NSR

(Nucleophilic substitution reaction)

 SOLVENT

There are two types of solvent:

1.Polar solvent.
2.Non-polar solvent. Polar Solvent

Polar protic solvent Polar aprotic solvent

H atom directly bonded to H atom is not directly bonded to
electronegative atom. electronegative atom.
Ex: H2O, ROH, CH3COOH, NH3 etc.
Solvent Category (PPS or PAS)

H2O

DMSO

Alcohol
DMA
DMF
Acetone
 NUCLEOPHILICITY AND BASICITY

Nucleophile : Attack on carbon Base: Attack on H+

OH act as a Nucleophile OH act as a Base

Factors affecting nucleophilicity :

1. A negatively charged nucleophile is a better than lone pair containing nucleophile

2. When negative charge is on same atoms then more availability of charge will
be good Nu (in other word less stable negative charge will be good Nu)

3. When negative charge is on different atoms of one period then negative charge on
less EN atom will be more available hence good Nu
(in other word consider less EN in a period)
 Factors affecting nucleophilicity :
4. When negative charge is on different atoms of one group then consider the role
of solvent

Polar aprotic solvent (PAS) :

(small size hence more electron density

so more available hence GOOD Nu)

Polar protic solvent (PPS) :

small size
More solvation(dissolve) in water
less donation hence WEAK Nu

NOTE: If nothing is mentioned then consider polar protic solvent (PPS).

 Factors affecting nucleophilicity :

5. Nucleophilicty is affected by steric effects also.

Nucleophilicity order

NOTE:
(Across the period nucleophilicity and basicity order is same)
(down the group nucleophilicity and basicity order may or may not be same)
Compare nucleophilicity order ?
AIPMT 2007
AIIMS 2014
AIIMS 2016
AIIMS 2018
AIIMS 2010
 LEAVING GROUP
Leaving group is a species that departs with the bonded pair of electrons.

Compare leaving group ability:

LEAVING GROUP
Q: Compare leaving group ability of the following?
 NUCLEOPHILIC SUBSTITUTION REACTION ( SN )

Mechanism : This reaction has been found to proceed by two

different mechanisms.

1. SN1 (Substitution Nucleophilic Unimolecular)

2. SN2 (Substitution Nucleophilic Bimolecular)

 SN1 REACTION (SUBSTITUTION NUCLEOPHILIC UNIMOLECULAR)

MECHANISM

1st step :

2nd step :

CHARACTERISTICS
1. It is a two step reaction.
2. Kinetics of reaction

3. Rate is independent of concentration of nucleophile.

4. Carbocation intermediate is formed. Rearrangement may be possible

during product formation.
 SN1 REACTION (SUBSTITUTION NUCLEOPHILIC UNIMOLECULAR)

5. SN1 reaction is favoured by polar protic solvent (Ex. H2O, ROH )

Helps in ionizing bond.

Helps in stabilization of charges.
 SN1 REACTION (SUBSTITUTION NUCLEOPHILIC UNIMOLECULAR)

6. STEREOCHEMISTRY OF SN1 REACTION

Retention product

ENANTIOMERS

Inversion product

Important:
In SN1 reaction, racemic mixture is expected but inversion product dominates over
retention product. Hence it shows Partial racemisation.
Means substrate has one chiral center will show Partial racemisation. More the
stability of carbocation, more will be racemization.
Remember: If C.C. not present then no racemisation.
 SN1 REACTION (SUBSTITUTION NUCLEOPHILIC UNIMOLECULAR)

7. Reactivity towards SN1 reaction stability of carbocation intermediate

If leaving group is different then R-I > R-Br > R-Cl > R-F

8. SN1 reaction does not take place in

Bredt’s rule violation

Vinyl halide Aryl halide

Compare rate towards SN1 reaction
Compare rate towards SN1 reaction
Compare rate towards SN1 reaction
Q: Which of following can show partial racemisation ?

Hint: substrate has one chiral center will show Partial racemisation.
If C.C. not present then no racemisation.
 SN2 REACTION (SUBSTITUTION NUCLEOPHILIC BIMOLECULAR)

MECHANISM

CHARACTERISTICS

1. It is a single step reaction.

2. Kinetics of reaction Rate of SN2 lkyl halide][Nucleophile]

3. Rate is dependent of concentration of nucleophile.

4. No carbocation intermediate is formed. Hence no rearrangement.
5. SN2 reaction is favoured by polar aprotic solvent. (Ex: DMSO , DMF , acetone etc.)
 SN2 REACTION (SUBSTITUTION NUCLEOPHILIC BIMOLECULAR)
6. STEREOCHEMISTRY OF SN2 REACTION

Transition state
(Penta-coordinated)

Inversion of configuration
(Walden Inversion)
NOTE:
SN2 reaction completes with 100% inversion of configuration.
 SN2 REACTION (SUBSTITUTION NUCLEOPHILIC BIMOLECULAR)

7. Reactivity towards SN2 reaction

Branching at beta
position decreases
rate of SN2
 SN2 REACTION (SUBSTITUTION NUCLEOPHILIC BIMOLECULAR)

IMPORTANT:
Allyl and benzyl halide shows SN2 reaction in good amount.

(Allyl halide) (Benzyl halide)

shows SN2 reaction in excellent amount

Rate towards SN2 reaction

 SN2 REACTION (SUBSTITUTION NUCLEOPHILIC BIMOLECULAR)

8. SN2 reaction does not take place in

Vinyl halide

Aryl halide

Neopentyl halide
NOTE :
SN1 and SN2 reaction does not take place at sp2 hybridized carbon atom
Compare the rate towards SN2 reaction
Compare the rate towards SN2 reaction
AIIMS 2018
AIIMS 2018
AIPMT
Q: Which has maximum reactive towards SN1 reaction ?

(1) (2)

(3) (4)
CPMT
AIIMS 2006
 HOME WORK on 01-01-2021

Module 3:
Chapter 4 (reaction mechanism-ii)
Bbox= 6
Ex 1= Q 35,40,45,46,47,50,
Ex 2= Q 5,8,13,14,17,20,29,51,53,
Ex 3= Q 11,12,15,16