SNi MECHANISM

Nucleophilic substitution of alcohol with HX gives

haloalkane but there is possibilities for the formation of
rearranged products especially when there is formation
of carbocations.

However when sulphur or phosphorous halides are
used , no rearrangement product obtained. It follows Sni
mechanism (Substitution Nucleophilic Internal)
Eg:

R-OH + SOCl2 R-Cl + so2 + HCl
MECHANISM
FIRST STEP:
The lone pair of oxygen attacks electrophilic centre of
SO2Cl2 (S)gives positive charge In oxygen and
negative on other to form an unstable ion pair which
eliminates a molecule of HCl to form Alkyl chloro
sulphite intermediate (similar to SN1)
SECOND STEP
Internal attack of the nucleophile Chlorin to the electrophilic
Carbon from the same side , breaking C-O bond with the
elimination of SO2 molecule
Here Nucleophile attacks from the same side of the
leaving group which leads to retention of configuration
Eg
NIGHBOURING GROUP PARTICIPATION
In some cases the rate of SN2 reactions is found to be
extremely high and the Product is obtained with the retention
of configuration. These reactions follows Nighbouring group
mechanism
Here nighbouring group acts as nucleophile.. Ie one of the
nucleophile is a part of the same molecule and is located at
the C atom or farther from the leaving group

As it involves two steps with Sn2 mechanism two
inversions leads to retention of
configuration
In the first step attack of neighboring group at the
carbon from the backside forming an unstable
intermediate with inversion of configuration ( SN2
reaction )
In the second stage nucleophilic attack takes place to form
the product with inversion of configuration ( Another SN2
reaction) ie two SN2 reactions with inversion of configuration
. Final product with retention of configuration
Eg::
First step
Second step
L-2- BROMOPROPIONATE
L-2- METHOXY PROPIONATE
FEATURES

1)High reaction rate compared to SN2

2)Followsfirst order keinetics (substrate only)

3)Retention as a result of two inversion

4)Also called Anchimeric assistance
E1CB MECHANISM
(UNIMOLECULAR MECHANISM FROM A CONJUGATE BASE)
In E1CB mechanism a proton is initially abstracted to generate
conjugate base at equilibrium which then loses L- giving
elimination products in therate determing step

As the proton has to be removed from a carbon from a neutral
species ( a difficult job)
A strong base is needed for E1CB reaction as in E2 reaction. More
over increase in strength of base and concentration of base
increase the rate of E1CB reaction
If more than one beta hydrogen more acidic hydrogen is removed
Better the leaving group, better will be the rate of E1CB reaction ( if
E1CB is operating) Because rds involve the leaving group otherwise if
the leaving group is so good It will leave before the anion is formed
leading to E2 mechanism
E1CB mechanism operates when the abstraction of proton is very easy
( removal from a highly electronegative atom)and the conjugate base
is resonance stabilised)
E1CB mechanism also operates when the expulsion of leaving
group is difficult ( Leaving group is bad like F-,-OH-,RO- etc or if
leaving group has partial double bond due to resonance)
Eg
Dehydrohaloganation of geminal halohydrin because H+ is
removed from highly
electronegative oxygen
2
Dehydrohalogenation of carbonyl compounds
because resultant carbanion is resonance stabilised
If the leaving group is a better leaving group, E1CB reaction will takes place
But if the leaving group is very good E2 reaction will takesplace
3-
Dehydroflurination of because fluoride is a bad leaving group
4 Dehydrohalogenation when halogen has partial double bond due
to resonance in vinyl halide and aryl halides
5 Dehydration in basic medium