Chapter-1

Jtntom son's Sqnthesis

Organic Chenisty
o -R
sodiun -her
a) Remer- emann eactton b) kotbe's RcacHon tolide -AHIKonfdJe
c flfarmSon's SynthesPs d)+Hvz leaction (Shn)
AiCyt -Hal fde 1ta with
e) Decarbexylaion. AHLoxfdeto qve ethes5 .
Sodiumn
femer- iemann eactfon
-X CHC+H, dTa0-CtH- (H TH CH)-0
0H h y t chl orfd e 5odfu CtH2CHta
h o r fede
cH t t aoH di-ethg
chioroform thyt chiorr de react of th sodium-ethcride to
Pheno
bydp gue di t h tther .
B enzalidehy de
(or) HV 2z eachon
aifca idehqde
c ed phos phe ro j
henc réac wfth dhlo rofosm and niaoH Pses cnee H (00H
heabingt g e 2 -hqdroz Benzal de hy de ter)
Hu ti-Coo
fteetic acid
5Rlicaldchq de . Chloro fcetic ac Fd.
Aetic ccid TcCccl oith ci, ded phes pho rocuj o
e l be's deatti en
gRve chloroAcetic acid
n h°s Te
NaDH
occtfonv-pos?Hon chlorinej are
Subs t u o taej píace .
Sod ium
Pheno
phenofde
-hyd o x
BPazofe acid
Decasboxyaton i
CoLO
Co) ON NaoH Ciy t NULE
Sod fum ha0o ale Methane
aoid
phcno coL uoth NaotHo9fue Sod fu m phen
o'de Sodiam-ethanoale he aHaq n fa the presence Soda
Farther fn the Drejea(e tH(Aeidic medium) qad co |me Cor) Naot t
ca0)to v e anct So diam
Methene
t o gfveá - hydro Benzoie aLd or 5aicyl'c acf d ,
Ccrbonale
 n Ehis rcacHoo ( is m u Cd in h e ormm o h e aledehydes ohieh have v- hydi0gjen ato msthose
o
N9 3 ny pastieipates o aldol cond ensation.
moles -than ol in-the
prcs ence (onC. NaoH
Cannt zard's reactPon Mdol (ondenSoutfo n e to
gtue. 6ul, -ene,I-au (or) -Btenal fs
)srifcatton d) CrosS Aldol CondlenSautfon cKnoon as aldol cond e nsat-?on.

a) Canai zaro's eactHon Osteifcation

(on
tH- t-C-H
NaOH

CH0H + H-C-0 a 4HC-oHt CtH3- CH2-H .

CH(-ocH, H3 ttH20

thancic add
formoldechyde metbyl Sodfum hano e t h i etha-

alcoho (cr) (or) Co1) noaic

mhan- CAce-il ac fd)
methouno (-Lthyl aicoh el)

h e aldchydes ohich do not have

d- hydroqen Ahetic aid reacl cofh eth{ al toh ol in-he picstnce
outoms hose nly poriipoles i n cannizor' eacion. Conc.H oith heatinqto q?ve f r u i t sSm eut o

Me les qormaid ch dey in -the pres coce nacH Ethylthanoate

+o gve meth olcDhei ( or) smethanol and Sodu
e edLrfis tglatfon
methancal e
înthis Teacion one alde hy de Conests into metb -A-nhy dsou) OcH Oct3
tCH3C AC
alceholRed uctien) and oan0 thes aidehyde convess
o
5odum metha nat (oxidavon) 50 dis pro pof tion ats Apisole methyl
chlorid -mcthl mehyl
plac Cansele an sot e

Cmino) ( majer)
b)AHdol cond ensolfon
Ans&be rcocl coth methy chlorid e in the
prcs enCe
ConC-Na0H o nhydiou to g've d -methyt anisole ( mino)bnc
CH CH C H

4-metht anfsole (majo),

etaud ehyde
Bat, 2-en e, i-al
Cor)
(or)
-hanal -13te nal
Friedal (1aftsAcelation Benzenc
b) Sand meyer ea tfon
+l3 oct'3 4Cl,l Hel
+obyd sDu) 4lcl
CH--c chloro Benzene

Ate
fAnisole chtosde o- meho rH +NL 3Omo Benzene
Accto phcnönc i - mcthRy
min or) Accto Beoane diazodiur CulnccN
phe n0ne chloride
Cqa no entene
Anisole ccacl oith Arcéy( chloride nthe mato
presentc didx on fym chloide fn the prestnce
Kenzene
aohydroqs A c l t o ive - methox e t phe non e
CU2l2 Hct (o r) cuzDT1 h13 t o 9ive chlo re 13ent ene
tcto pht nonc is no0n
a nd u-meah oX as
Or 3r Omo 3enzen
i c d a l l Crafaceratfon. 8enczeae diatonium chloside inthe presente o
Cucn EcN fogtve Cqcno Benrene,

n5) Sand- meyer Reaction

a)Ggattcsman Reaction
cDia zo tilouien
d a zotSlatfon d) carby Amfne Reactfon.
Dht happtDS hen nitcus acid Cor) Hn)er)
a) etttrman deacHon ano t Hel reculo PthAn°|ine
Nt2
N + lucl
NE N aNDL1
To)
Chloro (IO) ouS Aid
3en2eoe

Lo°- ' e 5enz ee dla x0niun

-Anlioe chtorfcde
Benzenee t N, cuC
Anlnetn-the presente Caia nto, 4 tHCl) or
d iaaooium to
Hnio n i o us eciol co f4h -'c mpera tare
chlorf de Boomo enzene
dexoa 'et m chlo sfel ce
v e e n zene
Pe9enee
hior?de fa he
5enzene diezofum
Benle 3 5rOmo
culo Cor) C[ Her-ttqfe chio ro
 methyl chioride and chtoro nzene rcad oith sod'um
d ) Car be amine Teaction (er corqanicle -tesl cer)
metal nthe prescroce o dh ethtY fo gve
Dcrc ion or
A m ocs
methyt Benzene
NH
NEC
CH c oH
A fittinq eadtion
Cale) dryethee
Anilin pheny Sso Cyao?ele -d t drNa + l K
Chlorefoin fAa.
C
bad smetlor
o u l Sm cel Chlo so Chloro
phen
cotth toH and 5enitn e enaenee
fniline scacl oih chlor0im at

heaag 9 fve bad 3m ell fphenyi so Cy a orde cal ai+h sod?um mefal in
2 mote chlo ro
Rena ene
-the prejcnde or dry ether t 9fue Bi p h e n .

5) Outz itnq reacton

a) Ourte reaction
i3 preparcd ?
c)ttinq Teacton d)tetylaon H o o is qiqnard eagen
diy ether
L

urts leaction mgx

Httmagnsium

& nacl
-AHy
CH U+ 2nia (tH CHat talide
talide

mehy methy hane dryether

chloride chlor? de + C+H3 mg Br

methyl Bromicle
meh maqntsTum
ia e Brom Pde
ehyl hloride s e a c i h sediam m eal
dT
PTCSence dry herto 9ive thane,

w a t 3 titing Reaction etng Cmctal) h t maq nesium

Brom'de Bromice

oyherr methyl 6romide r e c d o ë h mq meto he

CH &Na
Peence dry ether to g've .meHhyl mGqne a m
methy Chloro tncth
chlo ride Bromicle
Bengene 3enzcne
3 a gnard deagent
 Bromidl read oi th fel fn the
h mq mc Chaphr - 11
Presence o d cthesto gfve eyms19 nesum
AK Halides yHado
Bromde. Asenes
xplain Snand 3N 1Cactfon2
d) cross -
Al dol condensatton :
) Sn dcacHon yn? molceular Nu clco phic
nlhen ald el tc nclensalon bede en tD0 fse nl SubsHuion
eacHon
cond ensakon
atdchuydess nodn as crcss
-

-A dol o 3
a) H3CH=CH- H
C--d nuclt ophile
cH3
Scld
C3 B u-2tne
-
i c CH3 CH3
ConC nlacH
thanal CH2-CH = C 3Butyf ehioride 3 3 at alcoho
6) CH
cH3
a t 3°--Altyt tialiele
CH-CtH
-H meHhsl perl &-ehc,l-al
Doe 3°-But chlor?de
Propana
C)CHa-cH =C--
Crost In this N e acton Onl3-AlE4 Hal fdes
ameh B u U - c o t , 1-al
ldo ht TeatHo b ec ause 3- Altyo.
only Partcipalt
prodadh)CtH- CH2 -CH =C# 4H alrde giu Stable carbocauHons. acre in eimed iaie,

Penl 3-ene,l -a 3 - Buty chlo rfde tn h e pres cnce o o+nucleophile

o9iut 3 But ouleohol.

The roL-e o f h e Teactfon depeads on 3-13u

chloride ont
t s airst order Teachon= mo teculari tyis =
f s a o0 sttp eacH0n.
_ n +h is Jnu' Tcaction symetsic al bytalfel
Par Hcip auting +ogve eacim 'c mix tuie.
 SN eocHHon Bi moletdar nugle opll te
MarLS
5ubst-*
rac+fon
h a t is the strco chemi cal scsult S
and S T eactw'on 2
H-H, -t H3CtH2-oH c
Q e h e n s fon
+ 5O J Dn ve rS fon
Nucdeophi le
n rea cHon So Product

Product
mix tuse.
Ehy chlo ide e a cimít

dat ( h y t chlor?de) SN Ca cion 1 0 0 Ve ssion product

NucleOphile
cor) Ooul d en _nvcrsion
--44 ttHolfde )
Inthis S2 Ttach'on only 1AEyt Hali des only bh a are-Enantiomer5 9ve example
parHctpate-the rea c on . becadse H
is ono@n
NOn-Supes imposable mfr T0f ima qs
Haltde gfvc unsta ble o n s ?o n Jtat. are
aj nant OmersS
ote me diatt ,

a n d - lactic acid
chiorde in h e presence q o nucléeph?le x - - dacic aci el
hy eooH coeH

geeeth alco hol. H

ot-
The rah othe reacHan depen ds on thg
CH3 -

( actic
and ot nudeophile, l a c i c afd miror
Chiorfdec acfd
is s2-
s a Setondorder TcachOn .
molecula ri
in Pats
s tep seachon. Whi ch compound each o-thefoitowiaq
2 t 1s a one

oi e act aster in Snre acthon coih-oH

in+hs sn Teaction Assymetic
nuers Fo i) cH
Hal ide paricipaHng o 9ve 1e0
Br (Gi) ct32 )(CH)cel (r) cH
LOud e nvers fon
pro dact CH 2co1| eacfas er in Snsca ction beca use
2bond
bond dissocia-ioo en-thalpy o c -

Iess han C 13 Y bond.

Oc on b ecaus e
tt)H3-cl ot) Tead or sher 5e

H3-cl carbon car g

ohile compartd +o
(c113),td () (lhat arc ambiden! nucl cophtle?
Ore strucu re ollobin Nudcophil c5 oh fth possc-t0o nu
cOmpounds
caulled ambidcnl
dtophile_cenlers are
2 - chloso 3 -mehyl ptatane udeophi les
2 I-Brdmo -Sec -Buts-2-mhyl Benzene
-¬XCyanide fon Ccn" ) nrit fon ( No,
N '=
C ct-cH cH-cH3 4Crplaîn why he alty halidles thr
ou qh polar are

cHS immisble ith wale

AlEyl +Hdlides are
polar due to the
cH3 C- bond.
presentt o
Bul oul y Holides art
immisc?ble0 Hh
oaterbetause hey are
not able
frm hydnoqto
CtH f-C+H -CH3 bonds h oales molecuw es
ohich theJolloainq has hiqhest dipole 8)plainolooinq conuerstons
momcni? tha ne t o Bsonothant.
CHc Tolvene -to 8enzyl alcohol
c
) thant t o Bromo thane

H CH BT CH3-CH,-Brt+8r
hy
hane
=t6D 03D J OD
) Toluene -to B enzt olco hol
H hos hiq hesl dipole momenin -th?s C,2
o0 c-H bond poles not opposftc di rect-fonIt
clBet c tt2-

kot Ca)
T OH

-Hd
shoos dlipo le momcn
oluene Benz oleo ho)
chloy fde Ben t
9sit he rcactions Showinqhe major o nd olcLoH Cma jvf1
minor is ra c d CH-CH =CHC t Btne
PrOd dcts ohcn chlo ro Rcnzene
+ t 20 4ICI3
corth c H and ctHa(ocl n he Pres cn Afel C-H-Ct,-CH-CHg
anbyd buS B
+CH- and> cH - 3 rOmo Butone
cultEot
C H - C t H a - c H = CH2I - But ne

chloro methy Cmino)

Ben zene
chloridc chlosd tH20 CBr,
o Ivene P-chlorro
Cmino r) ol vene
Cmajor)

Ahyds ou)
+CH -tH3
chloro -chlo r0
Stnzenc CH3
Ar eto phenone
P-thlorO
minor) Ateto phe one

Cma j0r)
*Sogttzectf's de
In dthydro Hal oqlnalidn reacHons,
he preT Ted
alCene cohich haj eater
p roddcl ish a
ecttachecl rtmBotro
umber O C
ou Ps
d oubl e bonded carbon atom5
the

- Bromo Butane.
 chapter - 12(A)
3) LAArite the fol oofng ton v ersioo3 2

AAcohol, Phenol&Lthers a) Bromin aioo o

b) Benag altohol to
phtn ol t o , ,
en3ele aci d4
Gibromo pheno)

a p laln why pro panol ho s highe boilio Poi a) Baominolio n o phenol to ,4,6 bromo phenol
han h a t ofHyd rocarbun butane OH

)Propanol has higher boiling point beuause has +313 B

intr molcal ar hydrogen bonding phenol 3

carbon butane has Icssboling peit beca.us
i ) y dro ,, ribso me pheno
tdoes not have tn Ry mole tul as hyd roqtni bondli09
b) enz alcho holto tnjoic aid
Ctho e a Vander coallsorces H2- 0H
HCalin e

mn Cos)
(2-Hcohels Gre Compasaliuel more 5oluble nc0te r
Compo ra5it mo!e culas
than+Hydsocar bons C3engoic acic
xplain
3en2g Cat difid)
clcohol
ulco holb are mure 5cluble in oter becauje
bonds coth h l r i t e -the too pTepaations o phenol and oxid ason
cnotm inr molecwar hydroqen
i nd eduction propcities of
Coauter mpl ccules .
9 pheno
Hyd ro carbooS does not olublen oaler beca use
Prepantion o phenol
ft cannot form intermole ccular Hydidg t n bonds
From Chloro 3enzene
coi-th coa-ter.
Calrohel H c
ntr-molerudat H- ydio ra sbenl ) texosfnc .
bonds 300 atrm
phcno
Intti cldrultr f (Chlos o0 (sodl ium
Benzene) Phtooxid
Cnioro 3tnzene beac wi th Nao+ fn the prtgence
,0 O623 to 9ive
temp t Tate and 300 atm Psdssure

S0dium Phenox fde h e n f a loutd by t eid rc

-is i.

mediemm (HCL) to qive phcnol. ch romie acid

nt q2C 04
TOm (umeoe f 50
C heno Benzo Quinon c)
CH-C-0-à 4
041
P
Phene i n - h e presente ala, (r2 01 and HSo
cH Olaiv quinone
o) Ct1--(H3 o qve p- Benzo
C u m e h Cymen
Aretone -2
de (Phen phenols and
hy dYo Peyoxí naluic
Pr0pOne plafn-the Cccid?c

Cumene in he prescnce of Oxygen (or) oi6 9ive ltohols ?

COmpare cotth h o o
cumene hydro pero xide -then Cumcoc hyd rop eroxid e
Phenols asc&c idie tn nulure becausc -otheir
in preScn ce andH,oto give phe nol anc and ph enoxide ton
a-ffin*y to pro duce proton
Aceonc. -thocl is
phenoxid e fon s Stobilize d by rcsonance

eduction of pheno| ohy phenoxide fon more Sta blchan phenc!

O4 h e phtnoxide fon is mo re seson a nce 5tabilied

zn
Cdast)- tZno han phenol as does not iuOlue any ChCenqe
ance J rucku re .

epar ion
in s TCSon

CPhenel) Bcnzene) SinCersonance is nol

possf'ble n al Eoxidout-ion .

i n t h e presence of Z?nc dust o qive

phenol olcohol5 are cocater acidsthan pheno|
Bezenc.
OH

Cqclo+iekano
/phenel phenoxicle fon

Ephee)
inthe presence o f l n?La give cgc lo
Phcnol
Hexa nd

Oxidaubon sf phono ) phenoxide cesOnance

(-f
6
o heno
Phenol, e Sonance,
 ) alrite the -followinq conversi ons ?
phenotde fon rmore Shable-th an phenol 1)-Attele acid to-Acct chloride

-oH i)en2otc acid ts Benzamide

AIEoxide fon thloride
i) acied t o hcebyl
Areti
-Altoxide fon does nol exh6itregonanre - d + pocl, + Hd
phcnols are more acidfc-than c o hols . H-2-oH + pcl 3
3cHa oH Pcl 3C H3 + H3 Po3
b

-A
AHTang hefollowinq compounds in 1ntrtasing H -OH +30 cl - + 30, + H

order of their Property nd'coubed Acetic acid trety chlor ide

)-Atctalde hy deAtetonc, mc-4hyl ter: Bayl -kctooe Ben20i c acid to Benzam ide
- NH 2z

eact vitytoDard st1CN) (004 (odnlH

NH3
i) luoro-Atciic acid, mono chloro aceHe acd reH y
acid and dichloro eiC a td At idic stsenqth Benaoic Bcnzcic acid
acid m n oniu
3naoate
i)Order of eac ivityt-owards + C .
tts--ctt3 Ctt ct3 cHy-é-H
ATAranqethe follooinq in the incstasinq order
m ethor
their acidicstrtnq th:Ben zoic acid,
Rretonc Acetadde hy de etho Ben zoic aci d, -
n?tro -

Beazo fc c dd y -

methy tersary methy Benyi Benzofe aid

Butf tefo nc 'ne prts enCt c elce ron oft dra eoin q 9roap -No
r Order oAcidic stseng th increosetheac9dic strenqth o caboricccia3
The pscsence O elcctTon seleasfoq gDep(-cH3,
CtH-OH CH-ot ctl- -of LCHcDf ' oH decsease Lhe acciclie Strenqth o carboxqlfe
Aceic Cccid
acid
chloro Horo df ohlor .'.Octl3 hos moie electron cleasinq pe ower6an
Aretc ofd Acetic
Pe
acid.

oc
 l e ekophen one ves postHvt o d o o r m - t - e s t as t
COo COOH (ooH Coot

Condi4 ion Ct o4p oheit as en 7op h enon e

t i-te 4tg ) does not ron Foin

Benzcic
octH3
cid

u-m eth 3 enzoic -C- onN

-melhoj e B enzo?c acfd +3Nao CHI3t dnaeH
B en 7cfc acid
hea
a cid
Sodium
Acetophenone Ben Toat
I bd ofor m
y tlofcd
chloro
(9) Compare he acidic trenqth of At ctc a cid,
-Acetic acid, Benzoic actdl and phenol
NOOrl l2,
3 Nal NO eaction
acfds are acfd?c -than phenol duc heat
Carborylic more

e CarboTylote
fo qrtes tesOnance stab?lis akion
fon hao phenoxfcd e fon
he preacnte o electron oHh diauainq gouPs

rthcY intrcas e actclic streng th Carbo rtic

ac ds o
COOTI

CtH C-o M
, - ot (o
Bena e?c acid ph tno
Ch'orD aci d
aceFc

ccfd.
electron sith drawing powerOc
morethan c Hs

do yoa distinquih betoce n ret-a phen0ne

fo
on d 3 inxo ph en one,
 Benzenc diatonium chlor?de Teael co? th phenol t o
B.Oxganic Chemisty 9rVC pCkr aL hd Tory czo benient ef oange dye s

SAQS foImed
( ) H o do you prepase ethy cy an? d qnd ethj

Cyaniderom a (ommon oul Ey Halide.

Benz tne dia - An?ine
(43 C+2c+ tN c 4 - cH Cn t E c
onfum -13-348
chloride
eth chloide Ctbyl cganide
codcoholic
Para Ctmn o-
cthy chlori de rea c coth oltohol?c Cnl to give obenieoe
s
Cyetoo dye)
cthq ganid
e
ma os Produd Bcaztoe dia 20n'um chloride r eac oh

onine in-hC p TC5tntt 13 248 K g i rC

) c4H-CH2c tAg cN CH3 3 NE +Ag4cl
amina fro benzene
C toholfe)
Para o Cyutoo dye) fs-foimed
h t chlo rid e ethy
s otyanide 0ritt the
3) reducion_o nitho Benz tnt
Lthet chloride re ad th acohclicAg Cn NT2
Sh) Hct
giue e+hal _5 cCcqn adie
is
maor prod ut.
(Atedicmedian LA line
nl to N ANH
inthe Coupling
tirite the s&tps involved
ad phen ol.
BasTC ( Hyd ro7o Bea Lesl.
chloride okth anilioe
NiTo enzene
5 entoe diaqOnium
NHOH
nH
) NEN+ Neu ocl medium N-phe
Hgd 1o xg/aminc

Ben zene phtoo) Ai At H

33 R43
dic on fum N N-
Ch lori de Azo Beaz ene

Nitio Bengeoe n-the prc6 tn ce of Sn Hcl T ecl

h togfve antloe

alo bCa Z cn e
n KoHBasie mediun
N ito Benxene Tn h e presence of
poro hydrory
to 9ve hy COROBendene.
O rang e dye
 ncasal - 4 l ? n e -(o poro romo 7tnine
n N4tycl
N h o n ze in-fhe pitstoce Nt C0C t3 n i ine
tyd ox amine 11plott
medium)to9ve N-pheny ( , (o)
inthe pcsencc c iAl tl 1o give 3 Anil ne
° tro Bcnztne pa ra Bromo
pa o 13r0 mO
Aro3ent eoe.
ee-an?lidl e.
VSA@
A,8,C n theoloeoing 3oluble in wake r
Cnive the s t u t t u e o xploin why ethyl amioe 1s mo rc

cuCn NH3 cohea Cs

alin'ne fs n o S0fuble2
B

Soluble în d0oler becaasc t

Cucn 120/+ thy amine more

bonds co fLh
can fo sm inker molec ular bydsog e n
Beozenc diazonf um cyanoBcnz enc C4)
Chlortde
n Iine fs nol Soluble fn oder beca use t C a n
NH3
C Hs CODH inter molecular hyd req tn bonding f h
notosm
3 en a ami de
Ben2oic
a cid (BB) Cc)
ordér
in d re acis in q
rranqe the follosnq bas
Cano Reoze ne Cat)
ac fa p t b iuulaes? (2Hsnitt, ( tlg NHCH
=Ben z Ofe
and (o ffo hl tf 2
C =eazomide
lo-ocrthe pEb Value
fons iahcy the basic strenq th
s)xplainfollco?n q Con vers

)Bcnzoic aci d t B en zam ? de, C t Nti ( ticN RCtH3 CtNH C2is)2NH

Br omoAnilfnc
.

to ptb 3
A n t Itoe para
pcb:34
PIC6 9 fy pEb 3-2q

Benzomide
9) Benzo?c acidfo in ncreasing o rder
to0# - ni 22 oranqe-thefolloco fnq baSes
heis bas?c 5the0gthAn?linc, P- Ni0 aniline
O
Cnd p- To tau dfoe,
Beneofc Benz rafde.
acid
 A

An? ne c+H3
p-nitro
-olud ine
-An?linc.

Cabrtel phthaltmi de Sqnthes3 erculusiv*foms

Primary amin5 only (xplaio2

gabreel phthalimt de Sun-Lhesis in val ue he COnuCSYon

HCyHaltcle

CR-x) fo - am inc (R - r 2 )

h eodt
NREXx
-AH
po uss iam +ialide

bhthal mid 17thad imid el

K
naotfl a y
COna