Lecture 2

Ionic Reactions : 1) Nucleophilic substitution :

Y

R = aliphatic as well as aromatic

2) Eletrophilic substitution :
R H

3) Nucleophilic addition :
R1 X R2

R = aromatic
R1 X Y H R1 R2 XH Y

Y R2

X = O , NH

4) Eletrophilic addition :

+
5) Rearrangements :
R1 R
2

Y X X X

_X
R2 R3 X

R1

R1

Y
R2 R
3

R1 R2 Y R3

R3

Nucleophilic Substitution at a saturated carbon :

Two types of discrete mechanism : SN1 Substitution Nucleophilic unimolecular SN2 Substitution Nucleophilic Bimolecular

SN1 :
R X

slow

fast Y Rate = K[RX] R Y

SN2 mechanism :

R X

Y R

Rate = K[R__X ] [Y]

2nd order kinetics Q. Do all SN2 reactions follow 2nd order kinetics? Ans. If Y- is in large excess as compared to R-X, ( eg. If solvent is the nucleophile) then

K [Y ]

~K

Pseudo first order reaction

Rate = K1[R_X]

Effect of structure and solvent : Which mechanism will be operative will depend on structure and solvent polarity.

T.S. for SN2

_
C X Y

_
C

Inversion of configuration (Walden inversion)

R1 Y C H R2 X Y C H R2 R1

Why backside attack? To ensure maximum overlapping leading to stability of T.S.

Important Point to Remember :

Inversion of configuration does not mean R going to S or vice versa. It means that bond formation takes place opposite to that of bond breaking...which leads to the inversion. it is like inversion of umbrella in a storm.

Q.
C6H13 C Me H I

I*

C6H13 I* C

( )

Me H

(+)

Rate of racemization = 2 * rate of inversion or incorporations

For SN1 :
R1 R2 R3 C X R3 R1 R2 R1 R1 C R3 Nu

Nu

R2

+ Nu

C R3

R2

Racemization is expected Extent of inversion = extent of retention However, due to ion pair formation, more inversion then retention. Ion pair mechanism :
R2 R3 R1 C X R3 R1

R2 X

Problem : Rate of solvolysis in EtOH :

Br Br

More inversion than retention.

Br

Explain?

10-6

10-14

Q. Relative rate of solvolysis under SN1 condition

Me HC C C Me 1.0
Explain

Me Cl H2C C H C Me 10,000 Cl

Factors Affecting the Rates of SN1 and SN2 reactions : 1) The structure of the substrate 2) Concentration and Reactivity of Nucleophile (for bimolecular reactions only) 3) The effect of solvent. 4) The nature of leaving group (nucleofuge) Effect of substrate structure : For SN2 methyl > primary > secondary >> tertiary (unreactive)
R Substituent Methyl 1o 2
o

RY + X Relative Rate 30 1 0.02 0 X 0.00001

Compound H3C H3CH2C (H3C)2HC (H3C)3C (H3C)3CH2C X X X X

3o Neopentyl

N + CH3I

CH3 +

Explain the relative rate

Me

N 1.00

N 2.27

Me

N 0.47

Me

N
0.042

Me

Solvent effect For SN1 : Greater the ionizing ability of the solvent, faster will be the reaction. Dielectric constant reflects the ionizing ability.
H3C H2C H3C C OH

water
H3C H3C C Br

MeOH

H3C H3C

H3C H3C

OMe

Br

Rate of increase of [ Br- ] increases with increase in proportion of water. Dielectric constant
H2O MeOH 80 33

Q. Will a polar solvent favour the following reaction?

(CH3)3N + CH3-S(CH3)2

(CH3)3N-CH3 + S(CH3)2

Effect of Nucleophile :
rapid
CH3O

+ +

H3C

CH3OCH 3

+ +

very
CH3OH H3C I

CH3OCH 3

HI

slow
CH3OH

Nucleophilicity of

CH3O

>
OH

1) A negatively charged nucleophile is always stronger than its conjugate acid.

> > 2) In a group of nucleophiles in which nucleophilic atom is the same,

OH 2 NH 2 NH 3

nucleophilities parallel basicities.

OR OH

> a particular group, nucleophilicity increases > 3) In polar protic solvents, in

RCO 2 ROH OH 2

>

>

as we go down the group.

>
F

Br

>

Cl

>
Br

4) In polar aprotic solvents, reverse trend follows :

>

Cl

>

>

Problem
Ph

Relative rate of reaction of nucleophiles with PhCH2S

Ph

Nucleophile AcO Cl PhO HO PhS rate 3.9 4.0 3.8 74 107

Relative rate of reaction of nucleophiles with MeBr

Nucleophile AcO rate 900

Explain

Cl PhO 1100 2000

PhS HO 1.2x104 5x107

Relative Rates of Reaction of Alkyl Bromides with Lithium Iodide in Acetone

Alkyl group Relative Rate

Isopropyl Cyclopropyl Cyclobutyl Cyclopentyl Cyclohexyl Cycloheptyl

1.0 no reaction detected 0.008 1.6 0.01 1.0

Relative rates of SN2 reactions of alkyl chlorides with the iodide ion
Alkyl chloride Me Cl relative rate 200

0.02 Cl

Cl Cl

79

200

Me O Cl O Cl

920

1,00,000

I H H Br

Br

Nu