Consider the following reaction sequence starting from methylbenzene.

(a) Name the type of mechanism for reaction 1.

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

(b) Compound J is formed by reduction in reaction 2.

(i) Give a reducing agent for this reaction.

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

(ii) Write an equation for this reaction. Use [H] to represent the reducing agent.

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(1)

(iii) Give a use for J.

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(1)

Page 1 of 81
(c) Outline a mechanism for the reaction of bromomethane with an excess of compound J.
You should represent J as RNH2 in the mechanism.

(4)

(d) Compound K (C6H5CH2NH2) is a structural isomer of J.

Explain why J is a weaker base than K.

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(3)
(Total 11 marks)

Page 2 of 81
 (a) Ester 1 and Ester 2 were studied by 1H n.m.r. spectroscopy.
2

Ester 1 Ester 2

One of the two esters produced this spectrum.

ppm

Deduce which of the two esters produced the spectrum shown. In your answer, explain the
position and splitting of the quartet peak at δ = 4.1 ppm in the spectrum.

Predict the δ value of the quartet peak in the spectrum of the other ester.

Use Table B on the Data Sheet.

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(4)

Page 3 of 81
(b) Cetrimide is used as an antiseptic.

[CH3(CH2)15N(CH3)3]+ Br–

cetrimide

Name this type of compound.

Give the reagent that must be added to CH3(CH2)15NH2 to make cetrimide and state the
reaction conditions.

Name the type of mechanism involved in this reaction.

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(4)

(c) Give a reagent that could be used in a test-tube reaction to distinguish between benzene
and cyclohexene.
Describe what you would see when the reagent is added to each compound and the test
tube is shaken.

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(3)
(Total 11 marks)

Page 4 of 81
 This question is about the primary amine CH3CH2CH2NH2
3
(a) The amine CH3CH2CH2NH2 reacts with CH3COCl

Name and outline a mechanism for this reaction.

Give the IUPAC name of the organic product.

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

........................................................................................................................
(6)

(b) Isomers of CH3CH2CH2NH2 include another primary amine, a secondary amine and a
tertiary amine.

(i) Draw the structures of these three isomers.

Label each structure as primary, secondary or tertiary.

(3)

Page 5 of 81
(ii) Use Table 1 on the Data Sheet to explain how you could use infrared spectra in the
range outside the fingerprint region to distinguish between the secondary amine and
the tertiary amine.

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(2)

Page 6 of 81
(c) The amine CH3CH2CH2NH2 can be prepared by two different routes.

Route A is a two-stage process and starts from CH3CH2Br.

Route B is a one-stage process and starts from CH3CH2CH2Br.

(i) Identify the intermediate compound in Route A.

Give the reagents and conditions for both stages in Route A and the single stage in
Route B.

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(7)

(ii) Give one disadvantage of Route A and one disadvantage of Route B.

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(2)
(Total 20 marks)

Page 7 of 81
 Imipramine has been prescribed as an antidepressant. The structure of imipramine is shown
4 below.

(a) The medicine is usually supplied as a salt. The salt is formed when one mole of imipramine
reacts with one mole of hydrochloric acid.

Suggest why the nitrogen atom labelled b is more likely to be protonated than the nitrogen
atom labelled a when the salt is formed.

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(3)

(b) Deduce the molecular formula of imipramine and give the number of peaks in its 13C n.m.r.
spectrum.

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(2)
(Total 5 marks)

Page 8 of 81
 Ammonia and methylamine were dissolved in separate samples of water. The two solutions had
5 equal molar concentrations.

State one simple method, other than smell, of distinguishing these solutions.
State what you would observe.

Method ....................................................................................................................

Observation .............................................................................................................

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(Total 2 marks)

Page 9 of 81
 Each of the following conversions involves reduction of the starting material.
6
(a) Consider the following conversion.

Identify a reducing agent for this conversion.

Write a balanced equation for the reaction using molecular formulae for the nitrogen-
containing compounds and [H] for the reducing agent.

Draw the repeating unit of the polymer formed by the product of this reaction with benzene-
1,4-dicarboxylic acid.

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(5)

Page 10 of 81
(b) Consider the following conversion.

Identify a reducing agent for this conversion.

State the empirical formula of the product.

State the bond angle between the carbon atoms in the starting material and the bond angle
between the carbon atoms in the product.

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(4)

(c) The reducing agent in the following conversion is NaBH4

(i) Name and outline a mechanism for the reaction.

Name of mechanism ............................................................................

Mechanism

(5)

Page 11 of 81
 (ii) By considering the mechanism of this reaction, explain why the product formed is
optically inactive.

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(3)
(Total 17 marks)

The amide or peptide link is found in synthetic polyamides and also in naturally
7 occurring proteins.

(a) (i) Draw the repeating unit of the polyamide formed by the reaction of propanedioic acid
with hexane-1,6-diamine.

(2)

Page 12 of 81
 (ii) In terms of the intermolecular forces between the polymer chains, explain why
polyamides can be made into fibres suitable for use in sewing and weaving, whereas
polyalkenes usually produce fibres that are too weak for this purpose.

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(Extra space) ......................................................................................

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(3)

(b) (i) Name and outline a mechanism for the reaction of CH3CH2COCl with CH3NH2

Name of mechanism............................................................................

Mechanism

(5)

(ii) Give the name of the product containing an amide linkage that is formed in the
reaction in part (b) (i).

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

Page 13 of 81
(c) The dipeptide shown below is formed from two different amino acids.

Draw the structure of the alternative dipeptide that could be formed by these two amino
acids.

(1)

(d) The amino acids serine and aspartic acid are shown below.

(i) Give the IUPAC name of serine.

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

(ii) Draw the structure of the species formed when aspartic acid reacts with aqueous
sodium hydroxide.

(1)

Page 14 of 81
(iii) Draw the structure of the species formed when serine reacts with dilute hydrochloric
acid.

(1)

(iv) Draw the structure of the species formed when serine reacts with an excess of
bromomethane.

(1)
(Total 16 marks)

Page 15 of 81
 The hydrocarbons benzene and cyclohexene are both unsaturated compounds.
8 Benzene normally undergoes substitution reactions, but cyclohexene normally
undergoes addition reactions.

(a) The molecule cyclohexatriene does not exist and is described as hypothetical.
Use the following data to state and explain the stability of benzene compared with the
hypothetical cyclohexatriene.

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(4)

Page 16 of 81
(b) Benzene can be converted into amine U by the two-step synthesis shown below.

The mechanism of Reaction 1 involves attack by an electrophile.

Give the reagents used to produce the electrophile needed in Reaction 1.

Write an equation showing the formation of this electrophile.

Outline a mechanism for the reaction of this electrophile with benzene.

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(6)

Page 17 of 81
(c) Cyclohexene can be converted into amine W by the two-step synthesis shown below.

Suggest an identity for compound V.

For Reaction 3, give the reagent used and name the mechanism.

For Reaction 4, give the reagent and condition used and name the mechanism.

Equations and mechanisms with curly arrows are not required.

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(6)

Page 18 of 81
 (d) Explain why amine U is a weaker base than amine W.

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(3)
(Total 19 marks)

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

(a) Give the name of each of the circled functional groups labelled J and K on the structure of
atenolol shown above.

Functional group labelled J .........................................................................

Functional group labelled K .........................................................................

(2)

(b) 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.
Use Table 2 on the Data Sheet to suggest a range of δ values for this peak.
Name the splitting pattern of this peak.

Range of δ values .......................................................................................

Name of splitting pattern ……......................................................................

(2)

Page 19 of 81
(c) N.m.r. spectra are recorded using samples in solution.
The 1H n.m.r. spectrum was recorded using a solution of atenolol in CDCl3

(i) Suggest why CDCl3 and not CHCl3 was used as the solvent.

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

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

(ii) Suggest why CDCl3 is a more effective solvent than CCl4 for polar molecules such as
atenolol.

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(1)

(d) The 13C n.m.r. spectrum of atenolol was also 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)

(e) Part of the 13C n.m.r. spectrum of atenolol is shown below. Use this spectrum and Table 3
on the Data Sheet, where appropriate, to answer the questions which follow.

(i) Give the formula of the compound that is used as a standard and produces the peak
at δ = 0 ppm in the spectrum.

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(1)

Page 20 of 81
 (ii) One of the peaks in the 13C n.m.r. spectrum above is produced by the CH3 group
labelled q in the structure of atenolol.
Identify this peak in the spectrum by stating its δ value.

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

(iii) There are three CH2 groups in the structure of atenolol. One of these CH2 groups
produces the peak at δ = 71 in the 13C n.m.r. spectrum above.
Draw a circle around this CH2 group in the structure of atenolol shown below.

(1)

(f) Atenolol is produced industrially as a racemate (an equimolar mixture of two enantiomers)
by reduction of a ketone. Both enantiomers are able to lower blood pressure. However,
recent research has shown that one enantiomer is preferred in medicines.

(i) Suggest a reducing agent that could reduce a ketone to form atenolol.

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

(ii) Draw a circle around the asymmetric carbon atom in the structure of atenolol shown
below.

(1)

(iii) Suggest how you could show that the atenolol produced by reduction of a ketone
was a racemate and not a single enantiomer.

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(2)

Page 21 of 81
 (iv) Suggest one advantage and one disadvantage of using a racemate rather than a
single enantiomer in medicines.

Advantage ...........................................................................................

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Disadvantage ......................................................................................

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(2)
(Total 16 marks)

The compound (CH3CH2)2NH can be made from ethene in a three-step synthesis as shown
10 below.

(a) Name the compound (CH3CH2)2NH

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

(b) Identify compounds F and G.

Compound F ...............................................................................................

Compound G ...............................................................................................
(2)

Page 22 of 81
(c) For the reactions in Steps 1, 2 and 3,

• give a reagent or reagents

• name the mechanism.

Balanced equations and mechanisms using curly arrows are not required.

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(6)

(d) Identify one organic impurity in the product of Step 3 and give a reason for its formation.

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(2)
(Total 11 marks)

Page 23 of 81
 Haloalkanes are useful compounds in synthesis.
11 Consider the three reactions of the haloalkane A shown below.

(a) (i) Draw a branched-chain isomer of A that exists as optical isomers.

(1)

(ii) Name the type of mechanism in Reaction 1.

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

(iii) Give the full IUPAC name of compound B.

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(1)

Page 24 of 81
(b) The infrared spectra shown below are those of the four compounds, A, B, C and D.
Using Table 1 on the Data Sheet, write the correct letter in the box next to each spectrum.

(i)

(ii)

(iii)

Page 25 of 81
 (iv)

(4)

(c) Draw the repeating unit of the polymer formed by B and name the type of polymerisation
involved.

Repeating unit

Type of polymerisation .................................................................................

(2)

(d) (i) Outline a mechanism for Reaction 3.

(4)

(ii) State the conditions used in Reaction 3 to form the maximum amount of the primary
amine, D.

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(1)

Page 26 of 81
 (iii) Draw the structure of the secondary amine formed as a by-product in Reaction 3.

(1)

(e) D is a primary amine which has three peaks in its 13C n.m.r. spectrum.

(i) An isomer of D is also a primary amine and also has three peaks in its 13C n.m.r.
spectrum. Draw the structure of this isomer of D.

(1)

(ii) Another isomer of D is a tertiary amine. Its 1H n.m.r. spectrum has three peaks. One
of the peaks is a doublet. Draw the structure of this isomer of D.

(1)
(Total 17 marks)

Page 27 of 81
 Three isomers of C6H4(NO2)2 are shown below.
12

(a) (i) Give the number of peaks in the 13C n.m.r. spectrum of each isomer.

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

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(3)

(ii) Draw the displayed formula of the compound used as a standard in recording these
spectra.

(1)

(b) Isomer X is prepared from nitrobenzene by reaction with a mixture of concentrated nitric
acid and concentrated sulfuric acid.

The two acids react to form an inorganic species that reacts with nitrobenzene to form X.

(i) Give the formula of this inorganic species formed from the two acids and write an
equation to show its formation.

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

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(2)

Page 28 of 81
 (ii) Name and outline a mechanism for the reaction of this inorganic species with
nitrobenzene to form X.

(4)

(c) Isomer Y is used in the production of the polymer Kevlar.

Y is first reduced to the diamine shown below.

(i) Identify a suitable reagent or mixture of reagents for the reduction of Y to form this
diamine. Write an equation for this reaction using [H] to represent the reducing agent.

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

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(2)

(ii) This diamine is then reacted with benzene-1, 4-dicarboxylic acid to form Kevlar.
Draw the repeating unit of Kevlar.

(2)

Page 29 of 81
 (iii) Kevlar can be used as the inner lining of bicycle tyres. The rubber used for the outer
part of the tyre is made of polymerised alkenes.

State the difference in the biodegradability of Kevlar compared to that of rubber made
of polymerised alkenes.

Use your knowledge of the bonding in these polymer molecules to explain this
difference.

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(4)
(Total 18 marks)

(a) Name and outline a mechanism for the reaction of CH3CH2NH2 with CH3CH2COCl
13
Name the amide formed.

(6)

Page 30 of 81
(b) Haloalkanes such as CH3Cl are used in organic synthesis.

Outline a three-step synthesis of CH3CH2NH2 starting from methane. Your first step should
involve the formation of CH3Cl

In your answer, identify the product of the second step and give the reagents and
conditions for each step.

Equations and mechanisms are not required.

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(6)
(Total 12 marks)

Page 31 of 81
 Compound W can be formed via compounds H and S in the three-step synthesis shown below.
14

Identify compounds H and S and give reagents and conditions for Steps 1 and 2.

State the type of compound of which W is an example.

W reacts with a large excess of bromomethane to form a solid product. Draw the structure of this
product and name the type of mechanism for this reaction.
(Total 9 marks)

A chemist has discovered that the labels have fallen off four bottles each of which contains a
15 different organic liquid. These liquids are known to be propan-2-ol, propanal, hexene and
1-bromopropane.

Suggest a series of test-tube reactions which a chemist could use to confirm the identities of the
four compounds. State the reagents used and the observations expected.
(Total 10 marks)

(a) The repeating units of two polymers, P and Q, are shown below.
16

(i) Draw the structure of the monomer used to form polymer P. Name the type of
polymerisation involved.

Structure of monomer

Type of polymerisation .......................................................................

Page 32 of 81
 (ii) Draw the structures of two compounds which react together to form polymer Q.
Name these two compounds and name the type of polymerisation involved.

Structure of compound 1

Name of compound 1 .........................................................................

Structure of compound 2

Name of compound 2 ........................................................................

Type of polymerisation .......................................................................

(iii) Identify a compound which, in aqueous solution, will break down polymer Q but not
polymer P.

.............................................................................................................
(8)

(b) Draw the structures of the two dipeptides which can form when one of the amino acids
shown below reacts with the other.

Structure 1 Structure 2
(2)

(c) Propylamine, CH3CH2CH2NH2, can be formed either by nucleophilic substitution or by

reduction.

(i) Draw the structure of a compound which can undergo nucleophilic substitution to
form propylamine.

(ii) Draw the structure of the nitrile which can be reduced to form propylamine.

Page 33 of 81
 (iii) State and explain which of the two routes to propylamine, by nucleophilic substitution
or by reduction, gives the less pure product. Draw the structure of a compound
formed as an impurity.

Route giving the less pure product .....................................................

Explanation .........................................................................................

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

Structure of an impurity

(5)
(Total 15 marks)

(a) Name the compound (CH3)2NH

17
......................................................................................................................
(1)

(b) (CH3)2NH can be formed by the reaction of an excess of CH3NH2 with CH3Br. Name and
outline a mechanism for this reaction.

Name of mechanism ....................................................................................

Mechanism

(5)

(c) Name the type of compound produced when a large excess of CH3Br reacts with CH3NH2
Give a use for this type of compound.

Type of compound ......................................................................................

Use ..............................................................................................................
(2)

Page 34 of 81
 (d) Draw the structures of the two compounds formed in the reaction of CH3NH2 with ethanoic
anhydride.

(2)
(Total 10 marks)

Which one of the following reactions does not involve donation of an electron pair?
18
A H+ + CH3NH2 → CH3NH

B AlCl3 + Cl− → A1C1

C CH3Cl + CN− → CH3CN + Cl−

D Cl2 + I− → Cl− + I2
(Total 1 mark)

The following reaction scheme shows the formation of two amines, K and L, from
19 methylbenzene.

(a) (i) Give the reagents needed to carry out Step 1. Write an equation for the formation
from these reagents of the inorganic species which reacts with methylbenzene.

Reagents ............................................................................................

Equation .........….................................................................................
Page 35 of 81
 (ii) Name and outline a mechanism for the reaction between this inorganic species
and methylbenzene.

Name of mechanism ............................................................................

Mechanism

(7)

(b) Give a suitable reagent or combination of reagents for Step 2.

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

(c) (i) Give the reagent for Step 4 and state a condition to ensure that the primary amine is
the major product.

Reagent .............................................................................................

Condition ........................................................….................................

(ii) Name and outline a mechanism for Step 4.

Name of mechanism ...........................................................................

Mechanism

(7)
(Total 15 marks)

Page 36 of 81
 This question is about the following reaction scheme which shows the preparation of polymer P.
20

Polymer P is formed in a two-step reaction from N. The first stage is a neutralisation reaction.
The volume, in cm3, of a 0.20 mol dm−3 solution of H2NCH2CH2NH2 required to neutralise 6.8 ×
10−3mol of the acid N is

A 17

B 34

C 68

D 136
(Total 1 mark)

(a) Name and outline a mechanism for the formation of butylamine, CH3CH2CH2CH2NH2,
21 by the reaction of ammonia with 1-bromobutane, CH3CH2CH2CH2Br.

Name of mechanism ....................................................................................

Mechanism

(5)

Page 37 of 81
 (b) Butylamine can also be prepared in a two-step synthesis starting from 1-bromopropane,
CH3CH2CH2Br. Write an equation for each of the two steps in this synthesis.

Step 1

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

Step 2

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

(c) (i) Explain why butylamine is a stronger base than ammonia.

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

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

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

(ii) Identify a substance that could be added to aqueous butylamine to produce a basic
buffer solution.

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

(d) Draw the structure of a tertiary amine which is an isomer of butylamine.

(1)
(Total 12 marks)

Which one of the following is not a correct general formula for the non-cyclic compounds listed?
22
A alcohols CnH2n+2O

B aldehydes CnH2n+1O

C esters CnH2nO2

C primary amines CnH2n+3N

(Total 1 mark)

Page 38 of 81
 (a) Use the following data to show the stability of benzene relative to the hypothetical
23 cyclohexa-1,3,5-triene.

Give a reason for this difference in stability.

(4)

(b) Consider the following reaction sequence which starts from phenylamine.

(i) State and explain the difference in base strength between phenylamine and
ammonia.

(ii) Name and outline a mechanism for the reaction in Step 1 and name the organic
product of Step 1.

(iii) The mechanism of Step 2 involves attack by an electrophile. Give the reagents used
in this step and write an equation showing the formation of the electrophile.
Outline a mechanism for the reaction of this electrophile with benzene.

(iv) Name the type of linkage which is broken in Step 3 and suggest a suitable reagent for
this reaction.
(17)
(Total 21 marks)

Page 39 of 81
 Compound Z can be formed via compounds X and Y in the three step synthesis shown below.
24

Identify compounds X and Y and give reagents and conditions for Steps 1 and 2.

State the type of compound of which Z is an example.

Compound Z reacts with a large excess of bromomethane to form a solid product. Draw the
structure of this product and name the type of mechanism for this reaction.
(Total 9 marks)

(a) Outline a mechanism for the formation of ethylamine from bromoethane. State why the
25 ethylamine formed is contaminated with other amines. Suggest how the reaction conditions
could be modified to minimise this contamination.
(6)

(b) Suggest one reason why phenylamine cannot be prepared from bromobenzene in a similar
way. Outline a synthesis of phenylamine from benzene. In your answer you should give
reagents and conditions for each step, but equations and mechanisms are not required.
(5)
(Total 11 marks)

(a) Methylamine is a weak Brønsted-Lowry base and can be used in aqueous solution with
26 one other substance to prepare a basic buffer.

(i) Explain the term Brønsted-Lowry base and write an equation for the reaction of
methylamine with water to produce an alkaline solution.

Brønsted-Lowry base ..........................................................................

Equation ..............................................................................................

(ii) Suggest a substance that could be added to aqueous methylamine to produce a

basic buffer.

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

Page 40 of 81
 (iii) Explain how the buffer solution in part (a)(ii) is able to resist a change in pH when a
small amount of sodium hydroxide is added.

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

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

.............................................................................................................
(5)

(b) Explain why methylamine is a stronger base than ammonia.

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

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

......................................................................................................................
(2)

(c) A cation is formed when methylamine reacts with a large excess of bromoethane. Name
the mechanism involved in the reaction and draw the structure of the cation formed.

Name of mechanism ....................................................................................

Structure

(2)
(Total 9 marks)

(a) Synthetic polyamides are produced by the reaction of dicarboxylic acids with compounds
27 such as H2N(CH2)6NH2

(i) Name the compound H2N(CH2)6NH2

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

(ii) Give the repeating unit in the polyamide nylon 6,6.

.............................................................................................................
(2)

Page 41 of 81
(b) Synthetic polyamides have structures similar to those found in proteins.

(i) Draw the structure of 2-aminopropanoic acid.

(ii) Draw the organic product formed by the condensation of two molecules of
2-aminopropanoic acid.

(2)

(c) Compounds like H2N(CH2)6NH2 are also used to make ionic compounds such as X, shown
below.

(i) X belongs to the same type of compound as (CH3)4N+Br–

Name this type of compound.

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

(ii) State a reagent which could produce X from H2N(CH2)6NH2 and give a necessary
condition to ensure that X is the major product.

Reagent .............................................................................................

Condition ............................................................................................

Page 42 of 81
(iii) Name the mechanism involved in this reaction to form X.

.............................................................................................................
(4)
(Total 8 marks)

Page 43 of 81
Mark schemes
(a) Electrophilic substitution
1
Both words needed
Ignore minor misspellings
1

(b) (i) Sn / HCl

OR H2 / Ni OR H2 / Pt OR Fe / HCl OR Zn / HCl OR SnCl2 / HCl
Ignore conc or dil with HCl,
Allow (dil) H2SO4 but not conc H2SO4
Not allow HNO3 or H+
Ignore NaOH after Sn / HCl
Ignore catalyst
1

(ii) CH3C6H4NO2 + 6[H] → CH3C6H4NH2 + 2H2O

OR

Allow molecular formulae as structures given

C7H7NO2 + 6[H] → C7H9N + 2H2O
Qu states use [H], so penalised 3H2
1

(iii) making dyes

OR making quaternary ammonium salts

OR making (cationic) surfactants

OR making hair conditioner

OR making fabric softener

OR making detergents
1

Page 44 of 81
(c)

M3

NO Mark for name of mechanism

Allow SN1
M1 for lone pair on N and arrow to C or mid point of space between
N and C
M2 for arrow from bond to Br
M3 for structure of protonated secondary amine
M4 for arrow from bond to N or + on N
For M4: ignore RNH2 or NH3 removing H+ but penalise Br−
4

(d) lone or electron pair on N

If no mention of lone pair CE = 0
If lone pair mentioned but not on N then lose M1 and mark on

M1
1

in J spread / delocalised into ring (or not delocalised in K)

Ignore negative inductive effect of benzene
Allow interacts with Π cloud for M2

M2
1

less available (for protonation or donation in J)

M3

OR

in K there is a positive inductive effect / electron releasing)

M2

more available (for protonation or donation in K)

M3
1
[11]

Page 45 of 81
 (a) M1 Ester 1
2
If Ester 2, can score M3 only.
1

M2 peak at δ = 4.1 due to

When marking M2 and M3, check any annotation of structures in

the stem at the top of the page.
1

M3 (δ = 4.1 peak is) quartet as adjacent / next to / attached to CH3

1

M4 Other spectrum quartet at δ = 2.1-2.6 (or value in this range)

1

(b) M1 Quaternary (alkyl) ammonium salt / bromide

1

M2 CH3Br or bromomethane
Penalise contradictory formula and name.
1

M3 Excess ( CH3Br or bromomethane)

Mention of acid eg H2SO4 OR alkali eg NaOH loses both M2 and
M3.
1

M4 Nucleophilic substitution
Can only score M3 if reagent correct.
Ignore alcohol or ethanol (conditions) or Temp.
1

(c)
Bromine Acidified KMnO4

(penalise Br but (Penalise missing acid

mark on) but mark on)

Wrong reagent = no marks.

If bromine colour stated it must be red, yellow, orange, brown or any
combination, penalise wrong starting colour.
1

Page 46 of 81
Benzene no reaction / colour no reaction / colour
remains / no remains / no (visible)
(visible) change change

Ignore ‘clear’, ‘nothing’.

Allow colour fades slowly.
Allow ‘nvc’ for no visible change.
1

cyclohexene (Bromine) (Acidified KMnO4)

decolourised decolourised
1
[11]

Page 47 of 81
 (a) (nucleophilic) addition-elimination
3 1

M4 for 3 arrows and lp

Allow wrong amine in M1 but penalise in M3

Allow C3H7 in M3

Minus sign on NH3 loses M1 (but not M4 if NH3 also shown here)
• Allow attack by: NH 2CH2CH2CH3
• M2 not allowed independent of M1, but allow M1 for correct attack
on C+
• + rather than δ+ on C=O loses M2
• If Cl lost with C=O breaking, max 1 for M1
• M3 for correct structure with charges but lone pair on O is part of
M4
• 3 arrows in M4 can be shown in two separate steps.
• If M3 drawn twice, mark first answer eg ignore missing + if missed
off second structure
• Only allow M4 after correct / very close M3
• For M4, ignore RNH 2 removing H+ but lose M4 for Cl– removing
H+ in mechanism,
• but ignore HCl shown as a product.
4

N-propylethanamide must be this name even if wrong amine used

NOT N-propylethaneamide
1

Page 48 of 81
(b) (i)

Not allow ambiguous C3H7NH2

BEWARE No mark for the original amine CH3CH2CH2NH2
Label and structure must both be correct for each type to score the
mark.
1

Allow C2H5
Penalize wrong number of carbons but otherwise correct, first time
only.
1

(ii) Absorption at 3300−3500 (cm−1) in spectrum

Allow trough, peak, spike.
Ignore absorption at 750 − 1100 for C–C bond in secondary - this is
within fingerprint region.
Allow any number in this range.
If range missing, no further marks.
If range linked to tertiary, no further marks.
1

N–H (bond) (only) present in secondary amine or not present in tertiary amine
OR
This peak or N–H absorption (only) present in spectrum of secondary amine or
not present in spectrum of tertiary amine
1

(c) (i) M1 Route A: stage 1 KCN

Apply list principle for extra reagents or catalysts
NOT HCN NOT KCN / acid Not KCN / HCN
1

M2 Aqueous or ethanolic
M2 only scores after correct M1
ignore warm; acid here loses M1 & M2
1

Page 49 of 81
 M3 Route A Intermediate CH3CH2CN or propanenitrile
If M3 intermediate wrong, max 2 for M1 & M2 ie no mark for stage 2

Name alone must be exactly correct to gain M1 but mark on if name close
But if M3 intermediate close, eg “nitrile” or wrong nitrile, can award
marks in stage 2

correct formula gains M1 (ignore name if close)

If stage 1 correct and intermediate is missing, can award marks in
stage 2

contradiction of name and formula loses mark

stage 1 wrong & intermediate missing, no marks.
1

M4 Route A: stage 2 H2

H loses M4 but mark on

LiAlH4
Apply list principle for extra reagents or catalysts.
M5 only scores after correct M4
Not NaBH4 not Sn or Fe / HCl
Allow (dil) acid after but not with LiAlH4
Penalise conc acid.
1

M5 Ni or Pt or Pd

ether
1

M6 Route B NH3
With acid loses M6 & M7
Apply list principle for extra reagents or catalysts.
1

M7 Excess NH3
Ignore conc, ignore high P, ignore solvent.
1

(ii) Route A disadv Toxic / poisonous KCN or cyanide or CN− or HCN

Expensive LiAlH4
ignore acidified

OR lower yield because 2 steps

Allow H2 flammable / explosive etc.
Not just dangerous.
Ignore time reasons.
1
Page 50 of 81
 Route B disadv Further reaction / substitution likely
Allow impure product.
1
[20]

(a) M1 Lone pair on N labelled b more available / more able to be donated than lone pair
4 on N labelled a
Ignore N(b) more readily accepts protons.
Ignore N(b) is stronger base.
1

M2 lp or electrons or electron density on N labelled a:

delocalized into_(benzene) ring

QoL
1

M3 lp or electrons or electron density on N labelled b:

methyl / alkyl groups electron releasing or donating or (positive) inductive

effect or push electrons or electron density
QoL
1

(b) C19H24N2
Any order.
1

11
1
[5]

Measure pH with a meter

5
Chemical indicators not allowed for M1 (allow mark for M2 if student
describes differences in pHs but not for differences in colours).
1

Methylamine would have a higher pH / ammonia would have a lower pH

Use of CuSO4 not allowed.
1
[2]

(a) Sn / HCl OR Fe / HCl not conc H2SO4 nor any HNO3

6
Ignore subsequent use of NaOH
Ignore reference to Sn as a catalyst with the acid
Allow H2 (Ni / Pt) but penalise wrong metal
But NOT NaBH4 LiAlH4 Na / C2H5OH
1

Page 51 of 81
 Equation must use molecular formulae

C6H4N2O4 + 12 [H]
12[H] and 4H2O without correct molecular formula scores 1 out of 2
1

→C6H8N2 + 4H2O
Allow .... + 6H2 if H2 / Ni used
Allow −CONH− or −COHN− or −C6H4−
1

Mark two halves separately: lose 1 each for

• error in diamine part
• error in diacid part
• error in peptide link
• missing trailing bonds at one or both ends
• either or both of H or OH on ends
Ignore n
2

(b) H2 (Ni / Pt) but penalise wrong metal

NOT Sn / HCl, NaBH4 etc.
1

CH2
1

In benzene 120°
1

In cyclohexane 109° 28’ or 109½°

Allow 108° - 110°

If only one angle stated without correct qualification, no mark awarded

1

(c) (i) Nucleophilic addition

1

Page 52 of 81
 • M2 not allowed independent of M1, but allow M1 for correct attack
on C+
• + rather than δ+ on C=O loses M2
• M3 is for correct structure including minus sign but lone pair is
part of M4
• Allow C 2H5
• M1 and M4 include lp and curly arrow
• Allow M4 arrow to H in H2O (ignore further arrows)
4

(ii) M1 Planar C=O (bond / group)

Not just planar molecule
1

M2 Attack (equally likely) from either side

Not just planar bond without reference to carbonyl
1

M3 (about product): Racemic mixture formed OR 50:50 mixture or

each enantiomer equally likely
1
[17]

Page 53 of 81
 (a) (i)
7

Allow –CONH- or - COHN -

Mark two halves separately
lose 1 each for missing trailing bonds at one or both ends or error in
peptide link or either or both of H or OH on ends
1
Not allow –(C6H12)–
Ignore n
1

(ii) M1 in polyamides - H bonding

1

M2 in polyalkenes - van der Waals forces

Penalise forces between atoms or van der Waals bonds
1

M3 Stronger forces (of attraction) in polyamides

Or H bonding is stronger
(must be a comparison of correct forces to score M3)
Do not award if refer to stronger bonds
1

Page 54 of 81
(b) (i) (nucleophilic) addition elimination

Minus sign on NH2 loses M1

1
M2 not allowed independent of M1, but allow M1 for correct attack
on C+
+ rather than + on C=O loses M2
If Cl lost with C=O breaking, max 1 for M1
M3 for correct structure with charges but
lp on O is part of M4
only allow M4 after correct/ very close M3
For M4, ignore NH3 removing H+ but lose
M4 for Cl removing H+ in mechanism,
but ignore HCl as a product
4

(ii) N-methylpropanamide
Not N-methylpropaneamide
1

(c)

Allow –CONH– or –COHN–

1

Page 55 of 81
(d) (i) 2-amino-3-hydroxypropanoic acid
1

(ii)

Must be salts of aspartic acid

allow –CO2–
allow NH2–
1

(iii) Penalise use of aspartic acid once in d(iii) and d(iv)

allow –CO2H
allow +NH3–
don’t penalize position of + on NH3
1

(iv) Penalise use of aspartic acid once in d(iii) and d(iv)

(Br–)
allow –CO2–
must show C-N bond
don’t penalize position of + on N(CH3)3
1
[16]

Page 56 of 81
 (a) M1 Benzene is more stable than cyclohexatriene
8
more stable than cyclohexatriene must be stated or implied
If benzene more stable than cyclohexene, then penalise M1 but
mark on
If benzene less stable: can score M2 only
1

M2 Expected ΔHο hydrogenation of C6H6 is 3(–120)

= –360 kJ mol-1
Allow in words e.g. expected ΔHο hydrog is three times the ΔHο
hydrog of cyclohexene
1

M3 Actual ΔHο hydrogenation of benzene is

152 kJ mol-1 (less exothermic)

or 152 kJ mol-1 different from expected

Ignore energy needed
1

M4 Because of delocalisation or electrons spread out or resonance

1

(b) No mark for name of mechanism

Conc HNO3
If either or both conc missing, allow one;
1

Conc H2SO4
this one mark can be gained in equation
1

2 H2SO4 + HNO3 → 2 HSO4– + NO2+ + H3O+

OR

H2SO4 + HNO3 → HSO4– + NO2+ + H2O

OR via two equations

H2SO4 + HNO3 → HSO4– + H2NO3+

H2NO3+ → NO2+ + H2O

Allow + anywhere on NO2+
1

Page 57 of 81
 M1 arrow from within hexagon to N or + on N
Allow NO2+ in mechanism
horseshoe must not extend beyond C2 to C6 but can be smaller
+ not too close to C1
M3 arrow into hexagon unless Kekule
allow M3 arrow independent of M2 structure
ignore base removing H in M3
+ on H in intermediate loses M2 not M3
3

(c) If intermediate compound V is wrong or not shown, max 4 for 8(c)

or chlorocyclohexane or bromocyclohexane
1

Reaction 3

M2 HBr
1

M3 Electrophilic addition
Allow M2 and M3 independent of each other
1

Page 58 of 81
 Reaction 4

M4 Ammonia if wrong do not gain M5

1
Allow M4 and M6 independent of each other

M5 Excess ammonia or sealed in a tube or under pressure

1
If CE e.g. acid conditions, lose M4 and M5

M6 Nucleophilic substitution
1

(d) Lone or electron pair on N

No marks if reference to “lone pair on N” missing
1

Delocalised or spread into ring in U

1

Less available (to accept protons) or less able to donate (to H+)
1
[19]

(a) J (acid) amide

9
not peptide, not N-substituted amide
1

K (secondary) amine or amino

penalise primary or tertiary
allow N-substituted amine
1

(b) (δ =) 3.1-3.9
1

doublet OR duplet
Not 3.7 – 4.1
Not secondary
name required not the number 2
1

(c) (i) Solvent must be proton-free

OR CHCl3 has protons or has H or gives a peak

1

(ii) CDCl3 is polar OR CCl4 is non-polar

1

Page 59 of 81
(d) 11 OR eleven
1

(e) (i) Si(CH3)4 OR SiC4H12

ignore TMS
1

(ii) a single number or a range within 21-25

penalise anything outside this range
1

(iii)

allow ring around the C only and also allow

(f) (i) NaBH4

ignore name if formula correct
ignore solvent
allow LiAlH4 Zn/HCl Sn/HCl H2/Ni H2/Pt
1

(ii)

allow ring around the C only

1

(iii) (plane) polarised light OR light in a polarimeter

1

polarised light is not rotated or is unaffected

penalise bent/diffracted/deflected/reflected
Not just solution is optically inactive
1

Page 60 of 81
 (iv) adv cheaper medicine due to cost or difficulty of separation or
both can lower blood pressure

OR more effective/beneficial with a reason

or no need to separate
1

disadv may be side effects from one enantiomer in the mixture or

only half the product works or one enantiomer may be
ineffective or double dose required
1
[16]

(a) diethylamine OR ethyl ethanamine OR ethyl aminoethane

10
ignore N–
1

(b) For (b) and (c)

There are three valid routes for this synthesis called

Routes A, B and C below

• Decide which route fits the answer best (this may not be the
best for part b) to give the candidate the best possible overall mark.

• Mark part (b)

• For this best route mark the mechanism and reagent independently

• Migration from one route to another is not allowed

• Either name or formula is allowed in every case.

• Ignore conditions unless they are incorrect.

Route A Route B Route C

F CH3CH2Br or CH3CH2Cl C2H6 CH3CH2OH 1

G CH3CH2NH2 ethylamine OR CH3CH2Br OR CH3CH2Br OR

1
ethanamine OR aminoethane CH3CH2Cl CH3CH2Cl

Page 61 of 81
(c)
Route A Route B Route C
Step Reagent(s) HBr OR HCl H2/Ni (Not H2O & H3PO4
1 NaBH4) OR 1
H2O & H2SO4
Mechanism Electrophilic addition (allow Electrophilic
addition electrophilic OR addition
catalytic but not
1
nucleophilic)
ignore
hydrogenation

Step 2 Reagent(s) NH3 Cl2 OR Br2 HBr OR KBr &

H2SO4 OR PCl3
1
OR PCl5 OR
SOCl2
Mechanism Nucleophilic (free) radical Nucleophilic
1
substitution substitution substitution

Step 3 Reagent(s) CH3CH2Br CH3CH2NH2 OR CH3CH2NH2

OR NH3 but OR NH3 but
CH3CH2Cl penalise excess penalise 1
ammonia here excess
ammonia here
Mechanism Nucleophilic Nucleophilic Nucleophilic
1
substitution substitution substitution

(d) tertiary amine OR triethylamine OR (CH3CH2)3N

Quaternary ammonium salt
OR tetraethylammonium bromide OR chloride OR ion
OR (CH3CH2)4N+ (Br– OR Cl–)
1

further substitution will take place OR

diethylamine is a better nucleophile than ethylamine
1
[11]

Page 62 of 81
 (a) (i)
11

not allow C3H7

allow C2H5 bonded to C either way round
1

(ii) elimination
allow base – elimination
but penalise any other qualification
1

(iii) Z-pent-2-ene or cis-pent-2-ene either Z or cis is necessary

(allow Z-2-pentene or cis-2-pentene)
with or without brackets around Z
with or without hyphens
1

(b) (i) C
1

(ii) A
1

(iii) B
1

(iv) D
1

(c)

allow C2H5 bonded via C or H

must have both trailing bonds
ignore brackets or n
1

addition or radical or step or chain growth

QOL not additional
1

Page 63 of 81
(d) (i)

Allow SN1, i.e M2 first then attack of NH3 on carbocation.

Allow C2H5 in M3 bonded either way
Allow with or without NH3 to remove H+ in M4, but lose mark if Br–
used.
ignore δ+ or δ– unless wrong
+ on central C instead of δ + loses M2
4

(ii) excess NH3

ignore reflux
allow conc ammonia in sealed tube
1

(iii)

Allow C2H5 bonded either way

1

(e) (i)

Page 64 of 81
 (ii)

NOT (C2H5)2NCH3 which is tertiary with 3 peaks but its spectrum

has no doublet.
1
[17]

(a) (i) W 3
12 1

X 4
1

Y 2
1

(ii)

displayed formula shows ALL bonds

1

(b) (i) NO2+

allow + anywhere
can score in equation
1

HNO3 + 2H2SO4 → NO2+ + 2HSO4– + H3O+

1

OR

HNO3 + H2SO4 → NO2+ + HSO4– + H2O

or use two equations via H2NO3+

Page 65 of 81
 (ii) electrophilic substitution
Not Friedel Crafts
1

Allow Kekule structures

+ must be on N of +NO2 (which must be correct)
both NO2 must be correctly positioned and bonded to gain M2
M1 arrow from circle or within it to N or to + on N
horseshoe must not extend beyond C2 to C6 but can be smaller
+ not too close to C1
M3 arrow into hexagon unless Kekule
allow M3 arrow independent of M2 structure
ignore base removing H in M3
3

(c) (i) H2/Ni or H2/Pt or Sn/HCl or Fe/HCl (conc or dil or neither)

allow dil H2SO4
ignore mention of NaOH
Not NaBH4
Not LiAlH4
Not Na/C2H5OH
not conc H2SO4 or any HNO3
1

4H2O
Or 6H2
allow C6H4(NO2)2 etc ,
allow NO2– NH2–
i.e. be lenient on structures, the mark is for balancing equ
1

Page 66 of 81
 (ii)

allow –CONH
ignore [ ]n as in polymer

1st mark for correct peptide link

2nd mark for the rest correct including trailing bonds
2

(iii) M1 Kevlar is biodegradeable but polyalkenes not

allow Kevlar is more biodegradeable
1

M2 Kevlar has polar bonds/is a (poly) amide/has peptide link

comment on structure of Kevlar
1

M3 can be hydrolysed/attacked by nucleophiles/acids/

bases/enzymes
1

M4 polyalkenes non polar/has non-polar bonds

comment on structure of polyalkenes but not just strong bonds
1
[18]

(a) (nucleophilic) addition-elimination

13 1

Page 67 of 81
 N-ethylpropanamide
minus on NH2 loses M1
M2 not allowed independent of M1, but allow M1 for correct attack
on C+
+C=O loses M2
only allow M4 after correct or very close M3
lose M4 for Cl– removing H+ in mechanism, but ignore HCl as a
product
Not N-ethylpropaneamide
1

(b) CH3CN or ethan(e)nitrile or ethanonitrile

not ethanitrile
but allow correct formula with ethanitrile
1

for each step wrong or no reagent loses condition mark

contradiction loses mark
1

Step 1 Cl2
uv or above 300 °C
wrong or no reagent loses condition mark
1

Step 2 KCN
1

aq and alcoholic (both needed)

allow uv light/(sun)light/uv radiation
1

Step 3 H2/Ni or LiAlH4 or Na/C2H5OH

not CN– but mark on
NOT HCN or KCN + acid, and this loses condition mark
NOT NaBH4
Sn/HCl (forms aldehyde!)
ignore conditions
1
[12]

Page 68 of 81
 H CH3CN or ethanenitrile
14 1

S CH3CH2NH2 or ethylamine 1Step 1 KCN

1

aq/alcoholic
1

Step 2 H2
1

Ni
1

W secondary amine
1

nucleophilic substitution
1
[9]

Page 69 of 81
 Acidified potassium dichromate(VI)
15 1
Turns green with propan-2-ol and propanal
1
No reaction with hexene and 1-bromopropane
1
Tollens with propan-2-ol and propanal
1
only propanal gives silver mirror
1
Bromine water
1
Decolourised by hexane
1
No reaction with 1-bromopropane
1
Warm NaOH followed by acidified AgNO3
1
White ppt with 1-bromopropane
1
[10]

(a) (i) CH3CH=CHCH3

16 1

Addition or radical (QoL)

1

(ii) CH3CH(OH)CH(OH)CH3 or with no brackets

1

butan(e)–2,3–diol or 2,3–butan(e)diol
1

2,3–dimethylbutan(e)dioic acid 2,3–dimethylbutan(e)dioyl chloride

ignore –1,4–
1

condensation (QoL)
1

(iii) NaOH or HCl etc or Na2CO3

Allow conc sulphuric/nitric
NOT water nor acidified water nor weak acids
1

Page 70 of 81
 (b) Structure 1

Allow –CONH– and –COHN–

Allow zwitterions
NOT polypeptides/repeating units
1

Structure 2 either of

(c) (i) CH3CH2CH2Br

allow –Cl, –I
1

(ii) CH3CH2CN
1

(iii) (nucleophilic) substitution or from CH3CH2CH2Br

if reduction written here, no further marks
1

further substitution/reaction occurs or other products are formed

Allow reduction forms only one product
1

one of
(CH3CH2CH2)2NH
(CH3CH2CH2)3N
(CH3CH2CH2)4N+ Br–
Allow salts including NH4Br
Allow HBr
1
[15]

(a) dimethylamine
17 1

Page 71 of 81
 (b) nucleophilic substitution
1

(c) quaternary ammonium salt

1

(cationic) surfactant / bactericide / detergent / fabric softener or

conditioner/hair conditioner
1

(d)

(allow CH3COOH or CH3COO– NH4+)

2
[10]

D
18 [1]

Page 72 of 81
 (a) (i) conc HNO3
19 1

conc H2SO4
allow 1 for both acids if either conc missing
1

HNO3 + 2H2SO4 → NO2+ + H3O+ + 2HSO4–

or HNO3 + H2SO4 → NO2+ + H2O + HSO4–

1

(iii) electrophilic substitution CH3

1

horseshoe must not extend beyond C2 to C6 but can be smaller

+ must not be too close to Cl
3

(b) Sn or Fe / HCl (conc or dil or neither)

or Ni / H2 not NaBH4 LiAlH4
1

(c) (i) NH3

1

Use an excess of ammonia

1

(ii) nucleophilic substitution

1

4
[15]

B
20 [1]

Page 73 of 81
 (a) Nucleophilic substitution
21

M1, M2 and M4 for arrows, M3 for structure of cation

(Allow M2 alone first, i.e. SN1 formation of carbocation)
(Penalise M4 if Br– used to remove H+)
4

(b) Step 1 CH3CH2CH2CN 1

CH3CH2CH2Br + KCN → CH3CH2CH2CN + KBr balanced

1

(or CN–) (or Br–)

(not HCN)
1

Step 2 CH3CH2CH2CN + 2H2 → CH3CH2CH2CH2NH2

(or 4[H])
1

(c) (i) Lone pair (on N) (in correct context)

1

R group increases electron density / donates electrons /pushes

electrons / has positive inductive effect
1

(ii) Any strong acid (but not concentrated)

or any amine salt or ammonium salt of a strong acid
1

(d) CH3CH2N(CH3)2
1
[12]

B
22 [1]

Page 74 of 81
 (a) Cyclohexane evolves 120 kJ mol–1
23
(expect triene to evole) 360 kJ mol–1 (1) or 3 × 120

360 – 208 = 152 kJ (1) NOT 150

152 can score first 2
QofL: benzene lower in energy / more (stated) stable (1)
Not award if mentions energy required for bond breaking
due to delocalisation (1) or explained
4

(b) (i) phenylamine weaker (1)

if wrong no marks

lone pair on N (less available) (1)

delocalised into ring (1) or “explained”
3

(ii) addition – elimination (1)

structure (1) M3
3 arrows (1) M4

N-phenyl ethanamide (1)

6

(iii) conc HNO3 (1)

conc H2SO4 (1)

HNO3 + 2H2SO4 → O2 + H3O+ + 2HSO4– (1)

(iv) peptide / amide (1)

NaOH (aq) (1)

HCl conc or dil or neither
H2SO4 dil NOT conc
NOT just H2O
2

Page 75 of 81
Notes

(a) • 360 or 3 × 120 or in words (1);

• 152 NOT 150 (1); (152 can get first two marks)
• Q of L benzene more stable but not award if ΔH values used to say
that more energy is required by benzene for hydrogenation compared with
the triene or if benzene is only compared with cyclohexene (1);
• delocalisation or explained (1)

(b) (ii) or N-phenylacetamide or acetanilide

mechanism: if shown as substitution can only gain M1
if CH3CO+ formed can only gain M1
lose M4 if Cl– removes H+
be lenient with structures for M1 and M2 but must be correct for M3
alone loses M2

(iii) No marks for name of mechanism in this part

if conc missing can score one for both acids (or in equation)
allow two equations

allow HNO3 + H2SO4 → NO2+ + HSO4– + H2O

ignore side chain in mechanism even if wrong
arrow for M1 must come from niside hexagon
arrow to NO2+ must go to N but be lenient over position of +
+ must not be too near “tetrahedral” Carbon
horseshoe from carbons 2-6 but don’t be too harsh

(iv) reagent allow NaOH

HCl conc or dil or neither
H2SO4 dil or neither but not conc
not just H2O
[21]

Page 76 of 81
 X is CH3CN or ethanenitrile or ethanonitrile or methyl cyanide or
24 cyanomethane or ethyl nitrile or methanecarbonitrile
Not ethanitrile
but contradiciton of name and structure lose marks
1

Y is CH3CH2NH2 or ethylamine or aminoethane or ethanamine

1

Step 1: reagent KCN not HCN/HCl

condition (aq)/alcohol - only allow condition if reagent
correct or incomplete
2

Step 2: reagent H2 LiAlH4 Na Zn/Fe/Sn Not NaBH4

condition Ni/Pt/Pd ether ethanol HCl
2

Z is an amine or aminoalkane or named amine even if incorrect name for Z

secondary (only award if amine correct)
1

(Br–) + can be on N or outside brackets as shown

nucleophilic substitution
1
[9]

(a)
25

Further reaction / substitution / formation of 2° / 3° amines etc (1)

use an excess of NH3 (1)
6

Page 77 of 81
(b) repels nucleophiles (such as NH3) (1)

Notes

(a) allow SN1

penalise: Br– intead of NH3 removing H+ for M4
not contamination with other amines (this is in the question) not diamines

(b) allow because NH3 is a nuclephile or benzene is (only) attacked by electrophiles

or C–Br bond (in bromobenzene) is stronger / less polar or Br lp delocalized

HNO3 / H2SO4 without either conc scores (1) allow 20 – 60° for (1) (any 2 ex 3)

allow name or structure of nitrobenzene

other reducing agents: Fe or Sn with HCl (conc or dil or neither)

not conc H2SO4 or conc HNO3
allow Ni/H2
Not NaBH4 or LiAlH4
ignore wrong descriptions for reduction step e.g. hydrolysis or hydration
[11]

Organic points

(1) Curly arrows: must show movement of a pair of electrons,

i.e. from bond to atom or from lp to atom / space
e.g.

Page 78 of 81
 (2) Structures

penalise sticks (i.e. ) once per paper

Penalise once per paper

allow CH3– or –CH3 or or CH3

or H3C–

(a) (i) H+ or proton acceptor (1)

26
CH3NH2 + H2O ( ) CH3+NH3 (+) OH– (1)

(ii) CH3NH3Cl or HCl (1)

Or any ammonium compound or strong acid
name or formula

(iii) extra OH– reacts with

or reaction / equilibrium moves to left
or ratio salt / base remains almost constant (1)
Any 2
5

(b) lone pair (on N accepts H+) (1)

CH3 increases electron density (on N)
donates / pushes electrons
has positive inductive effect (1)
2

Page 79 of 81
 (c) nucleophilic substitution (1)

(1)
2
[9]

(a) (i) hexane-1,6-diamine or 1,6-diaminohexane (allow ammine)

27 or 1,6 hexan(e)diamine (1)

(ii)

Allow –CONH–
2

(b) (i)

(ii)

Page 80 of 81
(c) (i) quaternary ammonium bromide salt (1)
(not ion, not compound)
Allow quarternery

(ii) Reagent: CH3Br or bromomethane (1)

penalise CH3Cl but allow excess for any halomethane

Condition: excess (CH3Br) (1)

(iii) nucleophilic substitution (1)

4
[8]

Page 81 of 81