H

H
H

OH
H
C
H
OH
C
H

C
H
H
C
H
C
H
H

Q1

Which molecule has an odd number of peaks in its 13C NMR spectrum?
A

D
O

O
O

MgCl

Q2

A structural isomer of C5H11OH has a significant peak in its mass spectrum with an m / z value of 31.
Its 13C NMR spectrum shows four different peaks.
What is the isomer?

Q3

3-methylbutan-1-ol

3-methylbutan-2-ol

pentan-1-ol

pentan-2-ol

The diagram shows the 13C NMR spectrum of an alcohol of formula C4H10O.

200 180 160 140 120 100

80

60

ppm

What is the alcohol?

A

butan-1-ol

butan-2-ol

2-methylpropan-2-ol

2-methylpropan-1-ol

40

20

Q4

Dioxins can be formed during the combustion of chlorine-containing compounds in waste incinerators.
Dioxins are very unreactive compounds and therefore remain in the environment and enter the food chain.
Many dioxins are polychlorinated compounds such as tetrachlorodibenzodioxin (TCDD) shown below.
CO

CO

CO

CO

TCDD can also be analysed using

13

Deduce the number of peaks in the

C n.m.r.

13

C n.m.r. spectrum of TCDD.

[1]

H
H
H

C
H

Si
H

H
C

H
Si(CH3)4

H
C

O
C
O

ethanoic acid

Q5

The

H C

H C

O
C
O

13

C NMR spectrum of a compound with formula C4H8O2 shows peaks at 15 ppm, 20 ppm,

What is the structure of the compound?

HOCH2CHCHCH2OH

CH3COOCH2CH3
H

H
B

butanoic acid

propanoic acid

60 ppm and 175 ppm.

HCOOCH(CH3)2

HO

OH

Q6

Shikimic acid, right, occurs naturally in star anise.

HO

Using the numbers on the diagram of shikimic acids structure,

indicate (by putting numbers in the boxes) which carbon atoms in

HO

the molecule are responsible for each signal in its 13C NMR spectrum.

OH

OH

The precise order of carbons within the group of two and the group of three are not required.

200

180

160

140

120

100
/ ppm

80

60

40

20

0
[3]

Q7

Atenolol is an example of the type of medicine called a beta blocker. These medicines
are used to lower blood pressure by slowing the heart rate. The structure of atenolol is shown below.
OH
H2N

CH2

The

CH

CH2

CH3

CH

Q7 (a)

CH2

CH3
q

13

C n.m.r. spectrum of atenolol was recorded.

Use the structure of atenolol given to deduce the total number of peaks in the
13

C n.m.r. spectrum of atenolol.

[1]

Q7 (b)

Part of the

C n.m.r. spectrum of atenolol is shown on the right.

13

Use this spectrum to answer the questions which follow.

Give the formula of the compound that is used as a standard and
produces the peak at = 0 ppm in the spectrum.
[1]

Q7 (c)

One of the peaks in the

13

C n.m.r. spectrum is produced by

the CH3 group labelled q in the structure of atenolol.

Identify this peak in the spectrum by stating its value.
[1]

100

80

60

40

/ ppm

Q7 (d)

There are three CH2 groups in the structure of atenolol. One of these CH2 groups
produces the peak at = 71 in the

13

C n.m.r. spectrum above.

Draw a circle around this CH2 group in the structure of atenolol shown below.
OH
H2N

C
O

CH2

CH2

CH

CH2

CH3

CH

CH3
[1]

20

Q8

Many aromatic nitro compounds are used as explosives. One of the most famous is
2-methyl-1,3,5-trinitrobenzene, originally called trinitrotoluene or TNT, shown below .
CH3
O2N

NO2

NO2

Q8 (a) Deduce the number of peaks in the 13C n.m.r. spectrum of TNT.
[1]

Q8 (b)

Deduce the number of peaks in the 1H n.m.r. spectrum of TNT.

[1]

Q8 (c)

Using the molecular formula (C7H5N3O6), write an equation for the decomposition
reaction that occurs on the detonation of TNT. In this reaction equal numbers of moles
of carbon and carbon monoxide are formed together with water and nitrogen.
[1]

Q9

Imipramine has been prescribed as an antidepressant.

The structure of imipramine is shown below.

H 2C

CH2

N
H 2C

CH2

H 2C

CH3

H 3C
Q9 (a)

Deduce the number of peaks in the

13C

n.m.r. spectrum of imipramine .

[1]

Q9 (b)

Deduce the number of peaks in the 1H n.m.r. spectrum of imipramine .

[1]

absorption
of energy

11

10

/ ppm

3
1
2

Q10

Atenolol is an example of the type of medicine called a beta blocker. These medicines
are used to lower blood pressure by slowing the heart rate. The structure of atenolol is shown below.
OH
H2N

C
O

CH2

CH2

CH

CH2

CH3

CH

CH3
q

The 1H n.m.r. spectrum of atenolol was recorded.

One of the peaks in the 1H n.m.r. spectrum is produced by the CH2 group labelled p in
the structure of atenolol.
Suggest a range of values for this peak. Name the splitting pattern of this peak.
Range of values
Name of splitting pattern

Q11

[2]

The 1H NMR spectrum of butanone is shown below.

B

C
D
A

Without considering chemical shift data, which peak is produced by

Q11 (a)

the red hydrogens;

[1]

Q11 (b)

the blue hydrogens;

[1]

Q11 (c)

the green hydrogens?

[1]

Q12

The 1H NMR spectrum of triethylamine is shown below.

B
C

Without considering chemical shift data, which peak is produced by

Q12 (a)

the red hydrogens;

[1]

Q12 (b)

the blue hydrogens?

[1]

Q13

Haloalkanes have been used as aerosol propellants and refrigerants but are now
largely banned due to the damage they cause to the ozone layer.
Halon 1211 was once commonly used in fire extinguishers (now only found in fighter
jets) and Halothane is an inhalational general anaesthetic.
Further examples of haloalkanes are given in the table below.
Common name

Structural

Number of different

formula

fluorine environments

CFC-113

Cl2FC-CClF2

CFC-113a

Cl3C-CF3

HFC-134a

F3C-CH2F

CFC-11 (Freon-11, R-11)

CCl3F

CFC-12 (Freon-12, R-12)

CCl2F2

CFC-13

CClF3

Halon 1211

CBrClF2

NMR spectroscopy is a technique which reveals the number of different environments

of certain nuclei in a molecule. NMR active nuclei such as 1H, 13C and 19F are routinely studied.
Q13 (a)

Complete the table above indicating the number of different fluorine environments for
each of the compounds AG

Q13 (b)

[3]

The anaesthetic Halothane has the formula C2HBrClF3 and shows one signal in its
19

F NMR spectrum. Draw the two possible three-dimensional structures for Halothane.

[2]

Q13 (c)

The intensity of a signal in a 1H or 19F NMR spectrum is proportional to the number

of nuclei in that particular environment.
For each compound with more than one signal in its 19F NMR spectrum, indicate in
the appropriate column of the table the expected intensity ratio.

[2]

Q13 (d)

NMR spectra are complicated by coupling between nuclei. If an NMR-active nucleus

is within three bonds of another similar nucleus which is in a different chemical
environment, its signal will be split into a number of peaks instead of appearing as a
single peak. If a nucleus couples to n NMR-active nuclei, its signal will split into a
total of (n + 1) peaks.
The 19F NMR spectrum of one of the haloalkanes from the table is shown below.
Draw the structure of the haloalkane and indicate with an arrow which fluorines give
rise the signals X and Y.

[2]

Q14

The 1H NMR spectrum for ibuprofen is shown below.

On the structure of ibuprofen below, mark the protons responsible for the peaks A, B,
C, D, E and F on the spectrum. The integrals and expansions for each peak are shown on the spectrum.

O
CH3

OH
CH3

H3C
[6]

H
R

C
H

1H

2H

H
2H

C
H

2H

1H

2H

Q15

Below are the structures of a pair of isomers.

H
C
H

H
C
H

H
O

C
O

C
H

H
C
H

isomer 1

Q15 (a)

H
C
H

H
C
H

isomer 2

Give the molecular formula of these isomers.

[1]

Q15 (b)

What type of isomerism is shown by these two isomers?

[1]

Q15 (c)

Isomer 1 is named 2-phenylethyl propanoate. Give the name of isomer 2.

[1]

Q15 (d)

The 1H NMR spectrum of one of the isomers is shown in below.

integration

10

3
2

5
/ ppm

Explain which of the two isomers corresponds to the 1H NMR spectrum.

You should refer to the splitting patterns and integration values of all the peaks in y our
answer. Note that the phenyl group protons appear as a single peak.

[6]

Q16

An unknown compound T consists of carbon, hydrogen and oxygen atoms only.

T and the 13C NMR spectrum of T are both shown below.
The 1H NMR spectrum of T
Deduce the structural formula of the compound T and explain the form of the
spectra. This should include the identification of the atoms or groups of atoms
responsible for each signal.

11

10

6
1H

200

180

160

140

NMR spectrum of T

120
13C

100

80

NMR spectrum of T

60

40

20

0
/ ppm

0
/ ppm

[7]

Q17

A, B and C are three structural isomers of molecular formula C6H10O. They are all cyclic.
Isomers A and B have strong infra-red absorptions, A at 1720 cm1 and B at 1780 cm1;
C has an absorption at 1650 cm1 and a broad absorption between 3230 and 3550 cm1.

In the proton n.m.r. spectrum, A has three peaks (signals) with areas in the ratio
2:2:1 whereas B has two peaks in the ratio 3:2; C has 4 peaks with areas in the ratio 1:2:3:4.

C reacts readily with bromine water; A and B do not.

None of the three isomers can be oxidised by acidified potassium dichromate(VI).

Suggest structures for A, B and C, explaining your reasoning.

[10]