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THE UNIVERSITY OF THE WEST INDIES


ST. AUGUSTINE

EXAMINATIONS OF DECEMBER 2005

Code and Name of Course: CHEM 3267 (C30B) – BASIC ORGANIC CHEMISTRY II

Date and Time: Duration: Two (2) hours

INSTRUCTIONS TO CANDIDATES: This paper has NINE (9) pages and SIX (6) questions.

ANSWER ANY FOUR (4) QUESTIONS

1. (a) Study the reaction scheme below and provide a detailed mechanistic explanation
for the formation of nitrile (2).

NMe2 CN
NaCN

N N
H H

1 2
(10 marks)

(b) Propose a detailed mechanistic explanation for the synthesis of the fused indole (5)
from phenylhydrazine (3) and cyclohexanone (4) in acetic acid.

NHNH2 O

AcOH
+

3 4 H 5

(15 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 2

2. Write mechanisms to account for the products formed in the following reactions.

(a)
S

O
N
N
Bu3SnH SiMe3
H3 C
AIBN
H3C
H3C
H3 C
SiMe3

(b)

CH3
H3C
CH3 CH3
HCl +
Cl
CH3 Cl
CH3

CH3 H3 C

O
(c) H
N3 N
heat
O
toluene
NH2 N
H

[Hint: The -NH2 group is involved in the latter part of the reaction.]

(3 x 8 + 1 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 3

3. (a) Consider the following scheme which shows the Strecker synthesis of the amino
acid leu:

CH3 CH3 Loss of CH3 NH


O OH
NH3 (aq) NH2 H2O

H3C H H3C H H3C H


I II III

KCN (aq)

CH3 COOH CH3 CN


NH2 + NH2
H3O ,
H3C H reflux H3C H
leu IV

Write mechanisms for each of the steps involved in the conversion of compound I
to compound IV.
(10 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 4

Question 3 (continued)

(b) The Merrifield solid phase peptide synthesis is used commercially for the production
of peptides. Using the compounds shown below, outline with mechanisms and
explanations, the commercial production of the dipeptide, phe – ile.
(15 marks)

H H

H2N C COOH H2N C COOH

H C CH3 CH2
CH2Cl
CH2CH3
solid support
ile

phe

N C N

O DCCD

C
O Cl
FMOC

PLEASE TURN TO THE NEXT PAGE


© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 5

4. Write mechanisms to account for the products shown in the reactions below. Comment on the
stereochemical outcome in (b) and (c).

(a)
H3C CH3
O
H3C CH3
CHO
ButO-OBut +
100o

O H3C CH3

(10 marks)
(b)
H
Me
CuI

CO2Me
N2 CO2Me H

(7 marks)
(c)

H3C H3C
N N

CH3CH2OH

500
H H

Cl OCH2CH3
(8 marks)
PLEASE TURN TO THE NEXT PAGE
© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 6

5. Consider the structure of D-idose shown below:

CHO

HO H

H OH
D - idose
HO H

H OH

CH2OH

(a) Generate, using suitable drawings, the Haworth projection formula of:
(i) α - D – idofuranose
(ii) β - D – idopyranose
(6 marks)
(b) Account mechanistically for the following reactions:

(i) CHO HC NNHC6H5

H OH H OH

HO H 1 mole C6H5NHNH2 HO H

H OH pH 4 - 5 H OH

H OH H OH

CH2OH CH2OH

(5 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 7

Question 5 (b) (continued)

(b)
(ii) CH2OH
O OH

OH
OH H

OH

CH3NH2 , CH3OH
reflux

CH2OH CH2OH
O O H
NHCH3

OH OH
OH H OH NHCH3

OH OH

(6 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 8

Question 5 (continued)

(c) Using suitable mechanisms and explanations, account for the following
observations:

CH2OH CH2OH
O 18
O OCH2CH3 OH
+ 18
H / H2 O
OH OH

H OH H
OH

OH OH

CH3CH2OH
WHEREAS

CH2OH CH2OH
O OC(CH3)3 O OH
+
H / H218O
OH OH
OH H OH H

OH OH

(CH3)3C18OH

(8 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……


Page 9

6. (a) Provide a detailed explanation for the reaction of pyrrole (6) with acid that results in the
formation of a polymer.

N
H
6

(8 marks)

(b) For the reactions below, provide a detailed reaction mechanism that results in the formation
of the respective products.

1. POCl3
+ H NMe2 H
N 2. Na2CO3 N
H H
7 8 9 O

O
Me2NH
+ NMe2
N H H AcOH N

Me 11 Me
10 12
(17 marks)

END OF EXAMINATION PAPER

© The University of the West Indies Course Code CHEM 3267 (C30B) 2005/2006/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……

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