YOUR STUDENT NUMBER:

Year 2 Seminars, 06524, Semester 2, 2004

Bifunctional Chemistry Test ANSWERS
Q1

(a) Label all of the acidic hydrogen atoms on the molecules A - E shown.

H
H
H

H
O
H
H
H
H

OH
A

O
O

HH HH

H
H

D
Q1

(b)

O
H

H
H

H H H

H
H

Considering the most acidic hydrogen(s) of each molecule only, place the
molecules in order of acidity starting with the most acidic.
A (CO2H) > E (CH2) > B (CH2) > C > D

Q2

Consider the scheme below then answer the questions:

O

OEt
(a)

Br-(CH2)4-Br

ii) dilute H+ heat

Identify X and give a mechanism for its synthesis.

O

H H

i) aq. NaOH r.t.

2 eq. NaOEt

OEt

OEt

OEt

OEt

OEt
Br-CH2CH2CH2CH2-Br
O
O

O
H

OEt

OEt

O
OEt

EtO
Br

Br
resonance stablilized

intramolecular reaction faster than

intermolecular, especially if making 5-ring

Q2 continued overleaf

(b)

Give a mechanism for conversion of X into acetylcyclopentane (methyl

cyclopentyl ketone).
O

aq. NaOH r.t.

CH3
ONa
O

HCl (aq)
heat

CH3
OH
O

H3C

CH3

O H
O

OH

C
O

O
tautomerism

CH3
O

(c)

What would happen if acetone were allowed to react with 2 eq. NaOEt and 2 eq.
Br(CH2)4Br?

Acetone (propanone) has hydrogen atoms considerably less acidic than ethyl acetoacetate (see
Q2a). Therefore, in reaction with NaOEt (weak base) there is always ketone present in the
equilibrium mixture as well as enolate. An aldol reaction is therefore one possible side
reaction. Also the second deprotonation could take place at the same carbon as the first, or on
the other side of the C=O. Two moles of dibromide also complicates matters and so
dimers/polymers and dialkylated / and or cyclic products can form. Overall a right old
mixture would be produced!

END