A2 CHEMISTRY UNIT 4: IDENTIFYING ORGANIC COMPOUNDS

1.

A compound containing 58.8% carbon, 9.8% hydrogen and 31.4% oxygen is

subjected to mass spectrometry and found to give intense peaks at m/z = 43 and
m/z = 57, in addition to a molecular ion peak at m/z = 102.
Infra-red analysis of the molecule showed a sharp peak at m/z = 1710 cm-1.
A proton nmr spectrum of the molecule yielded the following peaks:
Chemical shift

Splitting

0.8
1.1
2.3
3.7

Triplet
Sextet
Triplet
Singlet

Integration
factor
3
2
2
3

Deduce the structure of the molecule and account for the formation of all the
peaks the spectra.

2.

This question concerns four isomers, W, X, Y and Z, with the molecular

formula C5H10O2
(a)

The
proton
n.m.r.
spectrum
of
W
shows
4
peaks.
The table below gives the chemical shifts, values, for each of these
peaks, together with their splitting patterns and integration values.

/ppm

2.18

2.59

3.33

3.64

Splitting pattern

singlet

triplet

singlet

triplet

Integration value

State what can be deduced about the structure of W from the presence
of the following in its n.m.r. spectrum.
(i)

The singlet peak at = 2.18

..................................................................................................

(ii)

The singlet peak at = 3.33

................................................................................................

(iii)

Two triplet peaks.

.................................................................................................

(iv) Hence, deduce the structure of W.

(b)

T ra n s m itta n c e /%

The infra-red spectrum of X is shown below.

0
4

3
W

(i)

a v

e n

2
1

e r / c m

What can be deduced from the broad absorption centred on 3000

cm1 in the infra-red spectrum of X?
............................................................................................................
2

(ii)

Given that the proton n.m.r. spectrum of X contains only two peaks
with the integration ratio 9:1, deduce the structure of X.

(c) Isomers Y and Z have the structures shown below.

H

3H

CC

3H

CC

3H

2H

Identify the two reagents you could use in a simple chemical test to
distinguish between Y and Z. State what you would observe when each
of Y and Z is tested with a mixture of these two reagents.
Reagents ....................................................................................................
Observation with Y
.....................................................................................................
.
Observation with Z
.....................................................................................................
.
3.

Compounds C and D, shown below, are isomers of C5H10O

C
(a)

C2

H
C
H

2
2

H
C
C
C
C
H

H
CC

H
O

Name compound C.
.....................

(b)

Use the Data book to help you to answer this question.

(i)

Suggest the wavenumber of an absorption which is present in the

infra-red spectrum of C but not in that of D.
...........

(ii)

Suggest the wavenumber of an absorption which is present in the

infra-red spectrum of D but not in that of C.
...........

(c)

Deduce the number of peaks in the proton n.m.r. spectrum of C.

.....................

(d)

Identify a reagent that you could use to distinguish between C and D. For
each of C and D, state what you would observe when the compound is
treated with this reagent.
Reagent ..
..
Observation with C
..
Observation with D
..

(e)

Compound E, CH3CH2CH2CH2CHO, is also an isomer of C5H10O

Identify a reagent which will react with E but not with C or D. State what
you would observe when E is treated with this reagent.
Reagent ..
..
Observation with E
..

4.

Each of the parts (a) to (e) below concerns a different pair of isomers.
Draw one possible structure for each of the species A to J, using your data
book to help you
(a)

Compounds A and B have the molecular

A decolourises bromine water but B does not.
A

(b)

formula

C5H10

Compounds C and D have the molecular formula C2H4O2

Each has an absorption in its infra-red spectrum at about 1700 cm1 but
only D has a broad absorption at 3350 cm1
C

(c)

Compounds E and F are esters with the molecular formula C5H10O2

The proton n.m.r. spectrum of E consists of two singlets only whereas
that of F consists of two quartets and two triplets.
E

(d)

Compounds G and H have the molecular

G shows optical activity but H does not.
G

(e)

formula

C3H6Cl2

Compounds I and J have the molecular formula C6H12

Each has an absorption in its infra-red spectrum at about 1650 cm 1 and
neither shows geometrical isomerism. The proton n.m.r. spectrum of I
consists of a singlet only whereas that of J consists of a singlet, a triplet
and a quartet.
I

5.
The proton n.m.r. spectrum of an organic compound F, C4H8O, is shown
below.

/p p m

The measured integration trace gives the ratio 0.5 to 0.75 to 0.75 for the peaks at
2.47 (quartet), 2.15 and 1.05 (triplet), respectively. The infra-red spectrum of
compound F has an intense band at 1715 cm1. In the mass spectrum of F,
dominant fragmentation peaks appear at m/z = 43 and m/z = 57.
(a)

Give the structural formula of the compound responsible for the signal at
0.00 in the n.m.r. spectrum.

(b)

How many different types of proton are present in compound F?

....................................................................................................................

(c)

What is the ratio of the numbers of each type of proton?

...................................................................................................................

(d)

Which alkyl group is responsible for the signal at 2.15 in the n.m.r.
spectrum?
....................................................................................................................

(e)

The peaks at 2.47 and 1.05 arise from one group in compound F.
Identify this group and explain the appearance of the splitting pattern
shown in the n.m.r. spectrum.
Group..........................................................................................................
Explanation ................................................................................................
....................................................................................................................
...................................................................................................................

(f)

Which group is responsible for the band at 1715 cm 1 in the infra-red

spectrum of compound F?
...................................................................................................................

(g)

Give the structures of the species responsible for the peaks at m/z values
of 43 and 57 in the mass spectrum.
Peak at m/z = 43.........................................................................................
Peak at m/z = 57.........................................................................................

(h)

Give the structure of compound F.

...................................................................................................................

6.

(a)

(b)

Describe how propanal, CH3CH2CHO, and propanone, CH3COCH3, can

be distinguished using
(i)

a chemical test

(ii)

the number of peaks in their proton n.m.r. spectra.

Compound Z can be produced by the reaction of compound X with

compound Y as shown in the synthesis outlined below.
C

3H

t e p
1
C HX O
S

3H

C3

S t e p
2
O
C HY

t e p

3H

CC

3H

C
3H

O
Z

i) Identify compounds X and Y. For each of the three steps in the

synthesis, name the type of reaction involved and give reagents and
conditions.

C h e m ic a l s h ift, /p p m

4 .3 4 .2 4 .1 4 .0 3 .9 3 .8 3 .7 3 .6 3 .5 3 .4 3 .3 3 .2 3 .1 3 .0 2 .9 2 .8 2 .7 2 .6 2 .5 2 .4 2 .3 2 .2 2 .1 2 .0 1 .9 1 .8 1 .7 1 .6 1 .5 1 .4 1 .3 1 .2

7.
The proton n.m.r. spectrum of compound X is shown below.

10

Compound X, C7H12O3, contains both a ketone and an ester functional group. The
measured integration trace for the peaks in the n.m.r. spectrum of X gives the ratio
shown in the table below.
Chemical shift, /ppm

4.13

2.76

2.57

2.20

1.26

Integration ratio

0.8

0.8

0.8

1.2

1.2

Answer the following questions.

(a)

How many different types of proton are present in compound X?

...............................................................................................................................

(b)

What is the whole-number ratio of each type of proton in compound X?

...............................................................................................................................

(c)

Draw the part of the structure of X which can be deduced from the presence of
the peak at 2.20.
...............................................................................................................................

(d)

The peaks at 4.13 and 1.26 arise from the presence of an alkyl group.
Identify the group and explain the splitting pattern.
Alkyl group ...........................................................................................................
Explanation ...........................................................................................................
...............................................................................................................................
...............................................................................................................................

(e)

Draw the part of the structure of X which can be deduced from the splitting of
the peaks at 2.76 and 2.57.
...............................................................................................................................

(f)

Deduce the structure of compound X.

...............................................................................................................................

11

8.

Compound Q has the molecular formula C4H7ClO and does not produce misty
fumes when added to water.
(a)

The infra-red spectrum of Q contains a major absorption at 1724 cm1.

Identify the bond responsible for this absorption.
....................................................................................................................

(b)

The mass spectrum of Q contains two molecular ion peaks at m/z = 106
and m/z = 108.
It also has a major peak at m/z = 43.
(i)

Suggest why there are two molecular ion peaks.

............................................................................................................

(ii)

A fragment ion produced from Q has m/z = 43 and contains atoms

of three different elements. Identify this fragment ion and write an
equation showing its formation from the molecular ion of Q.
Fragment ion ......................................................................................
Equation..............................................................................................

(c)

The proton n.m.r. spectrum of Q was recorded.

(i)

Suggest a suitable solvent for use in recording this spectrum of Q.

............................................................................................................

(ii)

Give the formula of the standard reference compound used in

recording proton n.m.r. spectra.
............................................................................................................

(d)

The proton n.m.r. spectrum of Q shows three peaks. Complete the table
below to show the number of adjacent, non-equivalent protons
responsible for the splitting pattern.
Peak 1

Peak 2

Peak 3

Integration value

Splitting pattern

doublet

singlet

Quartet

Number of adjacent,
non-equivalent protons

1
12

Using the information in parts (a), (b) and (d), deduce the structure of
compound Q.

(f)

A structural isomer of Q reacts with cold water to produce misty fumes.

Suggest a structure for this isomer.

Compound Q has the molecular formula C4H8O2

(a)

The infra-red spectrum of Q is shown below.

100

T ra n s m itta n c e /%

9.

(e)

50

R
0
4000

3000

2000
1500
W a v e n u m b e r/c m 1

1000

500

Identify the type of bond causing the absorption labelled R and that
causing the absorption labelled S.
R .................................................................................................................
S ................................................................................................................
13

(b)

Q does not react with Tollens reagent or Fehlings solution. Identify a

functional group which would react with these reagents and therefore
cannot be present in
Q.................................................................................................................

(c)

Proton n.m.r. spectra are recorded using a solution of a substance to

which tetramethylsilane (TMS) has been added.
(i)

Give two reasons why TMS is a suitable standard.

Reason
1 ............................................................................................
Reason 2 ...........................................................................................

(ii)

Give an example of a solvent which is suitable for use in recording

an n.m.r. spectrum. Give a reason for your choice.
Solvent ...............................................................................................
Reason ...............................................................................................

(d) The proton n.m.r. spectrum of Q shows 4 peaks.

The table below gives values for each of these peaks together with
their splitting patterns and integration values.
/ppm

2.20

2.69

3.40

3.84

Splitting pattern

singlet

triplet

singlet

triplet

Integration value

What can be deduced about the structure of Q from the presence of the
following in its n.m.r. spectrum?
(i)

The singlet peak at = 2.20

...........................................................................................................

(ii)

The singlet peak at = 3.40

...........................................................................................................

(iii)

Two triplet peaks

...........................................................................................................

14

(e)

Using your answers to (a), (b) & (d),deduce the structure of compound Q.

10. The proton n.m.r. spectrum of an ester, A, is shown below.

Chemical shift, /ppm

The measured integration trace gives the ratio 0.50 to 0.50 to 0.75 to 0.75 for
the peaks at 4.13, 2.32, 1.33 and 1.09, respectively.
(a)

The mass spectrum of compound A has a molecular ion peak at m/z =

102. Deduce the molecular formula of compound A.
15

...................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)

(b)

What is the ratio of the numbers of each type of proton?

.....................................................................................................................................
(1)

(c)

What can be deduced about the arrangement of protons from the splitting patterns in the
n.m.r. spectrum?
.....................................................................................................................................
(1)

(d)

Deduce the structure of compound A and label with the letters a, b, c and d the four
groups of equivalent protons.

(1)

(e)

Assign the various signals in the table below to the groups of protons in compound A
previously labelled a, b, c and d.
Chemical shift, /ppm

1.09

1.33

2.32

4.13

Label of group
(4)

16

11. Each of the parts (a) to (f) below concerns a different pair of isomers. Deduce
one possible structural formula for each of the species A to L.
(a)

A and B have the molecular formula C2H4O2. An aqueous solution of A

reacts with calcium carbonate to liberate carbon dioxide, but B does not.
A

(b)

C and D have the molecular formula C3H8O. C has a broad absorption

band at 3300 cm1 in its infra-red spectrum, but D does not.
C

(c)

E and F have the molecular formula C3H6C12. E has only one peak in its
low resolution proton n.m.r. spectrum but F has two.
E

17

(d)

G and H have the molecular formula C3H6O and both have strong
absorption bands at about 1700 cm1 in their infra-red spectra. G turns
acidified potassium dichromate(VI) solution green but H does not.
G

(e)

I and J have the molecular formula C4H9Br. I shows optical activity, but J
does not.
I

(f)

K and L have the molecular formula C5H10. K has a weak absorption

band at 1650 cm1 in its infra-red spectrum, but L does not.
K

18

ANSWERS
1.

Molecular formula = C5H10O2

infra-red spectrum:
peak at 1710 cm-1 indicates a carbonyl
proton nmr spectrum:
peak at 0.8 is CH3- adjacent to -CH2peak at 1.1 is -CH2- adjacent to CH3- and -CH2peak at 2.3 is -CH2CO- adjacent to -CH2peak at 3.7 is CH3Oso molecule is methyl butanoate, CH3CH2CH2COOCH3
mass spectrum:
peak at 43 from: CH3CH2CH2COOCH3+. CH3CH2CH2+ + .COOCH3
peak at 57 from: CH3CH2CH2COOCH3+. CH3CH2CH2CO+ + .OCH3

2.

(a)

(i)

C
O or RCOCH3;

(ii)

H3CO or ROCH3;

(iii)

CH2CH2 or two adjacent methylene groups;

(iv)

3H

2-

H3

- C

- O

O
OR
CH3COCH2CH2OCH3;
(b)

(i)

OH in acids or (carboxylic) acid present

(ii)

C
C

3H

3H

C
C

3H

(c)
reagent

+
K2Cr207 /H

no reaction

orange to green or turns

green
5

19

3.

(a)

Pentan-2-one

(b)

(i)

1680 1750 (cm

(ii)

3230 3550 (cm

(c)

1
1

(d)
Reagent

K2Cr2O7/H
+

Na

CH3COOH/
H2SO4

with C
with D

no reaction
goes green

no reaction
effervescence

no reaction
Sweet smell

1
1

Reagent
with E

Tollens
silver
(mirror)

Fehlings or Benedicts
red ppt or goes red
(not red solution)

(e)

4.

(a)

1
1

any C5 alkene

H
e t c

e n

H 2
a l i s e

H
H

(b)

O
H

H
O

Ho r

or CH3COOH
D

C
O

3H

or HCOOCH3

H
H

or HOCH2CHO
(c)

O
H

C
O

3H

3H

3H

20

O
C

3H

CC

H
O

(d)

2H

(C a Hl l o2 w5

C
H

2H

C o lr C

l2 H

H
H

H
H

(e)

CC

2H

o Cr H 3l

C
C

C
l

3H

3H

3H

2H
2H

3
3

C ( aH l l o2 w5

H hex-3-ene
)
NOT

1
[10]

5.

(a)

(CH3)4Si (1)

(b)

3 (1)

(c)

2 : 3 : 3 (1)

(d)

methyl or CH3 (1)

(e)

Group

ethyl or CH2CH3 or C2H5 (1)

Explanation

CH3 splits CH2 quartet or 4 peaks (1)

CH2 splits CH3 triplet or 3 peaks (1)

(f)

C = O (1)

(g)

Peak at m/z = 43
Peak at m/z = 57

3
1

+
+
CH3CO or [CH3CO] (1)
+
+
CH3CH2CO or [CH3CH2CO] (1)

21

(h)

CH3COCH2CH3 (1)

1
[11]

6.

(a)

(i)
Reagent

Tollens

Fehlings or Benedicts

+ I2/Na0H
K2Cr2O7/H
or acidified

Propanal

silver
(mirror)

red ppt or goes red

(not red solution)

goes green

No
reaction

Propanone

no
reaction

no reaction

no reaction

Yellow
(ppt)

(penalise incomplete reagent e.g. K2Cr2O7 or Cr2O7

+
/H then mark on)
3

(ii)

(b)

propanal 3 peaks
propanone 1 peak

ignore splitting even if wrong

1
1

X is CH3CH2COOH or propanoic acid

if both name and formula given,

both must be correct, but

Y is CH3CH(OH)CH3 or propan-2-ol

allow propanol with correct formula

Mark the type of reaction and reagent/condition independently.

The reagent must be correct or close to score condition
Step 1

Oxidation

+
K2Cr2O7/H or other oxidation methods as above
2 +
allow Cr2O7 H if penalised above (ecf)
reflux (not Tollens/Fehlings) or heat or warm

Step 2

reduction or nucleophilic
addition

reduction or
nucleophilic addition

reduction or
hydrogenation

NaBH4

LiAlH4

H2

in (m)ethanol or water or ether

or dry

ether or dry

Ni / Pt etc

22

Step 3

esterification or (nucleophilic) addition-elimination or condensation

(conc) H2SO4 or HCl
warm (allow without acid reagent if X and Y given as reagents)
or reflux or heat

1
1
1
1
[15]

7.

(a)

5 (1)

(b)

2:2:2:3:3 (1)
any order but not multiples
1

(c)
(d)

CH

(R )

(1)

CH3CH2 or C2H5 or ethyl (1)

4.13 (quartet) : CH2 peak split by CH3 / next to CH3 (1)
1.26 (triplet) : CH3 peak split by CH2 / next to CH2 (1)

(e)

CH2CH2 (1)

(f)

C H

(C O )
C
CH 2C H
O

(C O )
C
O C H 2 C H 3 (2)
O

allow (1) for CH3COCH2OCOCH2CH3

or CH3COOCH2COCH2CH3
Must be C7H12O3

8.

(a)

C=O (1)

1
or carbonyl

(b)

(i)

Cl has (2) isotopes (1)

35
37
Allow Cl and Cl without word isotope but must be correct
isotopes
+
must have 3 different elements, i.e. not C3H7 but allow balanced
+
equation including C3H7 for the equation mark

(ii)

Fragmentation: CH C = O (1)
3
must be an ion (*)

23

+
Equation: C4H7ClO CH 3 C O + C2H4Cl (1)

+
(*) allow C2H3O+ or any form of it (i.e. CH2CHO or
+
CH2COH ) in equation, be generous with position of + or
if fragment ion completely wrong (not m/z = 43) no further marks
(c)

(i)

CDCl3 or CCl4 (1) or D2O, C6D6

(ii)

Si(CH3)4 (1) or SiC4H12

(d)
Peak 1

Peak 2

Peak

Integration value

Splitting pattern

doublet

singlet

quartet

Number of adjacent, nonequivalent protons

(1)

C
(e)

3H

C
O

(1)

or CH3COCHClCH3
(f)

O
C

3H

o
C

9.

(a)

3H

C2

H
C

C
l

C2

o
(1)

r
C2

( C

R: O-H (alcohols) (1)

S: C=O or carbonyl (1)
2

(b)

aldehyde (1)

-CHO or RCHO (1)

1

(c)

(i)

Reason 1: TMS inert or non-toxic or volatile / easily removed

Reason 2: single (intense) peak
peak of 12 protons

24

has 12 equivalent protons

all protons in same environment
OR
peak / signal upfield of others
highly shielded
more shielded
peak away from others or = 0 or low
not solvent, not cheap
any 2 reasons (1)

(ii)

Solvent: CDCl3 or CCl4 (NOT D2O)

Reason: proton free (1)
allow no hydrogens (atoms)
+
NOT H / hydrogen ions
4

(d)

(e)

10.

(a)

C H

(i)

(1)

(ii)

OH (1)

(iii)

CH2CH2 (1)

CH

CH

CH

O H

(1)

A is RCOOR (1)
R + R = 102 44 = 58 (1) C4H10
C5H10O2 (1)

(b)

2 : 2 : 3 : 3 (1)

(c)

Two CH2CH3 groups present (1)

(d)

C H C H 2 COOC H C H 3 (1)
3
2

(e)
Chemical shift, /ppm

1.09

1.33

2.32

4.13

Label of group

a (1)

d (1)

b (1)

c (1)

25

11.

(a)

CH3COOH (1)

HCOOCH3

or HOCH2C
(b)

(c)

CH3CH2CH2OH
or CH3CH(OH)CH3 (1)

CH3CH2OCH3 (1)

C H

(e)

C l

(d)

(1)

C H

CH

C l

(1 )

CH

C H

C l

C l
(1 )

CH3CH2CHO (1)

CH3COCH3 (1)

H
CH

C H 2C H
(1 )

B r
(f)

C H 3C H 2C H 2C H 2B r
o r (C H 3 ) 2 C H C H 2 B r
o r (C H 3 ) 3C B r
(1 )

K
one alkene e.g.

C H 2= C H C H 2C H 2C H

L
one cycloalkane e.g.

C H

C H 3 C H = CH C H 2CH
(C H 3 ) 2 C = C H C H

(1 )
3

H 2C = C (C H 3 )C H 2 C H

e tc
3

(1 )
C H 2C H

C H

CH

26