Display of Mid-semester Answer Scripts

Date : 29. 10. 2004 (Friday)

Room No. : F-233
Time : 5.00 5.30 pm (*** Section 3 ***)
5.30 6.00 pm (*** Section 4 ***)

Lecture
4

T. K. Sarkar

Neighbouring group participation

Q.

HNO2

CO2H

OH H2N

H
O

HO

S
OH

N2
O

CO2H

O
O

H
O

Mustard gas a war gas that produces blisters all over the body surface
..
.S.
Cl

mustard gas

Cl

Cl

Cl
Nu

Cl

Nu

The toxicity of mustard gas is due to nucleophiles of cell

components becoming alkylated

Q.

O
Relative rate

1.0

0.014

0.14

4.85 x 10 4

Explain
Transannular participation of ether oxygen
O

..

II

III is more favorable than either I or II

Unfavorable polar effect of the C-O bond

III

OTs

OTs

Q.

CH3

CH3

O
I

II

Which compound solvolyses in HOAc faster ?

Predict the stereochemistry in each case
If I is optically active, will the solvolysed product be racemic ?
OTs
O

OAc
HOAc
OAc

AcOH
..
s

OAc

(+)

OAc

OAc

OAc

(+)

AcOH

Q.

When I undergoes SN1 solvolysis, it reacts more rapidly than isobutyl chloride II.
Explain.

CH3
H3 C

C
H
I

CH2Cl

H3C

C
H

C Cl
H2

II

phenonium ion

H
H3 C

H
H
Cl

H
H3C

H
Cl
TS

+ Cl
H
H3C

H
Sol

OH

Solvolysis products

 SN1 reaction may be substantially retarded by substitution of deuterium

atoms for hydrogen at one or more -carbons
Cl

Cl

(CD3)2CCD2CH3

(CH3)2CCD2CH3

kD
kH

0.43

H
C

0.71

stabilization by hyperconjugation
Stretching of the -C-H bonds in the activated complex
Since -C-D bonds are somewhat tighter bonds than -C-H bonds, substitution for
-hydrogens lower the extent of stabilization by hyperconjugation in the activated
complex, boost the energy of activation and thus retard the reaction.

H
empty p orbital

H 3C

CH3
H

H
H 2C

CH2
CH2
H

extra stabilization from

donation into empty p orbital of
planar carbocation

H3C
H2C

CH3
CH2
CH2
CH3

extra stabilization from

donation into empty p orbital
of planar carbocation

H
H

no stabilization: no electrons
to donate into empty p orbital
The C-H bonds are at 90 to
the empty p orbital and
cannot interact with it

A C-C bond is just as good as the C-H bond in donating electrons into an empty
p orbital and a C-Si bond is even better.

Q.

D
Ph

CH2Cl

D
HCOOH

Product

Me

Me

Cl

HCOOH

Product

Where do you expect D-effect should be considerably less?

Q. Which one reacts with MeI more rapidly ?

..N

..N

II

Q. Which reaction takes place more rapidly (I or 2) ?

Cl

Cl

H2O

H2O

Steric acceleration

OH

OH

HCl

HCl

(1
)

(2)

Phase transfer catalysis

aq. phase
Na+ CN -

aq. phase
+

Na CN
org. phase

+
Q X

Na+ X-

Q + CN

Q + CN
+

add Q + X -

RX

Q+X
+

CH2Cl2
+

QX = R4N X

RCN

RX

such as (CH3CH2CH2 CH2)4 N+ XHere no reaction takes place

because the nucleophile, CN -,
cannot enter the org. phase to
react with RX

org. phase
CH2Cl2

Here the PTC transports the cyanide ion

(as Q + CN -) into the organic phase where
the reaction
CN - + RX

RCN + X -

takes place rapidly

Phase- transfer catalysis of the SN2 reaction between NaCN and an alkyl halide

Example

CH3(CH2)7Cl

(in dioxane)

Bu4 NBr

CH3(CH2)7CN
aq. NaCN, 105 0C
(95 %)

Other types of reactions with PTC

H3C(H2C)5 HC

CH2 (benzene)

R4 N X
0

aq. KMnO4, 35 C

CH3 (CH2)5COOH
99 %

For the following reaction carried out in weakly ionizing solvent, acetone
n-C4H9OBs

if Li X is used
I > Br > Cl
if (n-C4H9)4 N X is used
Cl > Br > I

Explain

n-C4H9X

BsO