UNIVERSITY COLLEGE LONDON

EXAMINATION FOR INTERNAL STUDENTS

MODULE CODE : CHEM0016

ASSESSMENT : CHEM0016C5UC
PATTERN

MODULE NAME : CHEM0016 - Organic Chemistry

LEVEL: : Undergraduate

DATE : 11/05/2021

TIME : 10:00

This paper is suitable for candidates who attended classes for this
module in the following academic year(s):

Year
2020/21

Additional material Periodic table.pdf and Physical constants.pdf

Special instructions N/A

Exam paper word N/A

count

TURN OVER
 CHEM0016 page 2 of 6

Candidates should attempt ALL questions. Numbers in square brackets in the right-hand
margin indicate the provisional allocation of marks to the subsections of a question.

1. Answer ALL parts.

(a) Using the following data, deduce structures for the isomeric compounds A and B.
Fully assign the IR and NMR peaks.

Compound A: C5H10O2 [5]

max 2950s, 1715s cm–1
1
H NMR  1.21 (3H, t, J 7.0 Hz)
2.15 (3H, s)
3.59 (2H, q, J 7.0 Hz)
4.46 (2H, s)
13
C NMR   26.2, 63.6, 75.8, 206.0

Compound B: C5H10O2 [5]

max 3300s, 2960s, 1710s cm–1
1
H NMR  1.11 (3H, d, J 7.3 Hz)
2.17 (3H, s)
2.62 (1H, qdd, J 7.3, 6.8 and 4.9 Hz)
2.80* (1H, br s)
3.68 (1H, dd, J 11.4 and 6.8 Hz)
3.75 (1H, dd, J 11.4 and 4.9 Hz)
13
C NMR  13.0, 28.8, 49.2, 64.2, 210.0
*Signal disappears on the addition of D2O

[Question 1 continued overleaf

 CHEM0016 page 3 of 6
Question 1 continued]
(b) Compound C is reacted with D as shown below to give E.

Compound D: C8H8O2
max 3040m, 2950s, 2820m, 1695s, 1600m, 1500m cm–1
1
H NMR  3.89 (3H, s)
6.97 (2H, d, J 8.0 Hz)
7.82 (2H, d, J 8.0 Hz)
9.90 (1H, s)
13
C NMR  55.5, 114.3, 130.0*, 132.0*, 162.1, 198.0
*You do not need to assign these signals

Compound E: C16H13NO
max 3040m, 2950m, 2200s, 1620m, 1580m, 1500m cm–1
1
H NMR  3.95 (3H, s)
6.93 (2H, d, J 8.5 Hz)
6.99 (1H, d, J 16.4 Hz)
7.21 (1H, d, J 16.4 Hz)
7.51 (2H, d, J 8.5 Hz)
7.58 (2H, d, J 7.8 Hz)
7.64 (2H, d, J 7.8 Hz)

(i) Give a structure for compound D and assign the IR and NMR data. [4]
(ii) Give a structure for the major isomer of E formed and assign the IR and
1
H NMR data, explaining the coupling constants. [7]
(iii) Provide a mechanism for the formation of E from C and D, explaining the
stereochemical outcome of the reaction. [4]
 CHEM0016 page 4 of 6
2. Answer ALL parts.
(a) Propose a structure for A, giving mechanistic details. [5]
O O
O 1. HNO3,
O A
2. C5H5NO3
N

(b) Propose structures for B and C, accounting for their formation and any
regioselectivity. [6]
O

H NH2
O B 1. n-BuLi C

H3O+ C10H13N 2. O C13H17NO

Cl

(c) Propose reagents for D and structures for E and F, giving mechanistic details for
all transformations. [6]
O
D 1. NH2OH, H3O+ 1. Li/NH3, 1 eq t-BuOH
H E F
2. Ac2O C7H5N 2. 1 eq C10H12ClN
Br Cl

(d) Provide a retrosynthetic analysis of G, and outline a synthetic route, specifying

reagents. [8]
O
N
O2N
G
O
 CHEM0016 page 5 of 6
3. Answer ALL parts.
(a) Suggest reagents for the following transformation. More than one step will be
necessary. Rationalize any regio- and/or stereo-selective steps. [5]
O O O
O O
Me3Si O
O

O O O

(b) Suggest reagents for the following transformation. More than one step will be
necessary. Rationalize any regioselective steps. [6]

OH NH

(c) Suggest a structure for A. Provide the full mechanisms for steps (ii) and (iii),
rationalizing any chemo-, regio- and/or stereoselective steps. [6]
(i) O3 followed by PPh3
(ii) 1 eq.
PPh3
A
(iii) Excess mCPBA C13H24O3

(d) Provide a retrosynthetic analysis of B, and outline a synthetic route, specifying

reagents. [8]

O O

Cl
 CHEM0016 page 6 of 6
4. The synthesis of an alkaloid A is shown below.

(a) Give a mechanism for the conversion of B to C. [4]

(b) Suggest reagents for the conversion of C to D. More than one step is required. [2]
(c) Give a mechanism for the conversion of C to D. [6]
(d) Suggest a structure for E and assign the IR spectrum. [2]
(e) Give a mechanism for the conversion of D to E. [6]
(f) The major isomer formed on conversion of E to A has the stereochemistry shown.
The coupling constants between the protons Ha, Hb and Hc were found to be as
follows:
3
JHaHb = 9.4 Hz
3
JHbHc = 3.9 Hz
Draw a clear three-dimensional structure of alkaloid A and explain the magnitude
of these coupling constants. [5]

END OF PAPER