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 ***)

T. K. Sarkar

Q. Which compound solvolyses faster in HOAc containing NaOAc (I or II)? The product is the same from either I or II. What is the structure of the product?
S S

H Cl I II H

Cl

H OAc

Q. Which compound solvolyses faster in HOAc? (I or II). Give the structure of the product from I.
OTs OTs

II

OTs OAc

HOAc

I III

Participation of the electrons of the double bond gives the ion III , which would be stabilized by delocalization of the positive charge

Q. Suggest a mechanism for the following reaction

O Ph Ph O
O Cl Ph N O Ph O O Ph N H O Ph Ph OH Ph N O Ph Ph N O O O

O Cl N H2O Ph CH3CN, heat N H O O Ph

Q. Hydrolysis of PhSCH2CH2Cl is considerably slower than that of EtSCH2CH2Cl. Explain.

Crown ethers
O O O O O

:O
+

K+
O O O O:

K :O ..
O

18 - Crown - 6

K + CN

RCH2X

18-C-6 benzene
CH3CN

RCH2CN

K+ X -

C6H5 CH2Cl

KF

18-C-6

C6H5 CH2F +

K+ Cl -

100 %

Host-guest relationship The hole has diameter 2.7 A Diameter of K+ = 2.66 A

/ Examples of SNi reaction

Cl H3CCH CHCH2OH SOCl2 H3C C H CH CH2

Ether (only)
H3C H C OH CH CH2 SOCl2 H3C CH

Ether

C H

CH2Cl

(only)

Mechanism
H3C H3CCH CHCH2 O S O Cl CH2

.. .Cl .

..

O S O

H3C CH Cl

CH

CH2

SO2

Examples of SN2/ reaction

Cl D
NaOMe

OCH3 H

Cl D

Cl D

NaOMe

OCH3 D H

H3CO D

H O R H Bu
t

H N N +

But

R=Cl2C6H3-

Biological Nucleophilic Substitution

Biological methylation for an organic chemist

..Nu

CH3 I

CH3Nu +

For nucleophile in a cell, MeI cannot be used, because alkyl halides are insoluble in water

In biological systems, you have got predominantly aqueous environment

Lets take the case of methylation in the cells of plants and animals:

Here it involves the transfer of a methyl group from an amino acid (methionine)
CH3 H3C HO N+ CH2CH2OH CH3 choline

O2C CHCH2CH2 S CH3 + NH3

HO adrenaline

CH CH2NH CH3 OH

N CH3 N nicotine

Choline : important in the transmission of nerve impulses Adrenaline : causes blood pressure to increase Nicotine : makes smoking tobacco addictive

triphosphate group
nucleophile
OH OH O P O O OH P O OH

..
O2C CHCH2CH2SCH3 NH3

O CH2 O H

leaving group

O Adenine H

ATP

CH3 O2CCHCH2CH2 H3N S CH2 O H H

Adenine

OH

OH OH O P O O OH P O O OH P O OH

+
OH OH

Triphosphate ion

NH2 N

Adenine =
N N

H3C N H3C OH H3N

CH3

O2CCHCH2CH2

CH2 O H H OH H

Adenine

H OH

CH3 H3C N OH CH3

S-Adenosylmethionine (SAM)

O2CCHCH2CH2 H3N

CH2 O H H H

Adenine

choline
H OH OH

. . .

Nature makes use of high nucleophilicity of sulfur Weakly basic group (eg. triphosphate of ATP) functions as LG Attack at the less hindered CH3- rather at one of the more hindered -CH2- groups

Ambident nucleophiles
I
KCN + EtI Et CN
CN NC

Ag

AgCN + EtI

Et

NC

NaNO2 + RBr AgNO2 + RBr

RNO2 R O N O

Ag+, EtI OEt K +, EtI N O N .. O N Et H3C O MeI H C O Me

..

C H

CO2Et

H3C :.O : .

C H

CO2Et

CH3-O- CH2 Cl

H3C

CO2Et

H3C O

C H

CO2Et

CH2 OCH3