Section A: Answer ALL questions

1. Write chemical equations describing following reactions:

a) Friedel Craft alkylation.
b) Clemmensen reduction.
c) Wolff-Kishner reduction.
d) Wittig reaction.
e) Diazo coupling.
f) Friedel Craft acylation.
g) Williamson ether synthesis.
h) Fischer esterification.
i) Simmons-Smith reaction.
j) Sandmeyer reaction.
(10 marks)

2. Write a concept or term that is expressed by each of the following explanations:

a) A compound with a carbon-nitrogen double bond, formed by the reaction of a ketone or
aldehyde with a primary amine.
b) A derivative of an aldehyde or ketone having two alkoxy groups in place of the carbonyl group.
c) A reaction that joins two or more molecules, often with a loss of a small molecule such as water
or an alcohol.
d) A group used to prevent a sensitive functional group from reaction while another part of the
molecule is being modified.
e) An uncharged molecule containing a carbon atom with a negative charge bonded to a heteroatom
with a positive charge.
f) A complex of chromium trioxide with pyridine and hydrochloric acid used for the oxidation of
primary alcohols to aldehydes in excellent yields.
g) A finely divided, hydrogen bearing form of nickel made by treating a nickel-aluminium alloy
with strong sodium hydroxide.
h) A carbon atom bonded to three other carbons and bearing a positive charge.
i) A compound generally made by the reaction of a ketone or aldehyde with hydrogen cyanide.
j) The breaking of a bond in such a way that each atom retains one of the bond’s two electrons.

(5 marks)
3. Give systematic IUPAC names to the following compounds:
a) b) c)
O O

OH

O NO
COOH

d) e)
O
N

NH2
OH

(5 marks)

4. Show how the following chemical transformations can be performed using reagents and organic
compounds of your choice.
a) OH

OH

b)
O

c) OH
OH

d) O
H OH

H
H

O
O

e)
H
O N

(5 marks)

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5. Give the missing products in the following reactions.
a) O O HO
H3O+
+ ?

b) H2, Pd/BaSO4
H3C C C CH2CH3 + H2 ?
CH3OH
N

c) Na+CH3CH2O- + Br CH2CH3 ?

d) Br

Na+ CH3CH2O- + H3C C CH3 ?+ CH3CH2OH

CH3

e)
.
CrO3 Pyridine HCl(PCC) .
OH
CH2Cl2 ?
f)
CO, HCl
AlCl3/CuCl
?
H3C

g)
Ph3P CH2
O ?

h) O
NNH2

N2H4 KOH, 175oC

?
Diethylene glycol

i) NH2

(1) NaNO2, HCl

?
(2) CuCl

j)
O2N N N + O ?

COO

(5 marks)

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 Section B: Answer any TWO questions
6. a) Solving the following road-map problem depends on determining the structure of A (C7H14O),
the key intermediate. Identify compounds (or reagents) A through J.

S S
1-heptyne
(1) BuLi
(2) D
CH3 G
F(reagents)
E (1) Hg2+
(1) O3
(2) H3O+
(2) (CH3)2S

(1) B Na2Cr2O7
CH3(CH2)4MgBr C A(C7H14O)
(2) H3O+ H2SO4 (1) J
(2) H3O+
(1) I
(1) HCN (2) H3O+ OH
H (2) H3O+

OH CH3

CH3
O

(10 Marks)

b) Compound K is an optically active alcohol. Treatment with chromic acid converts K into a
ketone L. In a separate reaction, K is treated with PBr3, converting it into compound M.
Compound M is purified, and then allowed to react with magnesium in ether to give a Grignard
reagent N. Compound L is then added to the resulting solution of the Grignard reagent to give a
solution of product O. After hydrolysis of the product O, this solution is found to contain 3,4-
dimethyl-3-hexanol. Give skeletal structures for compounds K, L, M, N, and O.

K PBr3 Mg, Ether L H3O+

M N (Grignard reagent) O 3,4-dimethyl-3-hexanol

Na2Cr2O7, H2SO4
L

(5 marks)

7. a) An unknown compound P (C5H9Br) does not react with bromine or with dilute KMnO4. Upon
treatment with potassium t-butoxide, P gives only one product Q (C5H8). Unlike P, Q
decolorizes bromine and changes KMnO4 from purple to brown. Catalytic hydrogenation of Q
gives methylcyclobutane. Ozonolysis-reduction of Q gives dialdehyde R (C5H8O2). Deduce
structures for P, Q, and R consistent with this information and explain all the reactions observed.
(8 Marks)

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 b) Limonene is one of the compounds that give lemons their tangy odor. Draw the skeletal
structures of the major products expected when limonene reacts with an excess of each of the
following reagents.
(i) Mercuric acetate in methanol, followed by sodium borohydride.
(ii) Hydrogen and a platinum catalyst.
(iii) Peroxybenzoic acid.
(iv) Bromine water.
(v) A mixture of osmic acid and hydrogen peroxide.
Limonene
(vi) Methylene iodide pretreated with zinc-copper couple.
(vii) Borane in tetrahydrofuran, followed by hydrogen peroxide.
(7 Marks)
8. a) A research student wanted to synthesize a particular dibromotoluene. The student first attempted
this synthesis by methylation of benzene followed by direct bromination. Surprisingly the desired
product was not obtained even though the bromination was successful. After consultation it was
found out that the desired dibromotoluene could be obtained in good yield indirectly by the
following reaction scheme:

HNO3 (1) Fe, HCl Br2 (1) NaNO2, HCl

S T U V
H2SO4 (2) OH- FeCl3 (2) H3PO2

CH3

(i) Give the structures of the intermediate compounds S, T and U, and the desired product V in
the scheme.
(ii) Explain why the direct bromination of toluene could not give the desired product V.
(iii) What is the product(s) in the direct bromination method?
(iv) Explain the strategy used in the reaction scheme leading to the formation of the desired
product V.
(8 marks)
b) Amines are more soluble in ether than water but can be converted to water soluble amine salts by
reaction with acids such as HCl. Neutralization of the amine salt with a base such as NaOH
regenerates the amine salt. Using this fact design a separation scheme of the form given below
for a mixture of an amine with some organic and inorganic impurities in order to isolate or purify
the amine.

Mixture

(7 marks)