuIfiatI4rn
J
CH
[
-1- CH?_?_CH^_CCH_CH2
CH3
[
BUTYI. RUBBER

byndlelk PcIynws
POLYMER PROPERTIES AND STRUCTURE
Properties of polymers depend upon their molecular weight, branching and stereochemistry.
For example, as the molecular weight increases in a given family, the tensile strength increases
markedly. Like other organic molecules, polymers may have functional groups and asymmetric
centres. They can undergo hydrogen-bonding and dipole-dipole interactions. The chemical
composition of a polymer chain is known as its primary structure. How the chain is arranged in
relation to itself and to other chains is called the secondary structure. This secondary structure is
as important to the properties of a polymer as its chemical composition.
A polymer may be a tangled mass of continuous chains, or branched chains. The o ut is soft
amorphous solid such as soft rubber. On the other hand, a polymer may be composed cc tinuous
chains held together by hydrogen bonds or by other dipole-dipole attractions. This tv - of polymer
structure lends itself to fibres or hard, moldable plastics. A more-ordered polymer is said to have
higher degree of crystallinity than the amorphous, or noncrystalline, polymer.
A NONC'YSTALLIHt A CRYSTALLINE
POLYMER POLYMER
The differences in properties between crystalline and mm-crystalline polymers are beautifully
demonstrated by gutta-percha and natural rubber. Gutta-percha is a highly crystalline polymer,
while natural rubber has a molecular shape that does not lend itself to an ordered, crystalline
arrangement.
CH 3 CM3 CM3 CH3 CH3 CH3
NATURAL RUB8tR GOTTA-PERCIIA

(cis - potinopient) (Irans—polt aprtn).
Let us consider the polymerisation of propylene. There are three types of product that could
result from the polymerisation of propylene.

(a) (b) (C)
hilaclic In), SndiaIacik )h). and Alaclic )c) forms of Poispropylens

1304 Advanc8d Orgai* QsVy
This polymer in which all methyl groups are on the same side of the zig-zag carbon chain is
called iso(actk. The polymer in which the methyl groups regularly alternate on opposite sides of
the chain is called syndiotactic. The polymer in which the methyl groups are randomly oriented is
called atactic (Fig. 50.3). Because of their orderly arrangements, the chains of isotattic and
syndiotactic polymers can lie closer and the polymers are more crystalline. On the other hand, afar/ic
"tcr is soft and amorphous.
QUESTIONS
I. Explain what is nicant by each of the following terms -

(a) Polymer (b) Monomer
(c) Copolymer (d) Homopolymer
(a) Addition polymer (f) Condensation polymer
(g) Thermoplastic polymer h) Thermosetting polymer
2. State the key differences between
(a)Addition polymerisation and Condensation polymerisation
(b)Copolymers and Homopolyrncrs
(c)Syndiotactic polymers and lsotacitc polymers
(a) Isotactic polymers and Atactic polymers
3. Write notes on
(a)Addition polymers (Raiwra.s BSc, 1993)
(b)Condensation polymers (Jiwaji uSc, 1994)
(c)Synthetic rubbers (Saugw BSc, 1994)
(d)Vulcanisalion (Pondicherry LtSt-. 1994)
4. Cisc the names of the monomers that me used to produce:
(a) Dacron (b) Orion (c) Bakelite
(d) Nylon-6,6 (a) Teflon
Answer: POLYMER MONOMER

Dacron Dhtnethyl terephthalnte -+ ethylene glycol
Orion Vinyl cyanide
Bakelite Formaldehyde + phenol
Nylon-6,6 Adipic acid + hcxsnselhytene diatnine
5. How do thermoplastic polymers differ from rbccmosettsng polymers ? Give two examples of each type.
(Nor/h 57.vrem FhUItSc floor. 1994)
6. Classify the following polymers on the basis of the action of heal on them : Bakelite. Nylon, Dacron. and
Polyethylene.
Answer Nylon, Dacron and Polyethylene are thermoplastic polymers Bakelite is a rhersuoseuting polymer
7. Discuss the structure of natural rubber. -
8. Write a step-by-step mechanism for the polymerisation of ethylene in the presence of an organic pecosidc.
(Delhi BSc lions. 1993)
9. Discuss the mechanism for the polymerisation of propylene in the presence of l-1S0. (or HF) catalyst.
(GasahatiBScHow. /994)
Auswer. Following steps we involved:

Chain Initiation. Proton from H2SO or ElF odds to the C=C bond of propylene to give a stable 2 caiboniam ion.
H2SO4 —+ H + HSO4
+
CH 3— CH = CH + H+ —4 CH3—CH—CH3
21 URBONILIM KIN
Claim Propaption. The catbonrum inn adds to another propylene molecule to form a new carboniam ion, which can
.tnsilarly add to another molecule of propylene and soon.

synThetic Polymers 15
Cit 3 CH3
+ CM—CH 3 —+ CH3—H—CH3—tI-l—CH3
(A)
CR 3 Cit3 ct-is CR3

1 +
CH 3 —CHCH 2 + CH—CHz--fH—Cl-3 3 —+ C,4 3— CH---CH 2— CH—cH 3 —CH—CH ) •
(A)
Chain Termination. The chain rcacliioi can be terminated by iraovfrr of a proton from the carbcrniurn ion In HSO;,
fomirng a tem050) C C bond.
rH so,
H
I I I I
JCH2 — CF
CH2CHjCH C ' --4 CH2=cH–[CF-f2—CH H
cHJC3
n
PQLYPPOPYLUIE
Ill. Write a step-by-step mechanism for the polymerisation of vinyl chloride in the presence of an organic peroxide.
(Osmania USc lions. 1994)
Answer, Following steps we involved:

Chairs Initiation. Organic peroxides decompose In give hoc radicals
o 0 0
II II II
R—C-0--0—C—R — s 2R—C--0- — 2R + CO2
Chain Propagation. Fine radical produced in the above step adds to a vinyl chloride molecule to form a new free
radical.
R-4- CH2 --1H —4 R—CH2—H

ci ci
VINYL CHLORIDE
This free radical can and another vinyl chloride molecule and so on.
RCH,2^,^H^+jNz-!--*CH —S RCH2CH—CH2—H
C1 C1 C1 C1
RCH2 —S
CHC14 + nCH2=?H R±CH_CHCH2_?H
Mci C Ci] Cl
fl +t
Organic Clwinistr y - 83

1306 Atsd Organic chemistry
Chain Termination, The chain reaction can be interrupted when the free radicals combine or by disproporiionation.
RfCHz_H1CH 2_ cifcw 2Ei bLaH —4
n+1 H1^
'+ I
R-fCHz_CH1CH2_CH?CI + RfCH2-.CHtCH=CH
. Ct] I. cIj CI
fl11
POLYMER POLYMER
II. How will you oyulhessac the following polymers from the indicard staining materials
(a) Polythene from ethylene
(b) Polyvinyl chloride (PVC) from acetylene
(c) Polystyrene from benzcne (Meerut BSc. 1993)
(d) Dacron from ethylene andp.xyleae
(e) Bakelite from phenol (Vikram BSc, 1993)
ff3 Nylon-6,6 from I .3-Butadiene (Agra BSc. 1994)
(B) Neoprene from acetylene (Ban dolkhand BSc. 1994)
12. Define the teem 'polymerisation. Compound (A)was found to ha'e the composition :Carbon = 38.4%, Hydrogen
=4.8% andChtonne 56 8% Boiling with aqueous NaOH produced noeufect on W. Boiling with alcoholic NaOH produced
unsaturated hydrocarbon. (B). Two successive treatments of (B) with sodium in liquid ammonia and methyl iodide gave a
thmethyl derrvaiive. On addition of benzoyl peroxide. (A) polymerised rapidly to give (C). Identify the compounds (A), (B).
and (C), and explain the reactions involved (C = 12; H = I ; Cl 35.5)
Cl
nswer, (A) is CH I = CHCI ; (B) is HC CH ; (C) Is - (CH, CH). -

Chapter 51
Spectroscopy
Until about 1940, chemists interested in the detailed structure of molecules had to work mainly
by inference from their reactions. Elemental analysis and chemical tests, such as Lucas test, ToHens'
test, the iodoform test, and the Hinsberg test, to name a few, were the sole sources of evidence for
assigning composition and functional groups. Although chemical tests are useful, they are
time-consuming and somewhat uncertain, sometimes require a large amount of sample, and are
destructive (the analysis destroys or chemically modifies the sample). Today we can obtain a great
deal of information directly from molecules by the spectroscopic methods. Compared to chemical
analysis, spectroscopic methods are faster and more accurate, require less sample, and are usually
non-destructive.
We define spectorscopy as an area of study that probes molecular structure with
electromagnetic radlatlots. The Instruments used in such studies are called spectrometers. We
shall study several types of spectroscopy as they relate to organic molecules. To do that, we must
first understand how electromagnetic radiation interncts with molecules.
ELECTROMAGNETIC RADIATION AND MOLECULES

Electromagnetic radiation is a form of energy with wave properties. The electromagnetic
spectrum consists of a range of electromagnetic vibrations, which differ in certain of their wave
dimensions. Figure 51.1 shows a plot of the amplitude of an electromagnetic wave against its
progression (wave profile).
0
I-
-S
C.
x
PROGRESSION OF IHE WAVE
Fig. 511. Mot of the amplitudcofin electromagnetic wave

against Its pcogsuoe (a won prom).
The distance between two successive amplitude maxima or minima (or other corresponding
points) is the wavelength, designated by the symbol X (Greek letter labda). The number of
wavelengths that pass a given point each second is the frequency of the wave, designated by v (Greek
letter nu). Thus, the frequency is the reciprocal of the time elapsed (1) between the passage of two
successive maxima or minima (Eq. 1)
V = (that Es, wavelengths per unit time) (1)
130,
18 Advanced Organic C henstry
To understand these relationships, you may consider a wavelength as one cycle of a wave, that
is the distance between two successive corresponding points on the wave profile (Fig. 51.]). This
makes the frequency the number of cycles that pass an observer in a specified unit of time. Since
a wavelength ? takes a time T to pass a given point, the velocity (() of the wave is X divided by T
(Eq.2).
C (that is, units of length per unit ot frne ) .. (2)
In terns of the frequency of the wave, the velocity equals the product of wavelength and wave
frequency (Eqs. 3 and 4).
T = (From Eq. I) . . (3)
C = Ày substituting for Ti,, Eq. 2,) (4)

(11Y . V
The velocity (or speed) of light and other forms of electromagnetic radiation has the constant
value of 3 x 10" cm per sec (in vacuum). Therefore, dividing Eq. 4 by A shows that frequency and
wavelength are inversely proportional to each other and the proportionality constant (C) is the speed
of light (Eq. 5).
(5)
This means that electromagnetic radiation with a long wavelength has a low frequency;
a short wavelength means a high frequency.
Wavelengths are most often measured in centimeters (cm), nanometers (nm), or angstroms (A).
The relationship between thee units and other units of length is
l cut =l0 mm=l0m
I
I tim = 10 mm = 10' cm = lO a,
=lOnm =l0mm=llY1cm=l0°m
The units most used to express frequency are cycles (or vibrations, that is, wavelengths) per second
(cps), hertz (Hz 1 Hz I cps), and reciprocal centimeters (cm'). The last designation is called a
wave number and equals the reciprocal of the wavelength in centimeters (I/A in centimeters). Thus,
a wave number of 4,000 cm - 'corresponds to a wavelength of 0.00025 cm and tells us the number of
waves (cycles) per centimeter. The shorter the wavelength, the larger the wave number. In other
words, the wave number increases as the frequency increases. Note, however, that the units of wave
number are reciprocal centimeters (cm'), not cycles per second or hertz.
The Electromagnetic Spectrum

Table 51.1 shows the wavelengths associated with the various ranges of the electromagnetic
spectrum. Table 51.2 shows the wavelengths and frequencies associated with the regions of the
electromagnetic spectrum, which are of interest to organic chemists.
Table 51.1. Tic elecuomagodiespectrum.
Radiation Dewtiption Approximate Wavelength (A)
Short-wavelength end Comic rays 0.00005 am

Gamjniays OAnI-0.l4nm
Xraya 0.01-10 am
Ultnviolet 10-400 am
Visible 400-750nm
lmfrwed 750-50O,lXO am (0.5 mm)
Microwave . 500,)00-300.000,000 am (30 cm)
Lwavelengthcad Radiowivea. 30cm-100,))m

Spefros copy
Table 51.2. The infrared, visible and ultraviolet regions of the electromagnetic speetnan.

Wavelength (nm) Frequency (cm) Denaoo (Colour)
of the Radiation

50(L000-750 20-13,333 Infrared

750-620 13.333-16.129 Visible (red)

620-590 16,129 - 16,949 Visible (orange)

590-570 16,949-17,543 Visible (yellow)

570-500 17,943 - 201000 Visible (green)

500-450 20.01._22,222 Visible (blue)

450-400 22,222-25,000 Visible (violet)

400-It 25,003- iø Ultraviolet
Notice that the visible spectrum extends from approximately 750 nm to 400 nm. As pointed
out in Chapter 45, compounds that absorb electromagnetic radiation in the visibleregion arecoloured.
The colour they transmit comes from the visible wavelengths that are not absorbed, the ones that
reflect off the compound. Colourless compounds do not absorb radiation in the visible region, but
most do absorb in either the infrared or ultraviolet regions or in both. As we shall soon see, measuring
absorp tions in the infrared, visible and ultraviolet regions of the electromagnetic spectrum provides
information about the structure of compounds.
When a compound absorbs electromagnetic radiation, matter and radiation energy (waves)
interact. We can explain this interaction on the basis of quantum theory. Radiation energy interacting
with matter behaves as though it consisted of bundles of energy called quanta. The amount of energy
in each bundle or quantum, is given by the following equation:
E=hv (6)
where, E is the energy of a quantum, V is the frequency of the radiation that produced it and h is
Planck's constant (h= 6.62 x 10 erg see). This relationship between frequency and energy expresses
quantitatively what we have already stated qualitatively: The higher the frequency of the radiation,
the greater is its energy. Quanta in the high-frequency (shorter-wavelength) ultraviolet region, for
example, contain much more energy than quanta in the lower-frequency (longer-wavelength) infrared
region.
A quantum of energy (hv) it also called a photon. Molecules can interact with photons in
several ways, depending on the frequency of the photon and the structure of the particular molecule
the photon strikes. Certain photons can increase the rotational energy of molecules, that is, the
energy associated with the rotation of atoms around bonds. Other, more energetic photons contain
precisely the energy needed to increase the vibrational energy, that is, the energy associated with
the motions of atoms relative to one another, such as bond bcndings and stretchings. Photons of even
greater energy can be absorbed by increasing the electronic energy, that is, by exciting the electrons
in a molecule to higher energy levels.
Rotational, vibrational and electronic energy are quan:ised. This means that molecules have
discrete rotational, vibrational and electronic energy levels. Tbenergies of molecules can be only
at these quantised levels; they can never be at in between lev'els. A representation of rotational,
vibrational and electronic energy levels is shown in Fig. 51.2.
Moving from a lower rotational state to a higher one requires the input of precise amounts of
energy. Hence, molecules can absorb only certain frequencies of electromagnetic radiation (hVaor).
Likewise, an increase in vibrational energy demands photons with particular energies (hV,), but
these photons must be of higher energy (hence, higher frequency) than those that can produce a
change in rotational energy level. Again, though, the molecule can absorb only certain frequencies.
This is also true for electronic energy levels, which are much more widely separated than even
vibrational levels. Typically, in terms of calories per mole, electronic energy stale transitions demand
photons that aê two or three powers of 10 ( 1 02 to UP) mom energetic than those needed for vibrational
transitions. It turns out that rotational-vibrational transitions require photons in the infrared (IR)
region, whereas electronic transitions require photons in the ultraviolet and visible (UV-VIS) regions.

1310 Advanced Qrpanic alemisoy
E 2 ,l.ctronk energy i,vi rotoinnot energy i,v.1,
j }
en •
00.10
5=3
vibrational energy tevelsovfj

electronic •n.r51
Y1
v=O
Fig. 512. A repccscntOlioo of electronic, vibrauonal and rotational cncrgy irvels

Arrow (a) shows anCkdUOniC transition tr1)mEL,0O.3 r 70P02 l.j 3
the
Arrow (b) shows electronic transition from t 1,v l.j=4uptoE2,2.i= 3
To Summarise:
1. Electromagnetic radiation is a form of energy with wave properties.
2. Wavelength (A) and frequency (v) are inversely proportional.
3. The wavenuinber (cm- ') is the reciprocal of the wavelength in centimeters.
4. Absorptions in the ultraviolet, visible and infrared portions of the electromagnetic spectrum
provide useful structural infromation about organic compounds.
5. Photons are quanta of energy.
6. The energy (if) of a photon is equal to hv where h is Planck's constant.
7. The electronic, vibrational and rotational energy levels of a molecule are quanttsed only
certain photons can be absorbed.
8. Electronic transitions require UV—VIS photons vibrational-rotational transitions require
IR photons.
ULTRAVIOLET—VISIBLE (UV-VIS) SPECTROSCOPY

An instrument for measuring the interaction of molecules with ultraviolet and visible light is
called a UV-VIS spectrometer. Such an instrument has:
1. A light source that can produce ultraviolet and visible radiation.
2. A nnonochromator that separates light of many wavelengths into light of a single (or at
least only a few) wavelength.
3. A sample compartment where a sample can be placed, so that the light of known wavelength
can pass through it.
4. A detector that can analyse the light passing through a sample and tell if and when any
absorption takes place.
5. A recorder to make a continuous scan of the UV-VIS spectrum. The recorder pen moves
across a stationary piece of chart paper, or the paper moves and the pen responds from a
fixed position. In either case, the recorder traces a peak whenever the sample absorbs light.
The paper is calibrated with wavelength markings (usually in nanometers) on the horizontal
axis and radiation intensity markings on the vertical axis.
There is a variety of ways to measure the absorp ti on intensity. We shall use the molar
absorptivity, r (Greek letter epsilon) or its logarithm log c. The molar absorptivity or molar
Spectr$av,y 1311
" Unction coemdent, as it is called, equals the absorbance of a compound (a measure of the light
absorbing power) divided by the product of its concentration and the thickness of the sample cell that
contains it. This is called Beer-Lambert law.
C =—Xl (7)
where, e molar absorptivity
A =absortiance
c = concentration in moles per liter
= thickness of sample cell in centimeters

The absorbance (also called optical density) in turn, equals the logarithm of the ratio of the light
intensity before it passes through a solution of an absorbing compound (!) and after it emerges from
the solution (I).
A=log -j (8)
Peaks in ultraviolet and visible spectra are often quite broad. That is, they span many
wavelengths. It is convenient to specify the molar absorptivity (c) at the wavelength of greatest
intensity of absorption within a broad peak. That wavelength is given the symbol and the molar
absorption at this wavelength is ç,, (replaced for convenience by log r if E is very large). Figure
51.3 shows the UV spectrum of 4-methyl-3-buten-2-one in methyl alcohol.
12,000
0,000
8,000
I 6,000
4,000.
2,000
210 270 230 240 250 260 270 ILl 1v0
Fig. St.) The ut avioto specmim of 4-mhyl.3 . buten . 2-one in methyl alcohol
Interpretation of UV Spectrum
Since most organic compounds are colourless, the visible region of the spectrum (400-750 nm)
is of limited value, but the ultraviolet region, especially the wavelengths from 200-400 not, is very
helpful as a guide to the presence of certain functional groups, particularly the unsaturated ones. The
photons in UV light have the proper energy to raise the electrons to higher energy levels, higher levels
than they normally occupy in their ground state. These higher energy levels are called excited
states. When a photon kicks an electron from its ground state to an excited state, the process is called
electron excitation.

As a rule, one unsaturated grouping is not sufficient for very intense absorption in the 200400
am region. Isolated C = 0, C = N, N = 0, N = N groups do have absorption bands in this region, but
compared to compounds with conjugated multiple bonds, a singly unsaturated compound'will absorb
weakly ( r usually not more than 200). Compounds containing conjugated it bond system show very
intense bands; r is often in thousands (log r= 3-4), tens of thousands (log e= 4-5), and even hundreds
of thousands (loge = 5-6).
Groups that cause light to be absorbed are called chromophores. Table 51.3 gives partial
list of simple, unconjugated, p1-bonded chromphores, some specific examples which contain these
chromophores, and their A , and e, values. Notice that there are not many compounds that have
absorption bands (?) in the 200-400 nm range and those that do, absorb very weakly in this region.
ithle 51.3. UlIm yislet absorptions of some simple chrornophoits
Position Intennity
Clirorosophore Exempre(s) A (em)
\ /
C=C \ H2C-C1f, 170 15.500
/
(vinyl group)

CH3(c1l)4Ct1=CP41 175 13,

—CC— Cl15CH2CH5—CC—CFt3 178 10.000

(ecetytenc group) 195 2.000
150
223
0

C=O CH3—C--t1 160 20.000

(cabonyl group) 160 10.000
17
0

CH 5—C—Ca1 3 166 16.000

189 900

280 15
0

CI-43--C—OH 208 30
0

CH,—C—NH, 220 60
0

CH3—C---OCH5 210 so
Os 0

—N CNJCHiClliCHJN\ 201 5,000

274 I?
(isliro group)
—N—N- CH3—N—N—CH,

338 S
(ass group)
Functional groups that contain no it bonds but do have lone-pair (nonbonding) electrons on
atoms such asoxygen (as in alcohols), nitrogen (as irsamincs) and halogen (as in alkyl halides behave
similarly (Table 51.4).

1313
Spectrowy
Table 51.4. Ultraviolet absorption cnused by lone-pair (nonbonding) electrons.
Location of the
Nonbonding Electrons Example
- Oxygen CH2OH 183 not 150

Nitrogen (CH1),N 227 nm
Halogen CHI: 258 rot 316
The real diagnostic value of ultraviolet and visible spectroscopy, however, is to detect conjugated
unsaturated groupings. Tables 51.5 and 51.6 list a number of conjugated chromophores (and
compounds that contain them) that show characteristic absorptions in the useful UV-VIS region.
Table 51.5. Ultraviolet absorptions of conjugated clsmmophores (Aliphatic Compounds)
Absorplior
Apprommale Appro,iimst.
Pombon Intefusity,
Chrornophors(s) Example(s) 2 (nm)
C-- C— . CHCH—Cl-CH 217 21.800

CHCH_CCH_CaCHu 270 40.000
(5 = 3)
Ckf—(CFCH)_CH=CH2 310 60.
(n = 4)
cHcH—tCa.cHL—CH2=Calj 380 150.000

(a 6)
Ca1.=CH—(CHCH)4—CHCH 415
(5 - 8)
0 0
CC -C-- CH=Cl4—C-11 216 18,000
320 30
CH, \ /COOH
I,./
cc 206 13,500
"H 242 250
0
cfl==CH—C--CH3 213 7,800

320 30
3 0
(C-=CL---C— c8—(c.cH) 2—C---H 270 27.000
0
cH,—lcH=ca1)--c--H 343 40,000
0
393 63,000
CH1—(CH=Cl1),--C—H 415 65.000

1314 Advanced Organic Cttemiy
Table SLt Ultraviolet theoptions of conjugated np&o (Aromatic Compounds).
ABSORPTION
APPROXIMATE APPROXIMATE
POSITION INTENSITY
CM ROMOP HO R c(S ) EXAMPLE(S) X.,(nm ) E max
0 184
203
255
41,000
1,000
230
206 7,000
261. 225
211 6,000
0H
270 15,000
217 6,400
269 1,500
230 8,600
—NH2
280 1,400
248 14,000
280 800
250 11,400
C—CH3 246 10,000
230 fl,600
272 950
f=\
270 7,800
The most striking feature of the data in Tables 51.5 and 51.6 is the conjugation effect. Extended
conjugation shifts the A,,,, towards longer wavelengths (toward the so called red end of the spectrum).
It also increases the intensity of absorption. That is, the magnitude oft increases. The effect of
extended conjugation was recognised long before spectrometers were available because long enough
extension shifts the absorption into the visible region and gives the compound a visible colour
cdmplementary to the one it absorbs. Consider the example of the yellow pigment -caroene, which
occurs in carrots. The molecule has eleven carbon-carbon double booth.

1315
Specy
H 3 C 6C H 3 ^ I
CH3
-- --
0— CAROTENE -
This extended conjugation causes absorption in the blue-violet region of the spectrum. More precisely,
p-carotene has strong absorption bands centered at about 450 nm and 480 urns = 140.000 and
1.
120000, respectively). Molecules of -carotene extract' from white light the wavelengths covered
by these absorption bands and transmit the rest. The wavelengths they transmit appear yellow to the
human eye.
Lor
46000
.9
5000
.7
40
.6
I
e
.4
3000f
.3 2000
.2
1000
230 240 250 260 270 230 290 300 310 320 330 340 350 360
am
Fig. 51.4. The ultraviolet spectrum of naphthalene in methyl alcohol.
Figure 51.4 shows the UV spectrum of naphthalene. Absorptions of aromatic compounds move
to longer wavelengths with increasing size of conjugated system. For example, pentacene absorbs
far enough into the visible spectrum to look blue.
0 @©.
BENZENE NAPHFiALEHE ANTHRACENE
Xmau 202 no C 6900 'rna 215am t: $600 XmQa 375 am, e 7900
issam , 225) (X 312am £ 250)
@= -
HAPHTH&CENE PENTACENE
Xmax 473nm , C 11200 Xmaa 530 C 16000
(orange) (blue)
Use of UV-VIS Spectral Data in Quantitative Analysis

The UV-VIS spectral data can be used to measure concentration (how much compound is
present). If the compound is known, one of the easiest ways to do this is to plot absorption intensity
against concentration using solutions of known concentration prepared from pure authentic samples
of the compound. Once the plot is made, the absorption intensity of the solution of unknown
1316
concentration is measured and located on the plot. The concentration can then be read on the
concentration axis.
To Summarise :
I. The molar absorptivity (c) of a compound is a measure of its light-absorbing power.
2, 1 onjugated molecules give strong UV-VIS absorption bands.
3. Chromophores are groups that cause light absorption
4. Extended conjugation results in more intense absorption at longer wavelengths.
5. UV-VIS data can be used both qualitatively and quantitatively.
.y
INFRARED (IR) SPECTROSCOPY
The most useful region of the infrared radiation extends from above 2.5 to 16 microns (I micron
= I micrometer = 10 6 meter). It is more customary, however, to use wavenuisihers to specify the
positions of absorptions. The wavenumber of a particular radiation is the number of waves per
centimeter, which is simply one divided by the wavelength (A) in centimeters.
Wavenumbcr =
Wavelength in cm
An infrared spectrum is usually presented as a plot of the percentage of radiation of each wavelength
transmitted through the sample (0% transmission corresponds to total absorption by the sample)
Figure 51.5 shows a typical infrared spectrum.
maOrs
25 3 4 6 7 6 9 0 12 15
100
080
60
40
20
4000 3500 3000 2500 2000 1800 1600 1400 . 1200 1000 800 600
Fig. 513. Infrared sp cimmof t -txiiI

An infrared spectrometer, an instrument whose essential components are shown in Fig. 516, is
used to obtain the spectrum.
SAMPLE
LENGTH
ECTOR
RtCOR0ER
L I
DETECTOR
LT
Fig. 516. schematic diagram of an mIricd spectrometer.1liesourocemitiinfrared radiation spanning awide frequency
range. A wavelength selector permits only a Particular wavelength of radiation transmitted by the sample 10
fall on acjetecto al a given time. flse detector measures the lniensityof radiation and a plot otthis intensity
for each wavelength is traxd on paper by iecsxn]er.
Speclroscvpy 137
The infrared spectra shown in this chapter are of the layers of liquid organic compounds held
between two plates of sodium chloride (sodium chloride does not absorb in this spectral region).
Spectra can also betaken of gases or of compounds dissolved in a solvent. When a solvent is used,
absorption due to the solvent must be subtracted. Spectrometers ordinarily do this by measuring
the difference between the absorption of radiation by two sample cells one containing the solution
of the compound. the other containing only solvent A routine infrared spectrum takes only a few
minutes and a few milligrams of sample.
What happens to a molecule wnen it absorbs infrared radiation? The bond lengths and angles
for molecules are actually in constant motion relative to one another. Those motions that stretch
bonds and deform bond angles are known as molecular vibrations Figure 51,7 shows some of these
vibrations. Stretching vibratiOns change distances between adjacent atoms. Bending vibrations
change bond angles.
On absorption of a photon of infrared radiation, a molecule is excited to a higher energy level
in which vibrational transitions are more energetic. To some extent, vibrational transitions involve
all parts of a molecule. Some transitions, however, are relatively localised, involving mainly two or.
at the most, a few atoms. As a result, some structural features lead to infrared absorptions that appear
in a narrow frequency range, regardless of the structure of the remainder of the molecule. Such
characteristic absorptions make infrared spectra useful in providing structural information about
compounds of unknown structure.
cDc)
STRETCHING vieRAlloNs
Scissoring Rocking Twisting Wagging
5ENU1116 VIBRATIONS
Fig. 51.7. Siitsdiig md bciig vftvfim ivnIving only a kv ltoi.
For a vibration to result in absorption, it must change the dipole moment of the molecule. It is
fortunate that this selection rule applim since it reduces the complexity of 1K spectra, which
nonetheless contain more peaks than do UVV1S spectra. The dipole moment (&) is a vector quantity
that expresses, in units called Dcbye (D), the net charge polarisation in a molecule. For example,
hydrogen chloride has a dipole moment of slightly more than ID.
H—Cl
Ii = 1.030
1318 Advanced Organic Cbenvslry
The positive end is toward H the negative end is toward Cl. Most bonds in organic molecules have
bond moments (individual dipoles) that contribute to the net dipole moment. In some cases, however,
individual bond moments can cancel each otherouL Thus, while methyl chloride has a dipole moment,
carbon tetrachloride does nol
Interpretation of JR Spectra
Bending vibrations require less energetic photons than do stretching vibrations. Therefore, they
occur at lower frequencies (lower wave numbers).
WAVELENGTH (microns)
2.5 3 6 5 6 7 B 9 1012 14 16
I I I I
C — C,C — N,C-0 STRETCHING
CC 1 0EI4 STRETCHING
C=0 STRETCHING
O—H,N—H STRETCHING
tiiiiiiiiiiiiiiiiiiiiiiiiiiC=C STRETCHING
C—H STRETCHING
VARIOUS BENDING VIBRATIONS
FINGERPRINT REGION
4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 BOO 600
WAVENUMBER (crrCl
Fig. SI S RegixIs of stretching and bending viboolions.
Figure 51.8 shows some typical frequency regions. Particularly useful are the stretching
vibrations of bonds involving the very light hydrogen atom (C—H, 0—H, N—H), and multiple bonds
(C =C. C=0, CC, CN). Stretching vibrations involving single bonds between two heavy atoms
(C—C, C—N, C-0) tend to be more associated with movements involving many atoms and to
appear in broader frequency ranges. Moreover, these absorptions fall in regions also occupied by
bending vibrations. The region from about 1400 to 600 cm' is called the finger print region. It is
often difficult to assign all absorptions in this region to particular structural features, Yet like the
finger print of an individual, the absorption of an organic molecule in this region is complex and
unique.
Table 51.7 lists in more detail some important stretching vibrations. With this information we
can begin to relate some of the features of spectra to the structural features responsible for them.
The first two spectra in Figure 51.9 lack significant absorptions between 2800 and 1500 cm
Therefore multiple bonds are absent. The fairly sharp absorptions in the 2970 to 2850 cm' region
are characteristic of C—H stretching vibrations of a saturated carbon. Although these spectra of
isomeric alkanes have many s i milarities, they are unmistakably different, particularly in the finger
print region.
Spec1icvpy 1319
Table 51.7. artenuic infrared absorption frequenotis for some common sinjciu,aj units.
Functional Absorption range (Cm ')

F Bond ct.is (intensity or absorption)' Notes
C—Fl alkanc(--C -H) 2850-2910 (rn-i)
/H
atkene(C'=C\ 3010-3100 (m)
alkync (CC — H)- 3290-3320 (s)
3romatic (Ar--H) 3000-3100 (m)
aldehyde (C—It) 2720-2850 (m) sometimes IWO

absorptions in
this region
o -I-I alcohol fret • 3600-3640 (s) sharp
hydrogen bonded 3200-3600 (s) generally broad
carboxylic acid hydrogen bonded 2500-3500 (m) several broad,
overlapping
absorptions
3300-3500 )m)
N - H amities, amides
('C lkencs 000 1680 (v)
aromatic rings 450 1000 3104 absorptions
in this region
near I60 (V) these absorptions
near 580 )v) saty considerably
near 1500 (s) in intensity
nciir 1450 is) ovcrlap with ('--C
bndiig vibrations
C -C 21)8)226)) (v)
CN 2210-2200 Im)

C C) -.ilcoh.;ls, cthcrs. 050 1350 Is)
carboxylic acids,
esters
(. () a)dchydcs. ketones 1550 IX50 lii
carboxylic acids.
esters, amides,
acyl halides
C-- N amines 1020-1360 (s)
C--C1 800-600 (s)
C -- Br 600-500 (s)
The following abhrciat,ons arc used to indicate the intensity of absorption s, strong. Its. mcdium, .
Y. vsri.hk
Reconsider the spectrum in Figure 51.5. It resembles the spectra of the alkanes but also has a
strong, broad, band at 3340 cm -'. This absorption is typical of the 0-H stretching vibration of a
hydroxyl group. The particularly great width of this absorption is due to the presence of a number
of different hydrogen-bonded species, each having a somewhat different absorption frequency.
The spectra in Figures 519(c) and 51.10(o) are of the carbonyl compounds, consistent with this,
both spectra have strong absorption characteristic of a carbonyl group at about 1700 cm. The first
compound can be identified readily as an aldehyde because of the absorption at 2720 cm typical of
the C-H stretching of a -CHO grouping. The other compound must be a ketone.
lo Advanced &garic Chemistry
(i) micro
23 3 4 5 6 7 3 910 1 1 15
Ix
so
4000 3500 3000 2500 2000 1800 160D 140D 1200 1000 900 600
cn_I
(b) mk1oi
23 3 4 5 6 7 891012 IS
ix
4000 3500 30DO 2500 2000 1100 1600 1400 1200 1000 900 600
CM - 1
(C) micatis
23 3 4 5 6 1 8 910 12 IS
100
so
3500 Co 2500 2000 - 1100 16M 1400 1200 1000 600 600
fit. 51.9. Iah*rd ec8rao1(a) 2.2.4-uiuxthyIpta (b) 2.3,3-hy1pcmtac; (c) hcana],
A sharp absorption at 2220 cm in the spectrum in Figure 51.10(b) is characteristic of a triple

bond. The presence of an aromatic ring is indicated by the group of absorptions between 1600 and
1450 cm and is consistent with the absorption at 3060 an - 'typical of = C—H stretching vibrations.
The very broad absorption in the 2500 to 3500 cm region of the spectrum in Figure 51.10(c),
along with the stroog carbonyl absorption at 1710 cm, is representative of a carboxylic acid.

Spedmsco 1321
In attempting to deduce structural information about an unknown compound from its infrared
spectrum, our approach should be to look for the presence 01 absence of absorptions having the
frequencies characteristic of certain functional groupings. For example, a compound thought to be
a ketone must show a carbonyl stretching band in the 1550-1850 cm region. If it lacks the band,
it is not a ketone. Infrared spectroscopy is also used extensively to identify samples of already known
compounds. Identical infrared spectra are identical in a large number of features (Just as are identical
fingerprints) and almost certainly are of the same compound.
(a) microru
2.5 3 4 5 6 7 8 9)0 12 15
20
4000 3500
40
3000 2500 2000

Few(r7
800 1600 1400 3200 1000 800 600
I1
CM-1
(b) microns
3 4 S 6 7 8910 12 35
300
80
60
4000 3300 3000 2300 2000 1800 3600 1400 1200 1000 800 600
on1
(C)
microns
2.3 3 4 S 6 7 a 9 10 33 Is
tOO
20
4000 354)0 3000 2500 2000 3800 1600 1400 1200 1000 800 too
CM -1
fig. $30. Infrared specn* of (a) 2-rarthykyclobeannonc; (b) bcnzoaithk, and (c) 2-narthylbutanoic acid.
Organic Chemistr y - 84
it,aiced Organic Chemistry
To Summarise:
I. Absorption in the infrared results in vibrational excitations of bonds.
2. Different types of bonds require differing amounts of energy for vibrational excitations.
3. In an infrared spectrum, the region 1500-4000 cm' is useful for determination of functional
groups, while the region beyond this is the fingerprint region.
4. Polar groups usually exhibit stronger peaks in the infrared spectrum than nonpolar groups.
The absorption positions of—OH, —NH. and —NH 2 (a double peak), —COOH, and C=O
are particularly, distinctive.
NUCLEAR MAGNETIC RESONANCE (NMR) SPECTROSCOPY

Nuclear magnetic resonance (NMk) spectroscopy measures the energy absorbed when certain
nuclei undergo nuclear spin transitions. These transitions involve photons of much less energy
than those associated with electronic or vibrational transitions. Photons in the radio frequency region
of the spectrum have the proper energy but only for selected nuclei.
Atomic nuclei have a property called the spin number, I. Nuclei that have an odd atomic number
(number of protons) or an odd mass number (protons + neutrons) or both an odd atomic number and
an odd mass number have spin numbers that are not zero (I 0). Ordinary hydrogen ('H, one proton.
no neutrons in the nucleus, mass number= I) is an example of an element whose nucleus has a spin
number of. The carbon-12 isotope (°C), which has 6 protons and 6 neutrons in its nucleus, has
= 0. Carbon- 13 (°C) has 6 protons and 7 neutrons and, like 'H, a spin number of'. Only nuclei
with non-zero values for I will give NMR spectra.
Organic chemists deal mainly with 'H nuclear magnetic resonance and we shall concentrate on
this topic. The spectra of other nuclei, however, especially "C, can provide useful information 1(k).
One problem is that thc NMR active nuclei (other than 'H) of greatest use to an organic chemist are
"C (1 ='), "N (I = ), and '0(1 ='). The natural abundance of these isotopes is so low that a suitable
NMR spectrum requires special instrumentation or synthetic isotope enrichment,
One can think of nuclei with I U as spinning tops carrying charge. Fach such nucleus has a
characteristic magnetic dipole moment, which we can represent as an arrow, -. A nucleus with a
magnetic moment is like a small magnet with a certain magnetic strength (p) and with a north and
south pole. Let the arrow head be the north pole and the tail of the arrow the south pole When there
is no external magnetic field, a collection of such nuclear magnets will be randomly oriented. In a
magnetic field, however, each magnet will orient itself in one of a limited number of ways In other
words, the orientations are quantised.
The numerical value of I shows how many wa y s a nucleus can be oriented in an external
magnetic field. The number of orientations equals I + 1. Thus, both 'H and "C can assume
2(i) + I = 2 orientations. Two, and only two, orientations are allowed. These nuclei will line up
either with the field (1) or against the field (1) (Fig. SI. I I).
x1er noi
mogntP S

AGAiNST THE EXTERNAL FIELD
1N
nucl,or hv
magnetsis
INI N WITH THE EXTERNAL FIELD
Fig ii Rcprtscriiation of nuclear iiagrrcis in an external magnew held

Specfroscopy .
The two orientations have different energies. The amount of energy required to move from one
orientation to another, liv, will depend on the strength of the external field, H, and on t, the strength
(magnitude) of the nuclear moment. For nuclei in which 1 = , the relationship is expressed by the
following equation
E=hv=20 (9)
It turns out that at a magnetic field strength (H) of about 14,000 gauss 'H nuclei require photons with
a frequency of 60 million hertz (60 MHz), while ' 3C nuclei require a frequency of about 15 MHz.
When the magnetic field strength and the radiation frequency match so that energy from the radiation
is absorbed, the nuclei are said to be in resonance with the radiation.
An NMR spectrometer can be designed either to scan through appropriate frequencies (v) at a
set magnetic field strength (H) or to scan through a range of magnetic field strengthsat a set frequency.
Either way gives a match-up that will put the nuclei in resonance. In practice, the latter method is
usually used the magnetic strength is slowly increased, while the sample is bombarded with set
radio frequency. Common frequencies are 60 MHz and 100 MHz.
SAMPLE TUBE
NI S MAGNET
DETECTOR RECORDER
RADIO POEQUENCY
TRANSMITTER
Fig 51.12. Schematic diagram of an NMR spectronter.
Fig, 5.12 shows the essential features of an NMR spectrometer. The sample is placed between
the poles of a powerful magnet and is surrounded by a coil connected to a radio frequency transmitter.
In effect, the spectrometer measures and records the amount of radio frequency radiation absorbed
by the sample as the magnetic field strength is altered. Spectra are ordinarily taken of compounds
in solution, although rhry cisti be of pure liquids. Commonly used solvents include those like CCI4
that have no hydrogens to give interfering absorptions. Because deuterium ( 2H or D)
60 million Hz = 60 mega Hz = 60 M1t7 or 60 Mc (Mc r megacycles per second). Recall that v =

therefore ?= cv. Also, since 60 MHz = 6 x 101 cycles per sec. and c = 3 x 10° cm/sec.
3x 10 15 cm/sec
X"-----------0.5xt0 cat/cycle =500con =5m
6x 10 cycles/sec
Thus. the photons involved in nuclear magnetic resonance have rather long wavelengths.
AoVanCeti (kgalltc Gtieniistiy
1324
absorbs in a very different region than hydrogen, such solvents as CDCI 1 , in which all Its have been
replaced by D's, are also widely used. A few tenths of a milliliter of a 5 to 10% solution sufticies for
routine spectra. The recorder plots absorption intensity against relative absorption frequency, giving
the NMR spectrum. Figure 5 1. 13 shows an example of a 60 MHz spectrum.
CH,
CH "downfield" "upfleld'
4
CH,
8.0 70 6.0 5.0 4.0 3.0 2.0 1,0 Ut' P15(51
chemical shift (3)
Fig. 51.13. The F'IMR spectrum of tetrameihylulane (TMS). The chemical

shift of TMS protons is OCX) ppm by definitson
Interpretation of NMR Spectra

Figure 51.13 shows the NltR spectrum of tetraiutcthylsilane (CH 3 )4Si. It turns out that the
protons in tetramcthylsilane (TMS) absorb at a high field strength relative to other protons. Thus the
TMS signal is used to calibrate NMR spectra. Since nearly all proton signals are on the same
(downfield) side of the TMS signal, concern about plus or minus shifts is eliminated. TMS is a good
standard because it is relatively inert, soluble in most organic solvents and volatile enough (bp 27°C)
to be easily removed after the spectrum is obtained. Usually a small amount of TMS is added directly
to a sample before the sample is run. The difference - in frequency units between the sharp TMS peak
and the absorption signal of another proton is called the chemical shift
It may seem confusing that the location of absorption peaks is specified on a frequency scale
when we have said that the frequency is usually held constant and the magnetic field strength is
varied. Typically the field strength is varied, but the electronic components of the spectrometer and
recorder translate this to a print-out that tells us the energy of a particular absorption in hertz relative
to that of some reference such as TMS. We still say that TMS is at the 'high field" end of the spectrum,
however, and that most other protons absorb "downfield' from the protons of TMS.
Cheinkal ShUt. The chemical shift is expressed as a fraction of the operating frequency of the
NMR spectrometer. The units therefore will be hertz per million hertz (HzJMHz) or, in other words,
parts per million (ppm) on what is called the delta (8) st4le.
On the 8 scale the chemical shift of the TMS protons is arbitrarily set at 0. Another, older scale
is the tau (t) scale. On the 't scale the TMS signal is set at 10. It is easy to interconvert 8 and 't scale
values (t= 10-8) and (8= l0—t), both of which are s(ifl used.
Different hydrogen nuclei have different chemical shifts. For example, the dioxane protons
absorb well downfield from the TMS protons (Fig. 51.14). Also, most organic compounds give NMR
spectra that show at least several peaks. Consider the protons in 1,2dibromo.2.methYlPT0Pane,
which give an NMR spectrum with two peaks (Fig. 51.15). These observations prompt an important
question: Why do the chemical shifts of various hydrogen nuclei
drffer?

Swftowy 1325
A
H H
H H
H 0 H
TMS
5.0 70 6.0 5.0 4.0 3.0 2.0 1.0 0.0 ppn

chemical Shill ()
Fig 51.14. The NMRspecnio1dioxanc.
inlegralionI
curve I 41.1mm
a
BrI 13.7 mm
aib
CH,—C—CH2—Br
CH3
a
b,
IMS
signal
8.0 7.0 6.0 5.0 4.0 3.0 20 1.0 0.0
chemical shill (fi)

Fig. 5115 The NMR speemam of 12-dibeomo-2-me6y1propane
An atomic nucleus in a molecule is not insulated from its surroundings. Around it are other
nuclei, which are themselves like tiny magnets, each with its own small magnetic field There are
also negatively charged electrons in the vicinity of each nucleus and these have magnetic moments
too. Therefore, what any nucleus feels' in an external magnetic field is affected by the small local
fields of other nuclei and electrons near it. Some of the small local fields near a nucleus slightly
increase the effect of the external field, but others decrease it. The extent to which electrons shield
the nucleus - that is, modify the effect of the external field on it– is especially important in determining
chemical shifts.

1326 Advanced Ogancc Chemistry
CH3
Cu 1 — C—CH
CH3
IMS
6.0 7.0 6.0 5.0 40 3.0 2.0 1 0 0 0 ppm

chemical shill (6)
Fig 516 The NMR spccimmo12,2-dimeihylpanc.
Let us compare protons of TMS to those in 22dinie1hyIpropane (Fig. 51.16). The

2,2-dime thy lpropane protons absorb 55 He doantield from INIS at 60 MHz S = 0.92) First of all,
since both PAS and 2,2-dimethvlpropane have 12 hydrens. why is there only one peak in the NMR'
spectrum of each of these compounds ? The answer is that chemically equivalent hydrogens give
identical chemical shifts. This is the same as saying that hydrogens in identical environments will
absorb at the same field strength at a set frequenz Y. All the hydrogens in TMS are in the same
environment. Each hydrgoen in TMS is attached to a carbon that is also bonded to two other hydrogens
and an -Si(C)1 group The situation is similar for hydrogens in 2,2-dimethylprop4nc. except that
a carbon replaces silicon as the central atom. Thus, the NMR spectra of both of these compounds
have a single peak.
The hydrogens in TMS absorb at a higher field than those in 2,2-dimethylpropane because silicon
is less electronegative than carbon. Silicon pulls electron density less sironlv from its attached
methyl groups than does the central carbon in 2,2-dimethylpropane. This means that the electrons
in the C–H bonds in 2,2-dimethylpropane are more polarised toward the carbon of the methyl group
than the electrons in TMS are polarised toward silicon. Thus V the partial positive charge on each
hydrogen, is greeter in 2,2-diinethylpropane than in TMS.
H . u-I
4 lo__ o+
H —C(CH3)3
i
H
2,2 - O1HET1IILPROPANE TETRAPIETHYIS1LANE
(OMP) (TIPS)
In other words, the electron density around the 2,2-dimethylpropane hydrogens has decreased
relative to that around the TMS hydrogens. The electrons in 2,2-dimethyipropane shield thehydrogens
less. We say that these protons are deshielded relative to TMS. The more deshielded a proton is,
the further downfield it resonates. In effect, since electrons shield the hydrogens in TMS more thaii
they do those in 2,2-dimetliylpropafle it takes a higher applied external field to get them into resonance
at 60 MHz.
Number of Signals. Shielding and deshrclding by the local envtrrnimen! m what makes protons
in non-identical environments have different chemical shifts. With this basic principle in mind.
Spectroscopy 17
let us consider the 12-dibromo-2-methylpropane molecule again. Its NMR spectrum has two kinds
of protons in the molecule. (Remember that all protons are fundarnentatlly identical. This is just a
convenient way of saying protons are in two different environments).
cH3
CH3 — C —CH 2 13r 1,2 -OwRotlo-l- p iE THY LPRDPAIIE
Br
Closer took of the above formula shows that one kind of proton is the set of six methyl group protons
(labelled a) all of which are chemically equivalent. Another kind is the pairof equivalent methylene
hydrogens (labelled b). Now the question is, which peak in Figure 51.15 represents the a protons
and which b ? Two aspects of the spectrum provide an answer the relative chemical shift and the
relative intensity of peaks.
Bromine is an electronegative element. Therefore, it should have a strong deiieiding effect.
This effect should be experienced more strongly on the methylene protons b because they are bonded
to a carbon which is, in turn, directly bonded to a bromine. The methyl protons do not experience
the deshielding effect as strongly. This is because these protons are bonded to the carbon which is
one carbon removed from a bromine. The intervening tertiary carbon insulates the methyl protons
a to some extent from the pull of the bromine atom attached to it. The b protons are similarly insulated
from the pull of the bromine attached to the tertiary carbon, but they are not so insulated from the
bromine attached to the primary carbon. Our conclusion is that since the methylene protons are more
deshielded, they ought to appear more downfield. Therefore, we would like to assign them to the
shorter of the two peaks in the NMR spectrum (Fig. 51.15). The taller peak, would then be assigned
to the a protons.
Peak intensity and Integration curve. The relative sizes of the two peaks in the spectrum of
1, 2-dibroino-2-methylpropane (Fig. 51.15) also indicates how the y should be assigned. More
precisely , the area under the peaks is proportional to the nuns her ofprotons responsible for the signal.
The formula has six methyl protons and two niethylene protons. The relative area under the peaks
a and b are in a 6: 2(3: 1) ratio, which confirms our assignment on the basis of relative electron
shielding. The areas (or integrals) of peaks can be obtained electronically with NMR instruments.
A step-like curve is traced over each signal and the heights of the various steps are proportional to
the areas under the peaks. Figure 51.15 shows the integration curve traced over the peaks.
Number of Proton Neighbours. In addition to the information from chemical shift, the number
of signals and peak integration, an NMR spectrum also indicates the number of protons.
80 70 6.0 5.0 4.0 3.0 2.0 1.0 0.0 pDm
chemical shill (II)
Fig. Sit?. The NMR spectrum of L.t.itichtoruelhane

1328 Advatoed Orgapic Chemistry
The signal of a particular proton is affected by neighbouring protons with different

chemical shifts. For example, consider the NMR spectrum of 1,1 -dichloroethanc (Fig. 5117). The
signals clearly fall into two groups, one group at higher field that integrates for three protons and
another group considerably downfield that integrates for only one. There is no question about the
assignment the methyl group protons must be upheld pair of peaks (called a doublet) and the four
downfield peaks (called a quartet) must be due to the - CHCl 2 proton. But why do the signals split?
The nomenclature of split signals is as follows: One peak = singlet (s); two peaks = doublet (d);
three peaks = triplet (t) four peaks = quartet (q). More than four peaks is usually called a multiplet
(m).
Spin-Spin Coupling. The three equivalent methyl group protons in 1.1-dichloroethane are
affected by the way in which the single proton on the adjacent carbon interacts with the applied
magnetic field. If this proton lines up with the external field, then the effective field strength
experienced by the neighbouring methyl protons is enhanced slightly, lithe -CHCl 2 proton lines uj
against the applied magnetic field, it substracts slightly from the strength of the field affecting the
methyl protons. In effect, the methyl protons can experience two very slightly different fields
depending on whether the neighbouring proton is either with or against the applied field. Therefore,
in a collection of molecules resonance can occur at two slightly different frequencies, and the sample
will produce a double: absorption signal rather than a single: signal. This effect is known as spin-spin
coupling.
The effect of methyl protons on the appearance of the -CHCl 2 proton signal in 1 ,2-dichloroethane
is somewhat more complicated, but is a logical (if reversed) extension of the spin-spin coupling
concept first described. The three methyl protons can interact with the applied field in four ways
(Fig. 51.18). An upward pointing arrow (1') represents alignment with the field. A downward pointing
arrow (1) represents alignment against the field..
SPIN ALIGNMENTS OF —CH . PROTONS WITH EXTERNAL RELATIVE
',lK AREA
MAGNETIC FIELD
all against i I I 1
UNCOUPLED two against one with _____________

—CEI2 III
PROTON
SIGNAL two with one against

lit
oil with \_-it
Fig. St. t8. Spin-Spin Coupling. Splitting of the -CHCt, proton signal in CH,-CHCl 2 by the neighbouring -CM, group
As shown in Figure 51.18, there are three ways to align the three methyl protons so that rwo are
either with or against the external field. The permutations for this mode are two mirror-image sets,
each having a relative weighting of 3. However there is only one way to arrange them so that all are
either with or against the external field. This produces two mirror-image sets, each with a relative
weighting of 1. The net effect is to split the signal into four peaks with each of the two inside peaks
having three times the area of each of the two outside peaks. The amount of splitting (distance
between individual peaks) is constant within the peaks of the quartet and is identical to the splitting
observed for the two peaks of the methyl proton doublet.
Spin-spin coupling thus reveals the number of neighbouring hydrogens a particular pcotor, has.
A simple expression of this fact is that N equivalent neighbours produce N + I peaks. In using this
rule it is important to realise that the neighbours must be equivalent to each other, but must not be
equivalent to (that is, in the same environment as) the protons they are to split. Equivalent protons
do not split each other. Consequently, the methyl group protons in 1,1-dichloroethanc do not split
each other (Fig. 51.17). Similarly, the protons on adjacent carbons in dioxane do not split each other
(Fig. 5 1:14).
Spin-spin coupling is often associated with non-equivalent protons on neighbouring carbons
(1,2-coupling).
Specfmsay
1329
H0 Rb H0
A—C—C—X
H Hb
X
B Y
1,2-COUPLING 1,1- (OIJPI.ING
There are fewer examples of spin-spin coupling between non-equivalent protons on the same carbon
(1 I -coupling). Spin-spin splitting is not often seen when hydrogens are separated by more than two
other atoms.
Table 51.8. Approximate chemical shifts for different kinds of protons
Location Cheme6l
of hydrogen 55111
08-to
R --Cl-I-I) 12-I 4 ilkiocs R = saturated iikI)
I) -(II -R 5-I
it
46-5)1
,irurjici itksi
-_( -H 17-.))
Ai It 65-SO
/CH)
\
/ C=C \ 1.6-1.8 (R = I-I or xituiated alkyl)
R
Ai CH2 -25
9
C -CH 19. 2.6 aldchydcs. krtoncs. esters.
acetic acid
N -(H 22-29 amines, amides

/
-0 —CF4 3.3 39 nseihanol, eili'r, oslors

Cl- (H 3'
Br CFt
-CH - 92 -102 ildehydes

ROFI 1.5 - 55 alcohols
Ar Oil 4-8 phcncils
9
-(OH 11-13 carboxylic acid,
/
- J.s,IIIlIlII
1330 Advanced OrgarJc CheMtty
Table 51.8 lists some approximate chemical shifts for different kinds of protons. It is apparent
that the typical kinds of protons found in organic structures span a range of about 10 ppm on the 3
scale. There is a good separation of some types of protons. For example, vinyl and aromatic protons
absorb well down field from the saturated C—H types. A knowledge of the approximate cheini;al
CHI(9t
CHitCH1Br
(2)
1.0
(b)
(5.)
(3)
6.0 5.0 4.0 3.0 2.00
(cli
0
CHIN (9)
CH3—C—CH,
CH
:
IL
Rn in 6JO An An 1.0 10 In
Fig. 51.19 NMR spectra of (a) I -bmmo-2,2-dimclhylp!DPane (b)

toluene. and (c) p-eeributylbenzene.
Relive areas of absorptions am indicated by the numbers In parentheses.
Spectioscy 1331
shift p1rs consideration of shielding and deshielding effects allows us to predict where a signal for
a particular kind of proton should appear. Similarly, consideration of spin-spin coupling allows one
to predict the detailed form of the various signals. More examples of NMR spectra are shown in
Figures 5l.l9and 51.20.
) 1—T---.r
8.0 1.0
7.0 6.0 5.0 40 30. 20 .0 0
(b)j - V
I'
8.0 1.0 6.0 5.0 40 30 2.0 1.0 0
ff
80 7.0 6.0 50 4.0 30 2.0 0 0
Fig. 5 t 20 MMR spectra at (a) ethyl bromide; (5)),! -dich!oroelhanc and (c) 1, S ,2.thbromthaite
- Relative areas of absorptions air indicated 65 the numbers in paresiheses
To Summar ise:
1. NMR spectroscopy measures absorption of radio frequency photons when nuclear spin
transitions take place in a magnetic field.
. Tetramethylsilane (TMS) is used as a reference for NMR because its hydrogens have a very
highfield chemical shift.
3. The chemical shift of the TMS protons is assigned a value of 0 on the delta () scale. Most
other protons absorb downfield and have chemical shifts from 0 t 10.
4. The local environment of hydrogen affects its chemical shift.
5. Chemically eqtiivalent hydrogens have identical chemical shifts.
6. The more deshieldcd a proton, the more downfield from TMS is its chemical shift. Always
measure split signals at the centre of the muluplet.
7. The intergral of a signal (area under the peak or peaks) is proportional to the number of
protons producing the signal.
8. Protons with the same chemical shift do not split each other,
9. Protons with different cbemical shifts split one another if they are separated by no more than
two other atoms.
10. The number of peaks resulting from spin-spin coupling is N + I where N is the number of
equivalent neighbouring protons.
11. The approximate relative areas of peaks in a multiplel can be predicted by using Pascal's
triangle (a memorydevice used in algebra to remember the binomial coefficients). The
triangle may be extended to any size using only addition.
fl Pascal's Inc e Example

0 ri^ number of neighbour i ng protons
1 Ii For n = 2 , trrpIt is e x pected
2 121 From triangle, triplet areas I:21
3 1331
4 14641
5 15101051
12. Some typical proton chemical shifts are show below for ready reference.
—RCH2NR
0
0
r R — C — H —R — C A r R—C—CH2R ThIS
RC =— CH
to I 8 7 6 5 4
3 iç 1
I I I I I I
%C d
H3
R2C=CHR -RCH2X
-RCH2OR
IRCH2R
1—R CH
MASS SPECTROSCOPY
Mass spectroscopy is i technique that allows us to measure the molecular weight (mass)
of a compound. In addition, we can obtain valuable structural information about unknowns by
measuring the masses of the fragments produced when high-energy molecules fly apart. Fig. 51.21
shows the most common type of mass spectrometer.

Spedcossvpy '333
rGATIVaY CHAThGSD
4ACCELERATW,
PLATES
, -
7 REODRIDER
SAMPLE
INLET
ELECTRON MAGNETIC flEW
Fig. 51.2. Schematic diagsain of a mass spectron.
A small amount of sample is introduced into the mass spectrometci-and bombarded with a stream
of high-energy electrons. The energy of the beam of electrons is usually 70 eV (electron volts) or
1600 kcal/mole. When a high-energy electron stokes an organic molecule it disloges one of the
electrons of the molecule, producing a positively charged ion called the molecular ion.
__ +
P.1 I' M +e
MOLECULE MOLECULAR
ION
The molecular ion is not only a cation, but because it contains an odd number of electrons, it
also is a free radical. Thus it belongs to a general group of ions called radical cations.
In addition to causing ionisation, electron bombardment transfers such a large amount of energy
to the sample molecules that the molecular ions fragment; they literally Fly apart into numerous
smaller pieces some of which retain a positive charge, and some of which are neutral. The fragments
then pass through a strong magnetic field, where they are deflected according to their mass-to-charge
ratio (mM). Neutral fragments are not deflected by the magnetic field and are lost on the walls of the
instrument. Positively charged fragments, however, are sorted by the spectrometer onto a detector,
which records them as peaks at the proper ratios. Since the number of charges, e, is usually I the
peaks represent the masses of the ions. The mass spectrum of a compound is usually presented as a
bar graph with mle values (unit masses) on the x-axis, and intensity (number of ions of a given rn/c
striking the detector) on the y-axis.
The highest peak is called the base peak and is arbitrarily assigned an intensity of 100%.
Fig. 51.22 shows the mass spectra of methane and propane.
100
n/i ----+ .
(a)
Fig. 51.22. Ms spectra of (a) nr*hanc (CH, MW = 16),
The mass spectrum of methane is quite simple, since few fragmentations are possible. As
Figure 51.22(a) shows, the base peak has We = 16, which corresponds to the unfragmented methane

1334 Advanced Organic Cherrasir)?
U,
0
60
0
60
a
z
ID 40
20
0
m/e
(6)
Fig. 51 .22. (t) propane (CM., MW = 44
moleculear ion (M'). The mass spectrum also shows ions at nile = 15 and IA, corresponding to
cleavage of the molecular ion into CI-I and CR 2 fragments.
For larger molecules, the fragmentation patterns are usually complex and the molecular ion is
often not the highest (base) peak. For example the mass spectrum of propane (Fig. 51.22b) has a
= 29. In addition, many:
molecular ion (rn/c = 44) only about 30% as high as the base peak at rn/c
other fragment ions are noticed.

— H ' r+[cH3]+ H'
Ti/15
CH4 ..L^ H:C - _._]
I +
[cH 2]' -I- 21-1
m/e It
mk = Ii.
(molecular io n, t4)
Interpretation of Mass Spectra

The most important information that can be obtained by studying the mass spectrum of a
compound is its molecular weight (MW). For example, if we were given three unlabelled bottles
containing hexane (MW = 86), 1 -hexene (MW = 84), and I -hexyne (MW = 82), mass spectroscopy
would readily distinguish between them. We mull keep in mind, however, that not all compounds
show a molecular ion in the mass spectrum. AltF'eh M is usually easy to identify if it is abundant,
certain compounds such as 2,2-dimethylproparic fgment so readily that no molecular ion is observed
(Fig. 51.23).
100
—,
,'- so
LU
Li
z
o 60
z
40
tz 20
-I
LU
0
so "Ii --
m/e -
1.23. Mass spectrum cf 2,2.J)rneihy)prop3nu {-.11 . MW 72).

sy 1337
(c)CH3(CH24CH, and CH(C}I,),CH,
(d)CH3CH?OCHzCH I and CH,CH1CHCH5CH,
Oil
Answer
(a) UVSpuctroscopy. Since its double bonds are sot conjugated, the second isomer will not give an absorption
at a wavelength above 200 am. However, the first isomer has conjugated double bonds and will give an
absorption characteristic of a conjugated diene.
(b) NMkSpecrroscopy. The first compound will give only one absorption. The second will give two absorptions
(a doublet and a quartet),
(C) Meets Speczro.rcopy. The LWoconspotusds havediffereni molecularweightand their molecular ions will therefore
be different. Decane will have a peak at 142 and undecane will have a peak at 156. Note that IR, UV and
NMR spectra of these compounds will be similar.
(d) IR Spectroscopy. The alcohol will have a peak for the 0-I1 absorption in the 3200-3600 cm` region. The
ether will have no absorption in that uses.
6 A bottle of cyclobexanc to known to be contaminated with benzene. At 254 cm, benzene bass molar sbsorptsvity
of 204 and cyclohexane has a molar absorptivity of zero. A UV spectrum of the contaminated cyclohevane taken in 82.3cm
cell shows an absorbance of 0.07. What is the molar concentration of bensene?
Answer. 0.00017 M (Apply Beer-Lambert Law).
7. Cyclopentanotse (0.043 M in a 1.0con cell) has X., at 288 rim with an absorbance of 0.85. What is the molar
absorplivity of cyclopcstt.nnone at 288 am?
Answer. 19.7 (Apply Beer-Lambent Law),
8. The unsaturated aldehydes CH 1 (CHeCH),CH0 have UV absorption spectra that depend on the value of a, thcL
being 220, 270.312 and 343 not as changes from I1o4. Explain.
Answer. As the number ofdonblc bonds irtesease, so too does the extent of conjugation. Hence the absorption maximum
moves to longer and longer wavelengths.
9. Which one of the following compounds will absorb ultraviolet light at the longest wavelength?
(a)CH3CH-CH=CHCH20H
(b)CHfCH-CH=CH-4I
OH
(c)CH=CHJH-CHCH5
Answer. (hi will absorb at the longest wavelength because two doable bonds and the carbonyl double bond are
conjugated. (a) has only two conjugated double bonds, and (c) has no conjugated doable bonds.
00
10. The compound CH i CHi!(CHr mists in equilibrium with at tautomer. Its solutions show a strong UV absorption
with a at 272 nan. What it the structure of the taotonxcr? How could infrared spectroscopy he used to confirm your
suggestion?
Answer. The moe1sylene protom being between the two cattion y l group are the most acidic prownu in the molecule
and most likely to toatomsarrice
0 0
II II 0"
CHI—C—CH2—C—H3
kilo-FORM
HC"Nc'CH
H
ttmot -FORM
The enol form has a conjug ated system which is responsible for the long wavelength U V absorption. The infrared spectrum
of the enol form should show 0-H (Itydorgen bonded) stretch and C=C stretch, both not present in the keto form.
II. How would you dinttnguials between the following pairs of compounds by Itt upectroscopy?
(ci) CHrCH,CII 1N(CH1)2 and CH,CH3C}12NH1
(b) CHmCH5CH5COOH and C110IC001CH1
(c) CH5CH1COCH and CHCH5COOCH3
Answer, (a) CH,CFI5CH J NH1 shows N-H absorption at 3300-3500 can' while CHrCHmCH:N(CH does no
(h) CHICFI O217001`1 shows 0-H absorption at 2500-3500 an -'while CH SCHSCHSCOOCHJ does not.
(c) CH ICH 1COOCH J shows C-O absorption at 1050-1350 cm-' while CH 1CH1COCH ) does not.

1338 Advanced Organic CltentisUy
12.Briefly describe the main difference between the 111 spectra of ethylene glycol (HOCH 2CH 2OH( and acetic acid
(CHJCOOfI).
Answer. Ethylene glycol will show strong 0-fl abnoqHion at - 3500 cm. It will not show carbonyl absorptIon
Acetic acid will show 0-H absorption at - 3500 cm and carbonyl (CwO) absorption at 1700 cm.
13.Draw three isomers of molecular fonmulaC1H0. Dv' ribe how, using their 118 spectra, one could distinguish among
them.
Answer. The 3 isomers are
d
CH3— C — H WILL SHOW CO ABSORPTION Al ISSO-1650 r.
OH
CH2=CH WILL SHOW 0 — H ABSORPTION Al 3000- 3600
H2 C — CH 2 WILL NOT SHOW C0 or O''M ABSORPTION
0
14. How can the members of each pair of compounds be distinguished by a glance at their 118 spectra?
(a)CH,CH20CHCH 1 and CFl,CH2CH1CFO2OI'l
(b)(Cll1 ),N and CHCFl5C002NH,
(e) CH,CH2CeCH and CH,CH2CH'CH2
(d) CF0CHCH IC00H and CH,CH1COOCH,
Answer, (a) The alcohol will have a band in the 3200-36010 cut" region, characteristic of 0.-H;
(b) The prgiiazy amine will show an N-H absorption at 3300-35110 cm - '. but the tetliaty amine will not
(Cl The first compound an alkyne will have a band in the 2100-2260 cttsi region characteristic of CRC,
white atiicne will show a hand in the 1601)-1680 cm'region characteristic of C=C .and
(d( The first compound, a carbovylic acid, will show abroad 0-Fl absorption at 2500-3500 cm'
IS. A very dilute solution of ethyl alcohol in carbon tetrachloride shows a sharp infrared band at 3600 cm'. As the
solution is made more concentrated, anew. rather broad band appears at 3200-3600cm. Eventually the sharp band disappears
and is replaced entirely by the broad hand Explain.
Answer. These infrared data provide direct evidence for hydrogen bonding in alcohols. In dilate solution the alcohol
molecules are isolated, being vsrrmmnded by inert solvent molecules. The sharp band at 3600 cm- 'is due to the 0-H stretching
frequency in an isolated ethyl alcohol molecule. As the concentration of ethyl alcohol is increased, alcohol molecules come
in contact with one another to loon hydrogen bands. Hydrogen-bonded 0-H has a variable length (as the proton it transferred
buck and forth between oxygen atoms) Consequently, hydrogen-bonded 0-H absorbs at a lower frequency ond with a broader
range (32161-3600 cur 5 than the isolated 0-Fl group.
16. Explain why the 118 spectrum 'f glucose shows no significant absorption in the C0 stretching vibration region.
Answer. Glucose exists more than 99% in pynannse forms, which have no carbonyl group.
17.Two compounds, (A) and (B), have the same molecular formula C 2H5O. They have different IR spectra, Compound
(A) shows a s(rc,ngThroad absorption at 140,) cm ', while compound (18) does not Suggest formulas for (A) and (B) which
account for the difference
Answer. (A) is Ethyl alcohol (CH )CH 10H); (B) is Dinaclhyl ether (CH1OC}'l,). The strong absorption at 3400 ctn' in
(A) in due to the 0-H bond.
lB. flow many NMR signals would be observvd for each of the blowing compounds? In other words, bow many
different kinds of protons are present? Ignore any multiplicities resulting from spin-spin coupling.
(a) Chloroform (b) Acetone (c) AcetaJdchyde
(d) Tetrshydrofnrnn (e) 2-llutanone (/) Ethyl acetate
Answer, (a) One signal (b) One algual (c) Two signals
(d) Two signals (e) Three signals ff3 Three signals
19. How niany NMR signals do you expect in each of the following compounds
(a) l.l-Dichlorisnarthattc (b( Ethyl bromide (c) t,l-Dtchloeoetfsatse
(d) n-Butane (c) Neopentane () Allyl alcohol
(s) Toluene (h) Propanal
Answer. (a) Two signals (h) Two signals (c) Two signals
(d) Two signal. (e) One signal (.1) Four signals
(g) Two sign.' (It) Three signals
20. How many signals would be expected inNMR spectrum of each of the following compounds:
(a) CH3Br (b) CH5CH1Br
(c) CH5 H5CH2Br (d) CH3CH(Br)CH5
(e) (CHJ)4C (J) (CH3)3CCI
Answer, (a) One signal (b) Two signals (c) Three signals
(d) Two signals (e) One signal V) One
21. How would you distinguish between the following pairs of compounds by NMR spectroscopy 7
o 0
II
(a)CH,-C-CH, and C}{3CH2-C-H
O 0
II
(b)Cl13-C.-CH3 and CH,-C-OCH3
Answer. (a) CH3C0CH3 will give only one signal, while CH 3CH5CHO will give three signals.
(b) CH1COCH1 will give only one signal, while CFI 5COOCH J will give two signals.
22. What are the main differences in the NMR spectra of
0
(a) CH3-C-CH,
0
fbi CH3CH2-C-.H
(c) CH2CH-C}t10H
Answer. (a) shows-one NMR signal; (b) shows three NMR signals ; and (c) shows four NMR signals.
23. Draw the structure of a compound with each of the following molecular formulas that will show only one peak its
its NMR spectrum.
(4)C5H5CI1 (b)C3H2
(c) C,HSO (d) Cll3
Answer. Possible structures are
Cl CH,
(a) CH3-C-CH 3 (b) CH,-C-CH,
Cl CH
(c) CH3-43--CH, (d) CHIC • CCII1
24. Indicate how the members of each group of isomeric compounds can be distinguished by a quick glance SI their
NMR spectra.
0 0
(a)CH,-C-CH,
II
and CH'-C-H
(b)CH ICH1OCHCfI, and CH3CH1CII1CH3OH
(c)BrCHCH 5Br and CH3CHBr3
Answer. (a) Propionaldehydc exhibits three Absorptions, but acetone only one,
(b) Diethyl ether will give a simple spectium with two abscoplions in a 3:2 ratio, but bestanol will give a
complex spectrum with five different kinds of Absorptions in a ratio 3:2:2:2:1; and
(r) 1.2. Dibronwobassewjll give only one absorption, while, l.l-Dibromethanewjll give two peaks inaratio
of 3:1.
25. A chemist has two isoniesiccblompropunes (A) and (B). The NMR spectrum of (A) shows a doublet and a septet
(seven peaks), while tituS of (B) shows two triplett and series (sin peaks). idemify the structure of (A) and (B).
Answer, (A) is 2-chloropropane, and (B) is l-clsloropropsrie,
5eptif Sextet
/
(A) = CI (B) = CH3—CH2'--C142—Cl
(8)
Oojbi.t\ tOoobiit TnptCt\ Liripi.t

Ath'aj'sced Ofga' Ches7s8y

1340
28. How will you distinguish between the thsee dibromobenrenes by Limit ?4MR specisa?
Answer. o-Dibminobenzenc will show two peaks; m-dibmmobcnznrie will show three peaks; and pdshmmabenzeae
will show only one peak.
Br Br a
b 68 b—Br Br—'Br
o-OlBROMOENZE NE m - OIBRUIN)eENZENE p -OIBROPIOBENZENE

(two peaks) (three peaks) (nut peak)
1:1 1:2:1
27. Give a structure consistent with the following NMR dais
(a) Molecular Formula = CF10 (b) Molccslar Formula CaHIOS
a Singlet at 5 1.43, 1 a Triplet at 5 lOS. 3F1
b Singlet at 5 3.47, 311 b Singles at 5 2.13, .H
Quartet at 5 2.47, 2H
(c) Molecular Formula = CHSO (d) Molecular Formula = C11D0
a Triplet at 8 1.25, 3H a Singlet at 5 1.28.9H
b Singlet at 5 2 03, 3H b Singlet at S 1.35.91-1
c Quartet ai S 4,12,2H
(,) Molecular Formula = C 2 1'1 1Cl5 lJ) Molecular Formula C5H7Br
a Doublet atS3.93,2H a Doublet at 5 1,7l.6H
Is Triplet al5572,tFl 1' Septet at S 432, 1
1)
b a a c 1 b
Answer. (a) is Methyl alcohol = CH]-OH (b) is 2.Batanoae = CH,-CH2-C-CH,
0
a b
b 1 ca
(c) is Ethyl acetate = C11 3-C--OCH 1CH5 (r/3 is t.Butyl alcohol = (CH5)1C-OH
a b a h
(c) is 1,1 .2-Trichlometliane = flI 2CICH02 (/) is 2 . Bmmopcupane = (CH3)5CHBI
28. Write as ninny pos':ble iormuis.s as you can for hydrocarbons that show the following molecular ions in their miss
spectra
.
(a)M'4 (b) M= 186 (C) hi 58
Answer. In this problem we am given that all compounds represent hydrocarbons.
(a) For 64, possible ttsolecular formula tsC5H
(Is) For M '= 186, possible formulasare C, 4 H 11 and C,H5
(e) For hi 155, possible formula is C5H11

29.Corssider the mans spectrsn)of Ethylbest irate What causes the peak ,We =196? The base peak in the miss Spectrum
We peaks s178 and
sat ,rs'e = 91. What species do you he!i,'sc has a We 917 Explain. The mass spectrurts also contains
77 Explain rn/c = 91 peak
Answer. The nile = 106 is the molecular inst peak, which is the molecular weight OI ethylbeozenc. The.
in due to the beusyl. C5H5-6F1 1 . caibosium ion (very stable in resonance).
We = 78 is due to benzene, C5115 , and rn/c = 77
is riot to the pbeayl ion, C5H5'.
30. Write notes on:
(a) DV spectroscopy (Karnataka BSc, 1994)
(b) IR spectrosspy (Panjab BSc, 1993; Mudror BSc, 1994)
(c) NMR spectroscopy (Kerala BSc Ii, 1992: Baroda BSc, 1993; Delhi BSc lions, 1994)
(ri) Mass speracoscopy (Poona OSc 111, 19M
31. 01 the two compouds, ethylene and bistadiese, which absorbs at longer wavelength in DV speetroscoj.
(Delhi BSr. lIons, 1993)
Answer. Butadiene (CH 5=CH-c11H) will absorb at longer wavelength because of conjugation.
32. A chcriunt prepared 1,3,5-heeatriene and 1,5-hesaliene and placed them in separate flasks but forget to libel them.
How would you proceed to identify the two compounds by DV apectrcrscopy?
(Kerala BSc 2994)
) will have higher L.. than 1.5-hexadiene
Answer. 1,3,5.Hexatrtcac (CH 2 CHCHHCHCH 1
C1iCH). This is because I ,3,5-bexnnse is conjugated: whereas I .5-ltcxadleaie is not
(CH5=CHCH5CH 2
JR spectroscopy,
33, , Flow will you distinguish between the following pales of compounds on the buSs of
(a) Ethyl alcohol and diethyl ether. (Andhra BSc III, 199?)
(Is) Acetic arid and ethyl acetate
1341
Answer. (a) Ethyl alcohol shows a Amgtbmad absorption at 32)-364X) cm (due to 0-H bond) while diethyl ether
does not; and (di) Acetic sad shows a strong/broad absorption at 250)-35( cni' (due to 0-H bond) while ethyl acetate does
not.
34. Explain the importance of the finger print region in JR spectroscopy. How would you use JR spectroscopy to
distinguish between diethyl ether and acetone? (Pmpab 1/Sc. 1994)
35. Indicate bow can you use JR spectroscopy or distinguish between the following pales at compounds
0 0
II II
(a) C 5 H 5 -C-N11 2 and C6Hç-C-NHCFI1
Of ('H 1 OH
1 CFI and CH5-0-Cl15 (Mages/h BSc Hans. 1994)
36. How JR spectroscopy is used to distinguish between
0
11
(a) R C-NHR and R-CH.-N1IR
(Is) R-OH and R-NH, (Barodoi F/Sc, 1994)
37. Distinguish tsetweex the following pairs with the help of JR spectroscopy
(a) Saturated and a [l.snsalurated ketones
(Is) Ketone and aldehyde
(c)Carboxylic acid and ketone (Kerala F/Sc, 111, 1994)
38. Explain (a) The NMR spectra is useful in deciding the structures of ethanol and I .3 .diehlornptopane. and (b) ER
spectra is useful in determining the structures of acetophenoac and 2,4-diiuedhylpentane.
(Anna 1/Sc, 1993)
39. (a) What do you understand by shielding and deshiclding effect in the NMI8 spccsnon
(Is) Explain why do the protons of C'II 3 CH 5 Br not resonate at the same field strength
(c) How ate the (tan) and S (delta) scales related?
(Poona BSc, (994)
40. How many NMR signals do you expect from each of the following compounds. Indicate also the splitting pattern
of the various signals
(u)CH 1OCH 3 (Is)CH11)CHCI)1 (c)CH1CH2OH
(Punjab BSc, 1993)
Answer. (a) One signal (singlet); (b( Three signals (singlet, quartet, triplet); and (c) Two signals (singlet, quartet).
41. flow isiany NMR signals do ybu expect from each
(a) ClICFl 2 CH 5 Br (b) C5H1CH.CHCH1
(c(CH001 1 (le) H2CrCH.-CH1OFI
(Keisia BSc, 1993)
42. How many different kinds of protons are there in the NMR ipecunim at the following compounds:
(a) CHCH 1 CII 1 (di) CH1OCI11
0
)c) CS H I -CHCH S (sO CH3-C-CH5CH1
(Delhi BSc Hans, /994)
43. The NMR spectrum of a compound Cll,Br consists of a single sharp line. What as the structure of the compound?
- (Poona BSc, 1994)
Answer. The compound is xerr.Bntyl bromide, (CH5)3CBr.
44. Gives structure consistent with the following NMR data: -
Molecular Formula = C3H5C13
(a) Singles at 62-20,311 (Is) Singlet at 9402, 2H
Answer. CH2CI-CCl2-CH,
45 Suggest a structure consistent with the following NMR data
Molecular Formula = C,H51
(a) Singlet at 6 6.78, 311 Of Singlet at 82.25, 911
Answer. The compound is
Cl-I3
b HH b
MESJTYLENE
aH3 C CH30
H
46. Give the itructure consistent with following I4MR data:

Molecular Formula = C15H
(a)Singlet S 1.30,9H
(b)Singlet 8 7.29. SH (Kerala F/Sc ill. 1991)

1342 Mvanced Ot
Answer. The conopund is.
CH3/
b [.__c_,/)
CH3
47.Give the niruclure consistent with the following NMR data:

Molecular Formula = C0H13C1
(a) Singlet at S 1.57, 6K (6) Singlet at 5 3.07,2H (c) Singlet at 5 7.27. 5F1 (Punjab BSc, 1993)
Answer. The compound is:
CH3/
[ .. CH 2_ C_ CH 3 2-Cftl-OPO -2-METHYL-I- PHENYL PROPANE
48. A hydrocarbon CH,, gave as 'JMI( spectrum with threec signals:

(a) Quintet 5 2 04, 219 (6) Triplet 5 2 91, 411 (r) Singlet S 7.17. 4H (Poona BSc, 1994)
Answer. The hydrocarbon is
INSANE
49. Suggest a suitable structure consistent with the following NMR data
Molecular Formula = C9H1Br
(a) 8 2.15 (211, Quintet) (b) 5 2.25 (211, Triplet)
S 3.28(2K, Triplet)
(c) (rI) 5 7.25 (SR. Single[) (Sambaipur BSc F/ursa, 1993)
Answer. The compound is.
4 [_-CH2_ CH 2__ CH i_ Br 3-BROMO-I-PHENYIPROPANE
I t t
50.Suggest a structure consistent with the following NMR data
Molecular Formula = C.nH
(a) Singlet at & 712, 5F1 (6) Doublet at S 2.45. 2H
(ci MultipIct at 5 1 ,86. I H (d) Doublet at & 0.86, 6H (Nehu BSc Hosts, 1994)
Answer. The Compound it:
—Th
CH3
tlUTTLBEMZE
b
&I C— H3^
CHI
C)

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Chapter 46

Fused Polynuclear Aromatic Hydrocarbons

Naphthalene is the largest single constituent to 10 per cent) of coal-tar. It is obtained

NOMENCLATUR E OF NAPHTHALENE DERIVATIVES

t.ROMONAPHTHL'E 1, 6-D1MffHYVVA pm THAL ENE

Fig. 461 Formation of the bands in naphthalcne.

Also each carbon atom in naphthalene possesses an unhybridized p orbital containing

Fig. 462 Formation of the it molecular orbital in naphthalene.

(4) By Haworth Synthesis. This involves the following five steps

Advanced Organic Chemistry

Step 2. S.Benzoylpropionic acid is treated with amalgamated zinc in the presence of

© "CH2 2rP4gl CI4i

Substituted naphthalenes can be obtained by using toluene, bromobenzene, or ansole

(Physical). Naphthalene is a colourless crystalline solid. It melts at 82°C and boils

A. ELECTROPH] LIC SUBSTITUTION REACTIONS

MORE 3rABLE f-5085 7/rifT/ON

//A PH THALEM' 1- NtrRON,P//THALEN(

Step I. The electrophile (NOn is generated.

2f-ISO 4 + HONO -p 4 2HSOI + H30

Step 2. The electrophile attacks naphthalene at C-I to form the resonance-stabilised

(2) Sulphonation. Naphthalene undergoes sulphonation with concentrated sulphuric acid

1-NA P/-I THA LENt -

(3) HIogenation. Naphthalene undergoes ch1rination or bromination i n boiling car-

When the above reaction is carried at room temperature, naphthalene dichloride (1 4-

tIIrIJIII1J + ROO bI TEMP - H Cl

NAPM1HA1WE/C80R0NA P/I lilA (/V

(5) Friedel-Crafts Alkylation. Naphthalene undergoes alkylation with alkyl halides

latiOfl. Naphthalene reacts with formaldehyde and HCI in the presence

Reduction. Naphthalene undergoes reduction more readily than benzene. With

Oxidation of naphthalene with oxygen :uid .auadium 1citxde at 45 C y ields phthaiic.

Phthalic acid is an important industrial material. It is used in the manufacture of resins

Fused PlynucIeor Aromotic Hydrocarbons 1171

Classical Derivation of the Structure of Naphthalene

I. 4M/vONAP/1rNALFA'5 PI-iTHAIIC AC/fl

Substitution in Naphthalene Derivatives

IMPORTANT DERIVATIVES OF NAPHTHALENE

Preparation. l.Naphthol maybe obtained:

Sodium 1.nap4thalenesulphonate used in the above reaction may be obtained from

Conc: H2SO^ NaOH

1.Naphthylamme used in the above ruction may be prepared from naphthalene as

HAPk17f-AL(/1E JVJ7ROPiTHA( 1-/,4Pkf/y A i.7.'/E

Properties. (Physical). 1-Naphthol is a colourless solid, mp 94 C. it is only slightly

(Chemical). 1-Naphthol resembles phenol in its chemical properties.

SOVIUM ETiiY /-41PHrJJE e711ER

tWAPHTHOL ?.(HIORONAPHUi-AL (NE

(4) Azo-coupliog. l-Naphthol reacts with benrenediazoniurt chloride in a weakly alka-

7,2 -NA PH T#IAQU/NOftl(

(8) Reduction. I-Naphtholundergoes reduction with lithium metal in liquid ammonia

Reduction of 1-naphthol with sodium and isopentanol gives a;-tetrahydro-]-naphthol

PHTHALONIC ACID 1. MAPHTHOL 0

Oxidation o l-naphthol with ferric chloride yields a blue-violet precipitate of

Fused P.Iynuclear Aromatic Hydrocarbons Ill?

$ODIUM 50OUM 2-NAPfiTJ1O

Z1vAPHTHALE4'E 5111 P110/I/C

Properties. (Physical). 2-Naphthol is a colourless solid, mp 123°C. It is only slightly

2 -NAP/I T/IOt. SODIUM 2-NA PHI/lOX/Off

SoQLfM Z 'N4PHT/,0X IDE

Ethyl 2.naphthyl ether is known as nerolin. It is used as a perfume in artificial neroli

Reaction. 2-Naphthol reacts with ammonia and ammonium sulphite at

(4) Azo-coupllng. 2-Naphthol reacts with benzencdiazofliUn chloride in a weakly

(7) Oxidation. 2-Naphthol reduces ammonical silver nitrate. It is oxidised by alkaline

2-NA°t1TH01- PN7HAL ON/C ACID

Preparation. l.Naphthylamifle may be obtained: