Alkyl halides

SNi substitution nucleophilic intramolecular

• Term SNi stands for substitution nucleophilic internal
• SN1 gives Racemic mixture, SN2 gives inversion, but here we will
get Retention in configuration
• Four center type intermediate (Alkyl chlorosulfite)
• Example – chlorination of alcohols with thionyl chloride
(SOCl2), decomposition of alkyl chloroformates ROH + SOCl2 ,
ROH + PCl5 , ROH + PBr5 , ROH + COCl2
• The reaction between alcohols and thionyl chloride is second
order, which is predicted by this mechanism.
• In the SNi mechanism, one part of the leaving group must
be able to attack the substrate, and should detach itself
from the rest of the leaving group in the process.

• The first step in the SNi is similar as the very first step of
the SN1 mechanism, dissociation into an intimate ion
pair.

• But in the second step part of the leaving group attacks,

necessarily from the front since it is unable to get to the
rear, which results in retention of configuration.
Example

ROH + SOCl2  RCl + SO2 + HCl

Mechanism

Four center type intermediate

(Alkyl chlorosulfite)
Effect of pyridine

• Addition of pyridine to the mixture of alcohol and thionyl

chloride results in the formation of alkyl halide with
inverted configuration.

• Inversion results because the pyridine reacts with ROSOCl

to give ROSONC5H5 before anything further can take place.
And then Cl‾ freed in this process now attacks from the rear.
Reaction of ROH with SOCl2 in presence of pyridine
Elimination Reactions

 Elimination (- ) HH H
 Elimination (-)
 Elimination (-) H C-C-C-Cl
HH H
 Hydrogens give,  - Elimination
 Hydrogens give,  - Elimination
 Hydrogens give,  - Elimination
 - Elimination
Alkyl halide
HH H
H C C C Cl
HH H HH H
H C C C:
HH Carbene
 - Elimination

HH H Alkyl halide

H C C C Cl
HH H
HH H
H C CC
Alkene H H
 - Elimination

HH H Alkyl halide

H C C C Cl H H
HH H HCH
C C
Cyclic alkane H H
 Elimination (-) Dehydrohalogenation
1. E1 elimination
2. E2 elimination
3. E1CB elimination
E1 Elimination Reaction
• The E1 mechanism is a two-step process
• First step- rate determining step is ionization of the substrate to give
a carbocation
• Second step- loses a  proton to a weak base, usually the solvent
like H2O, CH3OH, CH3CH2OH.
• It is high temperature reaction
• Endothermic reaction (require high temperature)
• SN1 exothermic reaction (require low temperature)
• Rate depends on stability of carbocation and leaving group
• There would be both products (E1 and SN1) but at high temperature
(~60  C) E1 favoured, at low temperature (<20C) SN1 favoured
• If we will take strong base, it will not wait for removal of X‾. It will
attack on  carbon.
• Polar protic solvents are favoured (to help the formation of
carbocation)
• Reaction exhibits first-order kinetics.
• This mechanism normally operates without an added base.
• E1 mechanism related to the SN1.
• In fact, the first step of the E1 is exactly the same as that of the SN1
mechanism.
• The second step differs in that the solvent pulls a proton from the 
carbon of the carbocation rather than attacking it at the positively
charged carbon, as in the SN1 process.
• In a pure E1 reaction (without ion pairs, etc.), the product should be
completely non-stereospecific, since the carbocation is free to adopt
its most stable conformation before giving up the proton.
• Reactivity of alkyl halide for E1
3Benzylic > 3Allylic > 2Benzylic > 2Allylic > 3 > 1Benzylic > 1Allylic > 2 > 1
Mechanism

rds

Rate = k [Alkyl halide]

Example -1
Example -2
Saytzeff rule

More substituted alkene is more stable,

due to hyperconjugation
Example -3

H H 2 O, 60 o C
Br



H2O, 60C

H H
H H H
rearrangement
H
Hydride shift
Example -3 Cis and trans alkene

CH3OH