222

0) Nucleophilic Substitution Reactions

by the nafure of . Xhond
ne high teactivity ol haoalkanescan be explained carht.
C N bond js hiohlv holarised because Xis more electroneyative than
deteases as the eletronegativitydecreases from Fto) and he
nucdeophilic substitution
Ihe polatity of the C;Xbond is tesponsible for the
reacios of
halntane
8 C-NuX
Nu
Leaving group
Nuleorhile Substrate Product

SOme of the nucleophilic substitution reactions of haloalkanes are

(al.) >R-O KX
R- NC+ AgX Alcohol
Alkyl isocyanide
Na(0R
R- NO, +AgX < AyNO, >R0--RNaX
Ether
Nitroalkane RX (wilamson's synthesis)
NaStH
R-ONO + KX - KNO, >R-SH+ NaX
"Thioalcohol
Alkyl nitrite
KCN(alc.)
R'Ester
COOR + AgX RCOO Ay' >R-CN+ KX
Alkyl cyanide

Groups like cyanides and nitrites possess two nucleophilic centres and are called
Actually cyanide group is a hybrid of two contributing ambident
structures and therefore can act as a
different ways (C =N:C=N], i.e., linking through carbon atom resulting in alkyl nucleophile ts
nitrogen atom leading to isocyanides. Similarly, nitrite ion als0 represents an ambident cyanides and thr
different points of linkage(0-G-0J. The linkage through oxygen results in alkyl nucleophile th
nitrogen atom, it leads to nitroalkanes. nitrites while thr
The nucleophilic substitution can proceed via Sy1 mechanism or SE2 mechanism.
Unimolecular (SN1) Bimolecular (SE2)
It is first order reaction. It is second order reaction,.
HD
Generally carried outin polar proticcsolvents Carried out in polar aprotic solvents like acetone, DMS
like water, alcohol and acetic acid. acetonitrile or DME.

Takes place in two steps through carbocation Takes place in one step through transition state.
as the intermediate. H H
CH,
Step I
ÖH +
HH
CI’| HO----*Cl’ H0
(CH,),CBr + Br HH
Transition state
H,C CH,
CH,
+
+ OH Step II, (CH),COH
H,C CH,
Rate of reaction: 3° > 2° > 1° > CH, Rate of reaction : CH,> 1°> 2° > 3° halides
(fastest) (slowest) (fastest) (slowest)
bete
Greater the stability of carbocation, faster Less the steric hindrance in transition state, faster will
will be the reaction. reaction. CN
Tends to proceed with weak nucleophiles, Tends to proceed with strong nucleophiles, eg, CHH,O,
e.g., CH,OH, H,0, CH,CH,OH,etc. OH, etc. inversion.
Configuration is retained but in front attack Inversion of configuration takes place(Walden
inversion takes place (racemisation and
inversion).