Q.

Compound A reacts faster by the SN2 mechanism than the compound B

CH3

H3C

CH3

H3C

Br

Br

B
Nu

CH3
H

H H
H3C

Br

Nu

Br

H3C

H3C

less hindered
approach

Q. Compound A reacts faster by the SN1 mechanism than compound B

Br

Br

Epoxides

+
+

X
X

TS

Epoxides
H
H

OH

OH

(Product formed)

Q.

But

But
1. Ph3P, X2
CH2Cl2
2. H2O
O

~95%

Whereas

OH

But

But
1. Ph3P, X2
CH2Cl2
2. H2O
O

~95%

HO

X = Cl, Br, I

Bu

Bu

X
X

But

But

OH

Bu

Bu

E2 eliminations have anti-periplanar transition states

In E2 eliminations, the new bond

is formed by overlap of the C-H
bond with the C-X * antibonding
orbital

H3C

Br
C6H5

C6H5

OH

(faster)

CH3

C6H5

C6H5
H3C

Br
C6H5

C6H5

CH3

C6H5

OH

(slower)

C6H5

H
Br

Br
H3C

Ph

Ph

CH3

Ph
Ph

OH

OH

faster

slower

Br
CO2H

C6H5
H

CO2H

C6H5

C5H5N

COC6H5

COC6H5
H

Whereas

Br
C6H5

HO2C
H

C5H5N

COC6H5

C6H5

COC6H5

Br
H

C6H5
H

COC6H5
CO2H

C5H5N

C6H5

COC6H5

C6H5

CO2H

COC6H5

Predict the product of following reaction

OMe

HO2C
HO
NH2

HNO2

Q.

CH3

CH3

CH3
NaOEt
Cl

(faster
reaction)

1:3
CH3

CH3
NaOEt

(250 times

Cl slower)

Me

OEt
H
Me

Cl

Cl
Me

Cl
Cl

(slower reaction)

Me
H
OEt

Q.

Br
Br

(faster)
Br
Br
I

(slower)

Br

Br

fast

Br

fast
Br
I

Br
Br
I

slow

fast

Br

Br
I

Reactions of 2-bromo-4-phenylcyclohexanols with base and silver oxide

OH

OH or
C6H5

Ag2O

C6H5

Br

O
OH OH or

C6H5

Ag2O
Br

C6H5

OH or
Ag2O
C6H5

OH

Br
OH

Br

C6 H5

Br OH

C6H5

Ag2O

CHO
C6H5

C6H5

Br
OH

OH

C6H5

Predict the product

OH
Me

H+

Me
OH
OH2

Me
Me

Me
Me
OH

CHO

:OH
N2

..
OH

NaNO2, HCl

NaNO2, HCl

N2

OH
OH
NH2

NH2

OH
OH
NH2

NH2

..
OH
N2

:OH

NaNO2, HCl

NaNO2, HCl

N2
O
O

Q.

Br
Br

(faster)
Br
Br
I

(slower)

Br

Br

fast

Br

fast
Br
I

Br
Br
I

slow

fast

Br

Br
I

It is more difficult to form an acetal of compound A than of B.

Why?
O
O
HO

OH

H+

A
O
O
HO

OH

H+

Which compound should saponify faster (A or B)?

CO2Et

CO2Et

EtO

OH

Ans: B
vs

OH
O
OEt