Functional Groups and Transformations (CT-6005M)

Exam format:

1.5 hours.

Section A – Multiple choice. 30 questions, 1 mark per question giving 30 marks total

Section B – Short answer style, answer two questions from four, each question
worth 15 marks, giving 30 marks total.

Sample Questions:

Section A consists of questions across the whole module, plus a few relevant points
on mechanism you should remember from the Semester 1 module “Introduction to
chemical bonding and reactivity”. The majority of the questions will be of the style
“what is the product of the following reaction” or “what reagents would you use to
effect the following transformation”.

1. What is the product of the following reaction?

OMe Br2, Fe powder

?
O O O Br O
Br
OMe OMe OMe OMe

Br Br Br Br
a) b) c) d)
A – Ester electron withdrawing, therefore meta directing. Deactivating,
therefore only one Br goes on.

2. What is the product of the following reaction?

OMe DIBAl-H, -78oC

?
O O

H OH OH

a) b) c) d)
 a) The reduction stops at the aldehyde because the tetrahedral intermediate
(from the first addition of hydride) is stable.

3. What is the product of the following reaction?

1. BH3,
?
2. H2O2, NaOH

H H HO
OH
OH H OH H

a) b) c) d)
c)
The first step is a hydroboration. This is a syn addition (both the BH2 and the H add
to the same side of the double bond. Sterics dictate that the BH2 adds on the
least crowded end. The second step replaces the BH2 with an OH. Overal the
process gives the anti-Markovnikiv addition of water across a double bond
(compare with oxymercuration)

4. What conditions are used to effect the following transformation?

O
?

a) LiAlH4

b) H2NNH2, KOH ---------A Wolff Kishner reduction

c) mCPBA

d) conc H2SO4

5. Alkyl Grignard reagents are made by:

a) Adding magnesium hydride to a solution of the alkyl halide in THF
b) Adding an alkyl halide to magnesium turnings in ether
c) Adding an alkyl halide to magnesium turnings in ethanol
 d) Adding an alkyl amine to magnesium turnings in ether

6. Environmentally concerned chemists formulated the:

a) five tenants of green chemistry
b) twelve principles of green chemistry
c) seventeen guidelines for a greener future
d) eight ways chemists can be better

7. An SN1 reaction proceeds by

a) Two steps via a transition state
b) One step via a transition state
c) Two steps via an intermediate
d) One step via an intermediate

8. An SN1 reaction at a stereogenic centre will lead to:

a) Racemisation of the stereocentre
b) Inversion of the stereocentre
c) Retention of the stereocentre
d) Removal of the stereocentre

9. What is the product of the following reaction?

1. Hg(OAc)2, H2O

2. NaBH4
?
O

H
OH O
a) b) c) d)

a) Oxymercuration of an alkene gives the ketone, followed by reduction

gives the alcohol.
 10. What is the product of the following reaction sequence?

1.
O PPh3
MeO H ?
2. LiAlH4
O

a) b)
H H
O O

c) d)

OH
OH

d) First step Wittig reaction with an unstabilised ylide. Gives the cis double
bond.
Second step is a reduction. Powerful reducing agent, goes all the way to the alcohol.
 Section B questions will be based entirely on this module. Each question will
tend to be about a specific topic (see below for examples). Questions will ask
you to think about:
i. reactivity of molecules,
ii. what the products of a particular reaction are,
iii. the reagents required to perform a reaction,
iv. general points about a reaction (sensitivity to air/water, toxicity etc...),
v. plus some more ‘wordy’ answers that might ask you to describe a
concept from the notes.
Look closely at the marks associated with each part of the question. If there
are four marks for a mechanism plus product of a reaction, then there will
probably be one mark for the correct product, and three marks for the
mechanism, (consisting of one mark each for two curly arrows and one mark
for an intermediate, say). E.g.:
“Give the mechanism for the following transformation, and the product formed:

1) LiAlH 4

2) H2O
O (5 marks)

Your answer should look like this:

H
H Al H
H 1 mark for intermediate
1 mark

O Li O OH
1 mark Li 1 mark
1 mark
H O + LiOH
H
1. (a) The Wittig reaction is an excellent way of making both E and Z double bonds.
(i) Give the starting material from which to make the following phosphonium
salt (1):
O
O
PPh3
?
PPh3
Br
Br 1
(1 mark)

(ii) To make the ylide, the phosphonium salt (1) is treated with a base.
Suggest why nBuLi would not be a good base with which to make the
ylide (2), and suggest an alternative base.
O
O
PPh3
?
PPh3
Br
Br 1
nBuLi is a good nucleophile, would add to the carbonyl. This is not what
we want! Instead use a hindered base such as LDA.
(3 marks)

(iii) Give the mechanism for the reaction of the ylide (2) with propanal:

O
O O
+
H
PPh3 1 mark
1 mark 2

1 mark

1 mark O PPh3 O PPh3

H H
O O

(4 marks)
 (iii) Comment on the geometry of the double bond formed in the above
reaction:
Stabilised ylide (1 mark) See structure below (1 mark) or say: charge
delocalised onto the carbonyl (1 mark). Therefore trans double bond
product (1 mark)

O O

PPh3 PPh3
2

(3 marks)

(b) Alkenes are extremely useful in organic synthesis as many other functional
groups can be made from them.
(i) By what process are alkanes in crude oil converted into alkenes?
Catalytic cracking (1 mark)
(ii) Give three problems that have been suggested with being reliant on
crude-oil based chemical feedstocks:
Oil is running out
Geopoltical problems
Climate change
(3 marks)

(15 marks total)

 2. Directing groups exert control on the products formed from electrophilic
aromatic substitution.
(a) By drawing resonance (note the typo here) forms of nitro benzene explain
whether the nitro group is ortho, para or meta directing.
(5 marks)

O OH O O O O O O
N N N N

Electron density reduced at the ortho and para positions, therefore nitro group
directs meta.

(b) para Nitro aniline, is not made directly from aniline, as a mixture of
products would be formed in the reaction. Instead, the aniline is converted
into 4 prior to nitration.
(i) Suggest a reagent for converting aniline into acetanilide (4).

O
NH 2
HN
?

4 Aceticanhydride (Ac2O)

(1 mark)

(ii) Give three reasons why nitration of 4 proceeds cleanly to give the
para nitro compound 5 whereas nitration of aniline would not give
the para nitro product cleanly.
O O

HN HN
HNO 3, H2SO4

4 5 NO
2

1. Aniline very reactive, therefore will over nitrate. 1 mark

2. The acetate on Nitrogen reduces the electron density in the ring, therefore
only mono nitrates (2 marks)
 3. Sterics: Acetate group on Nitrogen means that that the ortho position is not
nitrated 1 mark

(4 marks)

(iii) Give a mechanism for the acid catalysed removal of the acetate
group.
O
NH 2
HN +
H2O / H

NO 2
5 NO (5 marks)
2

(15 marks total)

H
H H H
O O O O

HN HN HN H2N
O H O H
H H
O
H
proton transfer
5 NO 2
NO 2 NO 2 NO 2

NH 2
O
Compare with hydrolysis of an ester. Same mechanism!
HO

NO 2