UNIVERSITY

OF BOTSWANA EXAMINATIONS

2003-2004 SEMESTER

FRONT PAGE

COURSE NO:CHE232 TITLE OF PAPER

DURATION

2 HOURS

DATE: 2/12/2003

ORGANIC

CHEMISTRY

SUBJECT

CHEMISTRY

INSTRUCTIONS: ANSWER: QUESTION ONE AND ANY OTHER THREE

QUESTIONS

CANDIDA TES ARE ENCOURAGED KITS AND THE PROVIDED DATA

TO USE MOLECULAR

ID

GROUP NO

MC

TOTAL

DO NOT OPEN THIS PAPER UNTIL

YOU ARE

TOLD TO DO SO BY THE SUPERVISOR

of pages is 16 including

the cover page

Number

2
SECTION all questions A (2 marks each)

Answer 1

The term tautomerism refers to: (a) Reaction of amines with aldehydes and ketones (b) Reaction of enolates with aldehydes and ketones (c) An equilibrium between a ketone or aldehyde and its enol form (d) Formation of acetals from aldehydes

2. Cyclohexanone is the product when cyclohexene is (a) treated with acidic water followed by FCC (b) ozonolysed (c) treated with a Grignard reagent followed with acidic work-up (d) treated with sodium borohydride

3 Indicate the most stable carbocation.

a)

b)

c)

d)

d
set of groups

Monohalogenation of propane in the presence of a halogen and light gives two chloro products. The two products are obtained in the (a) propagation step (b) initiation step (c) termination step (d) both the termination and propagation steps

5 Indicate
(a) (b) (c) (d)

the correct priority order for the given -NHCH3> -OH> -OCH3> -CH2NH2 -OH> -OCH3> -NHCH3> -CH2NH2 -OCH3> -OH> -NHCH3> -CH2NH2 -CH2NH2> -NHCH3> -OH> -OCH3

6. The order

of reactivity

of alkyl

halides

in an SN

mechanism

is:

(a) 1> 2> 3 (b) 3> 2> }o (c) 2> }o> 3

(d) same for all alkyl halides

What is the most likely

product

for the following

reaction?

0 /Jl"", """,,CO2 H NaBH4

a)

/Jl"""",~
OH

0H

b)

/)""';~/

0H

0
c)

..-",u.,.../, H0 C
OH

d)

"""'~'""CO2H

8. The amine shown below is best classified

as:

N H

(a) (b) (c) (d)

Aromatic Secondary Primary tertiary

A mixture of benzene, propene and sulphuric acid reveals a number of facts. Which of the facts given below are true? (a) is an addition reaction, (b) an electrophilic substitution (c) it gives two products (d) all the above are true

IO.Treatment

of

ethene

oxide acid

with

sodium

methoxide

in

methanol

followed
(a) (b) (c) (d)

by Jones reagent (CrO3, H+ in acetone) gives

2-methoxyethanoic 2-methoxyethanol propanoic acid butanoic acid

Reduction

" " ~a) (b) (c) (d)

an an an an

. amIne alcohol imine aldehyde

of an amide with

lithium

aluminium

hydride

results

into

12.In organic reactions, protonation (a) slow and irreversible (b) slow and reversible (c) fast and reversible (d) fast and irreversible

with a mineral acid is known to be

3.The reaction of a Grignard reagent with a ketone followed by an acidic work-up yields (a) a product oxidisable with Jones reagent (b) a product that readily gives a carbocation in acidic media (c) a product impossible to undergo simple oxidation with Jones reagent (d) both (b) and (c)

4.Indicate the FALSE statement among the following: (a) Alcohols have higher boiling points than hydrocarbons of sim i jar molecular weight. (b) The conjugate base of an alcohol is an alkoxide

ethers

and

(c) Alcohols are more acidic than phenols (d) Low molecular weight alcohols are soluble in water

5 5. The reagent required for the self-condensation butenal is (a) sodium methoxide (b) hydrochloric acid (c) Tollen's reagent (d) pyridinium chlorochromate of ethanal to 2-

16.Ethanoyl chloride (a) reaction of (b) reaction of (c) reaction of (d) reaction of

can be prepared by: ethanoic acid with HCI ethanoic acid with methyl ethanoic acid with thionyl methanoic acid with ethyl

chloride chloride chloride

17.Reaction of methyl amine with a ketone gives

(a) (b) (c) (d) An An An An oxime acetal amide imine

I8.Acid anhydrides are: (a) less reactive than esters towards nucleophiles (b) as good acids as carboxylic acids (c) prepared from reaction of acid chlorides and carboxylate salts or carboxyl ic acids (d) hydrolysed by water to give amides

19.The correct name for 2-ethyl-l-propanol (a) 2-sec-butylmethanol (b) I-pentanol (c) 2-hydroxymethylbutane (d) 2-methyl-l-butanol

is

20.The
with

major
sulphuric

product
acid is

in the dehydration

of

I-methylcyclopentanol

(a) (b) (c) (d)

I-methylcyclopentene 2-methylcyclopentene methylenecyclopentane 3-methylcyclopentene

6 SECTION B

Answer any !!lr!: questions Question One

a) Give or draw a structural formula (preferably for each of the following compounds i. 3-0xobutanoic acid a line formula)
(2 marks each)

ii

2,2-Dibromohexanal

iii.

p-Bromophenyl

methyl

ether

IV

Propylene oxide

v. (R)-3-Methyl-l-hexyne

b) Use the IUPAC system or otherwise to name the following

compounds.

(2 marks

each)

(i)

(ii)

//""\.j/"'-"".:===

(v)

Question

Two below and answer the questions (8 marks)

a) Study the given reaction equations that follow

HCI
OH

80%

HCI, ZnCI2 heat

CI

]00% (i) What mechanism does each reaction follow and what are the competing mechanisms if any for each reaction?

(ii)

Write the mechanism for reaction conducted at 15 c.

(iii)

Which of the two reactions is likely to be faster

and why?

(iv)

What role does zinc chloride

play?

9 (b) 3-Buten-2-o1 reacts with HBr to give a mixture (i) Write a mechanism for this reaction. of products (5 marks)

(ii)

Consider the stereochemistry of each product With this in mind, draw and name each product.
(7 marks)

above.

10

Question

Three

a) Complete the following

0
i)

reactions
(2 marks each)

~A

HCN KOH

0
ii)

-)

1.

N +a C=CH
~

2. H30

0
iii)

1. NaBH4
~

0'"
0

2. H30

J
/

excess CH30H
H+

iv)

v)

Ag20

(b) Write equations for the synthesis of methyl propyl ether using the Williamson method. Consider all possibilities.
(4 marks)

(c)Arrange the following compounds in order of increasing acidity and briefly state reasons for your order: Trifluoroethanoic acid, ethanoic acid, ethanol, 2,2dichloroethanol
(6 marks)

12

Question Four
(a)
Provide the missing for reaction + products (ii i).
(14 marks)

in

the

following

reactions,

showing
mechanism

stereochemistry

where

necessary.

Provide

(i)

I-bromobutane

potassium

(-butoxide

in (-butanol

cis-I-bromo-4-methylcyclohexane solvent

NaCN

in an aprotic

(R)-3-bromo-3-methylhexane

+ aqueous acetone

13

(b) Which

will be more stable, cis- or trans-l,4-di-tertbutylcyclohexane? Explain your answer by drawing chair conformations for each isomer.
(6 marks)

14

Question Five
(a) Write a mechanism for the nitration of benzene in a mixture of sulphuric acid and nitric acid.
(6 marks)

(b)How does one convert the product above to aniline? Write an equation.
(2 marks)

15 (c) Show how the following compounds may be made from the given starting material. (i) Butanal as the only product from an alkene
(3 marks)

Methyl benzoate from benzene

(5 marks)

2-butanone

from ethyne

and alkyl

hal ide
(4 marks)

END OF EXAMINA

TION