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.

S OH H2N

H CO2H

HNO2 O O

H CO2H

H O OH S N2 O HO C H O O H O R O H

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

The toxicity of mustard gas is due to nucleophiles of cell components becoming alkylated

Q.
X

X O

X O

Relative rate

1.0

0.014

0.14

4.85 x 10 4

Explain
Transannular participation of ether oxygen
O

. .

II

III

III is more favorable than either I or II Unfavorable polar effect of the C-O bond

OTs

OTs CH3 CH3 O O

II

Q.
O
I

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 O AcOH .. s OAc
(+)

O HOAc O

OAc

OAc
R

OAc

OAc AcOH

O
(+)

OAc

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

CH3 H3C C H I CH2Cl H3C C H C Cl H2

II

phenonium ion

H H3C

H H Cl

H H3C TS

H H Cl H H3C Sol

+ Cl H H OH

Solvolysis products

 SN1 reaction may be substantially retarded by substitution of deuterium atoms for hydrogen at one or more -carbons
Cl (CD3)2CCD2CH3
kD kH 0.43 0.71

Cl (CH3)2CCD2CH3

H C C X

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 CH2 CH2 H

H H 2C

H3C H2C

CH3 CH2 CH2 CH3 H H H

extra stabilization from donation into empty p orbital of planar carbocation

extra stabilization from donation into empty p orbital of planar carbocation

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 C D
HCOOH

D CH2Cl H C D

Me C Me
HCOOH

Cl

Product

Product

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

Q. Which one reacts with MeI more rapidly ?

N ..
I

N ..
II

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

Cl

H2O

OH

HCl

(1 )

Cl

H 2O

OH

HCl

(2)

Steric acceleration

Phase transfer catalysis

aq. phase aq. phase Na CN org. phase

CH2Cl2
+ add Q + X -

Na CN

+ Q X
+

Na+ X-

Q + CN
-

RX

Q+X +

Q + CN +

QX = R4N X Here no reaction takes place because the nucleophile, CN -, cannot enter the org. phase to react with RX

RCN

RX

org. phase
CH2Cl2

such as (CH3CH2CH2 CH2)4 N+ XHere 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)

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

Bu4 NBr

Other types of reactions with PTC

H3C(H2C)5 HC CH2 (benzene) R4 N X aq. KMnO4, 35 C
0

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

n-C4H9X

BsO

Explain