AUGUST 2015 EXAMINATION

School of Life Sciences and Chemical Technology

(Diploma in Biomedical Science)

level 2

Time Allowed: 2 Hours

STRUCTURAL CHEMISrRY

(010492)

INSTRUCTIONS TO CANDIDATES:

1.

Check carefully to ensure you are sitting for the correct paper.

2.

Answer All questions.

3.

Begin each question on a separate page.

4.

Correlation tables are provided as Appendix 1.1 to 1.3 (pages 7 to 9).

5.

This paper consists of ~ pages including this cover page. Check carefully to
make sure your set is complete.

I
1STRCHM (BMS)

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Aug 2015 Exam

I
r

QUESTION 1 (50 marks)

1.1

(a)

What is the hybridisation of the nitrogen atom in the 2-nitrophenolate

ion (Figure 1.1)?
(1 mark)

1/

N+
\

Figure 1.1
(b)

Explain why this molecule is completely planar.

(4 marks)

(c)

Draw any THREE resonance structures of the 2-nitrophenolate ion.

Draw curved arrows to show how each form is derived from the other.
(12 marks)

1.2

The structure of menthol is shown below (Figure 1,2).

Figure 1.2
(a)

Assign R or S stereochemistry to the chiral centres labelled "a" and "b",

Show your working,
(6 marks)

(b)

Draw the enantiomer of menthol.

(3 marks)

(c)

Draw any ONE of the diastereoisomers of menthol.

(3 marks)

(d)

Draw the most stable chair conformer of menthol.

(4 marks)

(e)

Draw the Newman projection (looking down the Ca-Cb axis in Figure
1.2) of the most stable chair conformer of menthol.
(4 marks)

1STRCHM (BMS)

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Aug 2015 Exam

1.3

Barbituric acid is an acid and ionises as follows (Figure 1.3). Explain why this
compound behaves as an acid and why it is the hydrogen on the carbon
which is ionised rather than those on the nitrogen atoms.
(10 marks)

o
...

o
Figure 1.3
1.4

Assign R or S stereochemistry to the chiral centre, labelled "a" in D-threose

(Figure 1.4). Show your working.
(3 marks)

-;/'

HO

H " a\OH

,
,
\

-~

OH
Figure 1.4

QUESTION 2 (10 marks)

The ketone below (Figure 2) is ionised in the mass spectrometer.

o
Figure 2
2.1

Draw the molecular structure of the predicted detectable fragments if the

molecular ion undergoes the McLafferty rearrangement. Show the
(7 marks)
mechanism of the rearrangement.

2.2

Draw the molecular structure of the predicted detectable fragments if the

molecular ion undergoes alpha cleavage.
(3 marks)

Note: You do not need to calculate the molecular weights of the fragments in your
answer.
1STRCHM (BMS)

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Aug 2015 Exam

QUESTION 3 (15 marks)

3.1

Figure 3.1 shows the structure of L-methionine. Predict the coupling pattems
(with diagrams if necessary) for the hydrogen atoms attached to the a, 13
and y carbons (labelled in the Figure 3.1). You may assume coupling over 3
bonds only and ignore the coupling from the NH2 hydrogens.
(8 marks)

o
OH

Figure 3.1
3.2

You have a bottle labelled 'diethyl ether' but you suspect it contains tert-butyl
alcohol (Figure 3.2) instead. How could IR, 13-C or proton NMR be used to
determine which chemical is in the bottle?
(7 marks)

CH3

H O + CH 3

H3C/'--O/'--CH 3

CH 3
Figure 3.2: Diethylether (left) and tert-butyl alcohol (right)
QUESTION 4 (25 marks)

USing the MS, IR, NMR and other data provided (Figures 4.1 to 4.4). identify
compound A and explain your reasoning. You should assign as many peaks as
possible in the NMR spectra (Figures 4.2 and 4.3). For the mass spectrum (Figure
4.1) you need to identify the six largest peaks. For the IR spectrum (Figure 4.4) you
only need to assign peaks which help to confirm the identity of the compound.
(25 marks)
Elemental analysis of compound A:

C(81.04%) H(8.16%)

1STRCHM (BMS)

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Aug 2015 Exam

100
MS-NW-~02G

80
>-.

+"'

'00
c:

(J)

+"'

60

.f;
(J)

.2
+"'
0

qj

40

20

25

75

50

125

100

150

m/z
Figure 4.1: Mass spectrum of compound A
The six largest peaks are at m/z=43 , 77, 91, 105, 133 and 148

200

180

160

140

120

100

80

60

40

20

COS-OO-370

Figure 4.2: 13-C NMR of compound A

Peaks at 207.72,141.03,128.50,128.32,126.11,45.08,29.93, 29.76 ppm

1STRCHM (BMS)

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Aug 2015 Exam

jL

j)

11

10

ppm

HSP-01-46S

Figure 4.3: 1-H NMR of compound A

Peaks: 6.99-7.41 ppm (5H, complex); 2.87 ppm (2H, triplet, J=5.0 Hz); 2.75 ppm
(2H, triplet, J= 5.0 Hz); 2.11 ppm (3H, singlet)

100,-----------------------------------------------------------------,

3000

cnoo

eOilll

1500

5DO

LOOO

Wavenumber
(cm 1)

Transmittance

Wavenumber

Transmittance

Wavenumber

Transmittance

(cm- 1)

(%)

(cm- 1)

(%)

Wavenumber
(cm- 1)

Transmittance

(%)

(%)

3067
3063
3028
3004
2947

62
63
38
58
53

2926
1717
1603
1497
1454

50
4
50
27
27

1409
1081
1031
1358
1163

41
65
56
26
27

750
700
549
506
498

22
16
66
53
58

Figure 4.4: IR spectrum of compound A

1STRCHM (BMS)

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Aug 2015 Exam

Appendix 1.1: Correlation table for 13-C NMR

@
'T

I
<

,
J
~
I
~
q\ UTi .~.c:
~

~u

.11

-I

+~

- +~

:z:

.
l? l>

~o"~
~
~

!:it f
<

1STRCHM (8MS)

~8

II

+u

gz

~ ..8

ti
II

~
OC

--~

r1

I
~~~

.. 0

+0

-=

0=Y

mI

+0I

m
I

..:

i-< a"
JI

'""'~

1-<
~~

S
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Aug 2015 Exam

)0
"C
"C
CD

(J)

-i

0.5

6.0

::0

(")

,~~

"

7~.7----_ _ _-!5.!0--44.5 ('("Otj

V

:c
~

OJ
~

!!J

I R-NH
1.0
-2

3.1

5.7

5.2

...........

I
A C"C/~
2
..... R .....H

5.0 4.6

R2 C=C......

2.5
I

'II(

10
,

R-CO~

";0

9.69.5

oII

A-ceC-J:1

3.3

C1I

0'

0.0

:::::I

it

tT

....

R-C-!j

CD

-2

O'H

3.83,6
I000o-4
6.0

0
.....
~

R-C!:!, OH V

J:

I~-

i:
::0

1.7 1.4 ....... R"C-J:1

R-C~2 - CI

1.4 1.2

3.B 3.4
.... R-C!::!1- Br
.....

(yCII.

3.3 3.1

Si (Ct!3J"

2.1 D
.....--...R/ C, Cl:I,

3U3 R_CH OR 1t!,!6

9.5

.....

.......

en

::t>

;C'

2.52.2

o
I

(Q

!':?

2.6

13

:::::I

0..

.....c R-CH-R
-,

R-CH-I
-2

1.0 0.8
~

-eH
-3

11.0

10.0

9.0

8.0

7.0

6.0

5.0

4.0

3.0

2.0

1.0

-1.0

Chemiclilihift. 6 (ppm)

(J)

-1

"a
"a
CD

Approximate' infrared absorption frequencies of various groups

::u

o
:::r

I---tCH

s::
C5
s::

!E

C .. C.rH """"-""CH 2 ;CH 3

...... C = CO'l'Iin!c
I - - - -..... C-

1---------4U---tCH.r

1----4+CH.,

~C_CH

H....C=C

I---tC==C-H

I-t

C-C

::s

~CH2

Cat

..........

Q.

;C'

c,.,

patterns

oo

C=C

""I

C-C

trans

cis

ii'
!:!:.

1 - - -...1A.c:i(j

::s

.....----11 Anhydride

lit

........ Acid chloride

C"

CD

1--4
>I
>I

to

m
:::s
a.
o

...

C"'N

C=O

1------"'"4"'40H

""I

......- . . . . c -o

......Ester

IOH

Q)

(1)

"1>I

l----.IIte - C I

........ Amide

II
~C-H

1----4INH

~Aldehvde$

an(j ketones

l-----tINH

.--tNH amides

(J'I

m
)(
III

Wavenumber (em-1)

Q.

en

(')

..........C-N3

;'

"a
CD

.....- -..., NH amines

(Q

::s

'"'tl
"C

.....

Substitution

U(')J

o
~