A2 Organic Book 1 2020

a2
book-1
Page 3 of 231
Organic worksheet for A2 Level
1. The common analgesic drug paracetamol has the following structure.
(a) Name the two functional groups in the paracetamol molecule
.............................................................. and ........................................................... [2]
(b) Draw the structural formulae of the molecules or ions formed when paracetamol reacts
with
(i) Br2(aq),
(ii) NaOH(aq) in the cold,
(iii) NaOH(aq) under reflux.
[3]
(c) Paracetamol can be synthesised by reacting 4-aminophenol with compound X.
(i) Suggest a possible identity of X.
..................................................................................................................................
(ii) What reagent would you use to convert ethanoic acid, CH3CO2H, into X?
.................................................................................................................................. [2]
[Total: 7]
2. Methylbenzene can react with chlorine in two ways, depending on the conditions of the
reaction.
(a) State the condition needed for
(i) reaction I,
..................................................................................................................................
(ii) reaction II..
............................................................................................................................ [2]
Page 4 of 231
(b) One of the two compounds A and B reacts with NaOH(aq), but the other is inert.
(i) Which one (A or B) does not react? Give a reason for your answer.
..................................................................................................................................
..................................................................................................................................
(ii) Write an equation for the reaction with NaOH(aq) that does occur.
[2]
[Total: 4]
3. Phenylamine is an important intermediate compound for the production of dyes.
(a) Phenylamine can be synthesised from benzene in two steps. Draw the structural formula of the
intermediate Y in the scheme below, and suggest reagents and conditions for steps I and II.
reagent + conditions for step I .........................................................................................
reagent + conditions for step II ........................................................................................ [4]
(b) Phenylamine is a weak base.
(i) Write an equation showing phenylamine acting as a base.
(ii) How would you expect its basicity to compare with that of ammonia?
..................................................................................................................................
(iii) Explain the reasoning for your answer in (ii).
..................................................................................................................................
.................................................................................................................................. [3]
(c) Dyes can be made from phenylamine by first converting it into benzenediazonium
chloride, and then coupling this with a phenol.
Page 5 of 231
(i) State the reagents and condition needed for step III.
..................................................................................................................................
(ii) What reagent is the phenol dissolved in for step IV to be effective?
..................................................................................................................................
(iii) Suggest the structural formula of the dye formed when benzenediazonium
chloride is coupled with 2-methylphenol.
[4]
[Total: 11]
4. Benzene can be converted into nitrobenzene by a nitration reaction.
(a) State the reagents and conditions necessary to carry out this reaction.
..........................................................................................................................................
...................................................................................................................................... [2]
(b) What type of reaction mechanism is this?
...................................................................................................................................... [1]
(c) The reaction proceeds via two steps:
(i) Draw the structure of the intermediate Y in the box.
(ii) Identify the cation X+..................................................................................................
(iii) Identify the cation Z+..................................................................................................
(iv) Write an equation to show how X+ is produced from the reagents.
................................................................................................................................... [5]
(d) Some aromatic poly-nitro compounds are used in perfumes as artificial musks. An
example is ‘Baur musk’.
Page 6 of 231
(i) Draw the structural formula of the hydrocarbon that could be nitrated in order to
produce Baur musk.
(ii) Suggest the structural formula of the compound formed by reacting Baur musk with
an excess of tin and concentrated hydrochloric acid.
[2]
[Total: 10]
5. Amides can be made by reacting amines with acyl chlorides, as in the example below.
(a) What type of reaction mechanism is this?
...................................................................................................................................... [1]
(b) What compound could CH3CH2COCl be made from, and what reagent would you use?
..........................................................................................................................................
...................................................................................................................................... [2]
(c) The amine CH3CH2CH2NH2 can be made from CH3CH2Br in two steps.
(i) Draw the structural formula of the intermediate in the box provided.
...................................................................................................................................
(ii) State the reagents and conditions for step I.
...................................................................................................................................
(iii) State the reagents and conditions for step II.
................................................................................................................................... [4]
(d) Kevlar is a low weight, high strength polyamide used as a reinforcement in car tyres,
aircraft wings and in bullet-proof vests. A portion of its chain is shown below.
(i) What type of polymerisation produces Kevlar?
...................................................................................................................................
(ii) Draw the structural formulae of the monomers from which Kevlar is made.
Page 7 of 231
(iii) Suggest a reason why Kevlar is much stronger than most other polyamides.
...................................................................................................................................
(iv) What reaction conditions are needed to break the amide bonds in Kevlar?
................................................................................................................................... [4]
[Total: 11]
6. Chloroacetophenone (compound D, below) was formerly the most widely used tear gas,
under the codename CN. It was used in warfare and in riot control. It can be synthesised
from ethylbenzene, A, by the following route.
(a) Suggest reagents and conditions for step I.
...................................................................................................................................... [1]
(b) Suggest reagents and conditions for converting ethylbenzene into compound E, an
isomer of B.
...................................................................................................................................... [1]
(c) Draw the structure of the product obtained by heating ethylbenzene with KMnO4.
[1]
(d) Describe a test (reagents and observations) that would distinguish compound C from
compound F.
reagents
..........................................................................................................................................
observation with C
..........................................................................................................................................
observation with F
.......................................................................................................................................... [2]
Page 8 of 231
(e) The efficiency of a tear gas is expressed by its ‘intolerable concentration’, I.C. The I.C.
of the tear gas CN has been measured as 0.030 gm–3 of air.
How many moles of chloroacetophenone need to be sprayed into a room of volume
60 m3 in order to achieve this concentration?
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [2]
(f) Residues of CN can be destroyed by hydrolysis with an aqueous alkali.
Compounds G and H are isomers of compound D.
(i) Arrange the three isomers D, G and H in order of increasing ease of hydrolysis.
...................................................................................................................................
(ii) Explain the reasoning behind your choice.
...................................................................................................................................
...................................................................................................................................
................................................................................................................................... [3]
[Total : 10]
7. (a) Acyl chlorides are useful intermediates for making various acid derivatives. The
following reaction scheme shows some of the reactions of ethanoyl chloride.
(i) Suggest a reagent for step I.
...................................................................................................................................
Page 9 of 231
(ii) Write an equation showing the reaction between phenol and NaOH(aq), the
reagents in step II.
...................................................................................................................................
(iii) Draw the structural formulae of products J and K in the boxes above. [4]
(b) The diacid L occurs naturally and is used as a food additive to enhance the acidic
flavour in some fruit drinks.
When the diacyl chloride of L is reacted with HOCH2CH2OH, a polymer is formed.
(i) What type of polymerisation is occurring here?
...................................................................................................................................
(ii) Write an equation showing the reaction between one mole of the diacyl chloride of
L and two moles of HOCH2CH2OH.
[3]
(c) The following formula represents a section of another polymer.
(i) What type of polymer is this?
...................................................................................................................................
(ii) Draw the structural formula of each of the monomers that make up this polymer.
[3]
[Total : 10]
8. Ethyl 4-hydroxybenzoate, E, is a permitted food preservative.
(a) Name two functional groups in E.
..........................................................................................................................................
...................................................................................................................................... [2]
(b) Draw the structures of the compounds formed when E reacts with
(i) sodium metal,

Page 10 of 231
(ii) NaOH(aq) under reflux,
(iii) Br2(aq).
[4]
(c) Compounds F and G are isomers of E.
(i) Suggest the order of acid strength of E, F and G.
...................................................................................................................................
...................................................................................................................................
(ii) Based on their relative acidities, suggest how samples of E, F and G could be
distinguished from each other by the use of NaOH(aq) and Na2CO3(aq).
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
................................................................................................................................... [3]
[Total : 9]
9. The amino acid alanine, K, can be obtained from 2-hydroxypropanoic acid, H, by the
following route.
(a) Suggest a test you could use to distinguish H from its isomer 3-hydroxypropanoic acid, L.
reagents ...........................................................................................................................
observation with H ............................................................................................................
observation with L ........................................................................................................ [2]
(b) How would the acidity of chloropropanoic acid, J, compare with that of propanoic acid?
Briefly explain your answer.
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [2]
Page 11 of 231
(c) Alanine reacts with both acids and bases.
Write an equation for the reaction between alanine and sodium hydroxide, drawing the
displayed formula of the organic product.
[2]
(d) In solution, alanine exists as a zwitterion. Draw the structure of this ion.
[1]
(e) Alanine is one of about 20 amino acids that make up proteins.
(i) What type of bond joins amino acids together in proteins?
...................................................................................................................................
(ii) Draw the displayed formula of the compound formed when two alanine molecules
are joined by this bond.
[2]
(f) An excess of benzoic acid in the body (present as a preservative in many foodstuffs, or
formed by oxidation of aromatic compounds present in food) is excreted as hippuric
acid, M.
(i) Suggest a reagent that could be reacted with glycine in the laboratory to form
hippuric acid.
...................................................................................................................................
(ii) Suggest the reagents and conditions needed to re-form glycine from hippuric acid.
...................................................................................................................................
................................................................................................................................... [3]
[Total : 12]
10. This question is about the reactions of some functional groups.
(a) (i) Draw the structural formula of an amide of your choice containing four carbon atoms.
(ii) What reagents and conditions are needed to hydrolyse this amide?
...................................................................................................................................
Page 12 of 231
(iii) Write a balanced equation showing the hydrolysis of the amide whose structural
formula you drew in part (i).
............................................................................................................................... [4]
(b) (i) Draw the structural formula of an acyl chloride containing three carbon atoms.
(ii) What starting material and reagent are needed to form this acyl chloride?
...................................................................................................................................
(iii) Write a balanced equation showing the formation of an ester containing five carbon
atoms from the acyl chloride you drew in part (i).
............................................................................................................................... [3]
[Total: 7]
11. (a) State the reagents and conditions needed to convert benzene into
(i) chlorobenzene,
...................................................................................................................................
(ii) bromobenzene,
...................................................................................................................................
(iii) nitrobenzene.
................................................................................................................................... [4]
(b) The nitration of benzene is a two-step reaction that can be represented as follows.
(i) Identify the cation A+. ...............................................................................................
(ii) Draw the structure of the intermediate B in the box. [2]
(c) The position of substitution during the electrophilic substitution of arenes is determined
by the nature of the group already attached to the ring.
Electron-withdrawing groups such as –CO2H or –NO2 direct the incoming group to the
3-position.
Page 13 of 231
On the other hand, electron-donating groups such as –CH3 or –NH2 direct the incoming
group to the 2- or 4- positions.
Use this information to suggest a likely structure for the organic product of each of the
following reactions.
12. Much research has been carried out in recent years investigating the exact structure of silk. The
silk of a spider’s web is at least five times as strong as steel, and twice as elastic as nylon. A
silk fibre is composed of many identical protein chains, which are mainly made from the amino
acids glycine, alanine and serine, with smaller amounts of four other amino acids.
(a) Amino acids can exist as zwitterions. Draw the zwitterionic structure for glycine.
[1]
(b) Amino acids can act as acids or bases. Write equations to show:
(i) the reaction between alanine and HCl(aq),
...................................................................................................................................
(ii) the reaction between serine and NaOH(aq).
................................................................................................................................... [2]
Page 14 of 231
(c) Draw the structural formula of a portion of the silk protein, showing three amino acid
residues. Label a peptide bond on your structure.
[3]
(d) What type of polymer is silk protein?
...................................................................................................................................... [1]
(e) The Mr of a silk protein molecule is about 600,000. Assuming it is made from equal
amounts of the above three amino acids, calculate the average number of amino acid
residues in the protein chain. [Mr (glycine) = 75; Mr (alanine) = 89; Mr (serine) = 105]
number of residues = ................................... [3]

[Total: 10]
13. This question is concerned with organochlorine compounds.
(a) State the conditions needed to produce the two compounds A and B.
(i) conditions for reaction I
...................................................................................................................................
(ii) conditions for reaction II
.............................................................................................................................. [2]
(b) State the reagent needed to carry out the following reaction.
reagent for reaction III: ................................................................................................. [1]

Page 15 of 231
(c) The three chloro-compounds A, B and C vary in their ease of hydrolysis.
(i) Place a tick in the box corresponding to the correct relative rates of hydrolysis.
[the symbol ‘>’ means ‘faster than’]
(ii) Suggest an explanation for these differences in reactivity.
...................................................................................................................................
...................................................................................................................................
.............................................................................................................................. [3]
(d) Draw the structural formulae of the organic products of the following reactions of
compound C.
Page 16 of 231
14. Compounds D and E are both ketones.
(a) State which one of these compound reacts with alkaline aqueous iodine, and draw the
structural formulae of the products formed during this reactions.
(i) compound (D or E) ....................................................................................................
(ii) products
.............................................................................................................................. [3]
(b) The reduction of D with NaBH4 produces just one alcohol, but a similar reduction of E produces
two isomers in equal amounts. Explain these observations, drawing structures where appropriate.
..........................................................................................................................................
..........................................................................................................................................
[3]
[Total: 6]
15. Both phenol and phenylamine react similarly with aqueous bromine.
(a) State two observations you would make when these reactions take place.
..........................................................................................................................................
..........................................................................................................................................
..................................................................................................................................... [2]
(b) Describe a simple test-tube reaction you could use to distinguish between phenol and
phenylamine.
..........................................................................................................................................
...................................................................................................................................... [1]
(c) The compound 3-aminobenzoic acid can be prepared by the following series of
reactions.
Suggest suitable reagents and conditions for
reaction IV, .......................................................................................................................
reaction V, ........................................................................................................................
reaction VI. .................................................................................................................. [4]

[Total: 7]
Page 17 of 231
16. (a) Give an expression for Ka as applied to the weak acid RCO2H.
..........................................................................................................................................
.................................................................................................................................... [1]
(b) The Ka values for three carboxylic acids are listed in the table below.
(i) Describe and explain the trend in acid strength illustrated by these values.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Calculate the pH of a 0.100moldm–3 solution of ClCH2CO2H.
(iii) Calculate the pKa value for Cl2CHCO2H.
[5]
(c) The acid ClCH2CO2H features in the industrial synthesis of the important weedkiller
2,4-D.
(i) Suggest a possible reagent for reaction I.
..................................................................................................................................
(ii) What type of reaction is
reaction I, .................................................................................................................
reaction II? ...............................................................................................................
(iii) Describe a test (reagents and observations) that would distinguish phenol from
compound A.
Page 18 of 231
reagents ...................................................................................................................
observation with phenol ...........................................................................................
observation with compound A .................................................................................. [5]

[Total: 11]
17. The antipyretic (fever-reducing) drug antifebrin can be made from benzene and ethanoic
acid by the following route.
(a) (i) What type of reaction is reaction I?
..................................................................................................................................
(ii) Suggest the reagents and conditions for reaction I.
..................................................................................................................................
(iii) Complete the following scheme showing the mechanism of reaction I, by drawing
appropriate formulae in the three boxes.
(b) (i) What type of reaction is reaction II?
..................................................................................................................................
(ii) Suggest the reagents and conditions for reaction II.
.................................................................................................................................. [2]
(c) Suggest the reagents and conditions for reaction III.
.................................................................................................................................... [1]
(d) (i) Apart from the benzene ring, name the functional group in antifebrin.
..................................................................................................................................
(ii) What reagents and conditions are needed to hydrolyse antifebrin?
.................................................................................................................................. [2]
[Total: 11]
Page 19 of 231
18. Rodinol is used as a photographic developer. In alkaline solution it is a mild reducing agent,
providing electrons according to the following half equation.
Rodinol ‘develops’ a latent photographic image by reducing activated silver bromide grains to
silver metal and bromide ions.
(a) Construct a balanced equation for the reaction between rodinol and AgBr.
.................................................................................................................................... [1]
(b) Suggest, with a reason, how the basicity of rodinol might compare to that of ammonia.
..........................................................................................................................................
..........................................................................................................................................
.................................................................................................................................... [2]
(c) Suggest structural formulae for the compounds E, F and G in the following chart of the
reactions of rodinol.
(d) Rodinol can be synthesised from phenol by the following route.
(i) Suggest reagents and conditions for step I.
..................................................................................................................................
(ii) What type of reaction is step II?
..................................................................................................................................
Page 20 of 231
(iii) Place a tick in the box by the most suitable reagent for step II.
(place a tick in one box only)
(e) Rodinol is also an important intermediate in the commercial production of the

analgesic drug paracetamol.
(i) Name two functional groups in paracetamol.
..................................................................................................................................
..................................................................................................................................
(ii) Suggest a reagent to convert rodinol into paracetamol.
.................................................................................................................................. [3]
[Total: 12]
19. Hydrophilic polymers find important uses in the manufacture of contact lenses and wound
dressings. Their chemical structures allow them to bond with water molecules, which keeps them
soft and flexible. Sections of two hydrophilic polymers are shown below.
(a) What type of polymerisation has produced
(i) polymer H? ...................................................

Page 21 of 231
(ii) polymer J? .................................................... [2]
(b) What type of attractions might occur between these polymers and molecules of water?
.................................................................................................................................... [1]
(c) Chains of polymer H can be ‘cross-linked’, i.e. joined together, by reaction with a small
bifunctional molecule.
(i) Which one of the following molecules would be most suitable for such crosslinking?
(place a tick in one box only)
(ii) What type of bond would be formed during the cross-linking?
.................................................................................................................................. [2]
(d) (i) Suggest the reagents and conditions needed to hydrolyse polymer J into its
monomers.
..................................................................................................................................
(ii) Draw the structural formulae of the two products of this hydrolysis reaction.
.................................................................................................................................. [3]
(e) The last compound in the list in (c)(i) above is 3-aminopropanoic acid. This can be
made from potassium chloroethanoate by the following 3-stage route.
(i) In the box above write the structure of the intermediate in this route.
(ii) Suggest reagents and conditions for
stage II .....................................................................................................................
stage III .................................................................................................................... [3]

[Total: 11]
Page 22 of 231
20. The amino acids tyrosine, lysine and glycine are constituents of many proteins.
(a) State the reagents and conditions you could use to break proteins down into amino
acids.
..................................................................................................................................... [2]
(b) Draw a ring around each chiral centre in the above molecules. [1]
(c) In aqueous solution amino acids exist as zwitterions. Draw the zwitterionic structure of
glycine.
..................................................................................................................................... [1]
(d) For each of the following reactions, draw the structure of the organic compound formed.
(i) glycine + excess NaOH(aq)
...................................................................................................................................
(ii) tyrosine + excess NaOH(aq)
...................................................................................................................................
(iii) lysine + excess HCl (aq)
...................................................................................................................................
(iv) tyrosine + excess Br2(aq)
................................................................................................................................... [5]
(e) Draw the structural formula of a tripeptide formed from all three of these amino acids,
showing clearly the peptide bonds.
..................................................................................................................................... [2]
(f) The formula of part of the chain of a synthetic polyamide is shown below.
(i) Identify the repeat unit of the polymer by drawing square brackets around it on the
above formula.
Page 23 of 231
(ii) Draw the structures of the two monomers from which the polymer could be made.
................................................................................................................................... [3]
[Total: 14]
21. Benzocaine is an important local anaesthetic used in skin creams for sprains and other
muscular pains. It can be made by the following route.
(a) Suggest reagents and conditions for each of the above four reactions.
I ...................................................................................................................................
II ...................................................................................................................................
III ...................................................................................................................................
IV .............................................................................................................................. [6]
(b) Draw steps to show the mechanism of reaction I.
[2]
(c) Another local anaesthetic is amylocaine, which can be made from compound X.
(i) Apart from the benzene ring, name two functional groups in the molecule of
compound X.
...................................................................................................................................
...................................................................................................................................
(ii) Explain whether compound X would be more or less basic than benzocaine.
...................................................................................................................................
................................................................................................................................... [3]
[Total: 11]
Page 24 of 231
22. Ethylbenzene is an important starting material for making polystyrene (poly(phenylethene)).
(a) (i) State the conditions needed to carry out reaction I in the laboratory.
...................................................................................................................................
(ii) State the reagent and conditions needed for reaction II.
...................................................................................................................................
(iii) Draw the structure of the repeat unit of polystyrene.
(iv) There are several polymers that consist of phenylethene co-polymerised with other
monomers. The following formula shows part of the chain of one such co-polymer.
Deduce the structural formula of the other monomer.
[5]
(b) Compound B undergoes the following series of reactions.
(i) Suggest reagents and conditions for reaction III.
...................................................................................................................................
(ii) What would you see when reaction IV was carried out?
...................................................................................................................................
(iii) Draw structures for C and D in the boxes above.

[4]
Page 25 of 231
(c) Ethylbenzene can react with chlorine under a different set of conditions to give
compound E, an isomer of compound B. Compound E undergoes the following
reaction.
(i) Draw a structure for E in the box above.
(ii) Describe the conditions used for reaction V.
...................................................................................................................................
(iii) State the reagents used for reaction VI.
................................................................................................................................... [3]
[Total: 12]
23. 4-Amino-1-methylbenzene, F, is a useful starting material for making several dyes. The
following chart shows some of its reactions.
(a) (i) Suggest reagents and conditions for reaction I.
...................................................................................................................................
(ii) Draw the structural formulae of compounds G and H in the boxes above.
(iii) Name the functional group you have drawn in compound G.
................................................................................................................................... [4]
Page 26 of 231
(b) The dye J can be made from F by the following series of reactions.
Suggest reagents and conditions for
(i) reaction IV, ................................................................................................................
(ii) reaction V.
................................................................................................................................... [4]
(c) Many dyestuffs used as food colourings, such as Sunset Yellow, contain sodium
sulphonate (–SO3–Na+) groups attached to the rings. Suggest, with an explanation, a
reason for this.
.....................................................................................................................................
[2]
[Total: 10]
24. The following scheme shows some reactions of methylbenzene.

Page 27 of 231
(a) Suggest reagents and conditions for reactions I to IV.
I ........................................................................................................................................
II .......................................................................................................................................
III ......................................................................................................................................
IV ..................................................................................................................................... [4]
(b) What type of reaction is each of the following?
reaction I ..........................................................................................................................
reaction III ........................................................................................................................ [2]
(c) Compound F can be converted into 2-phenylethylamine in a two-stage process.

Suggest a structure for the intermediate, H, in the box below, and suggest reagents and
conditions for the steps V and VI.
reagents and conditions for step V ..................................................................................
reagents and conditions for step VI ................................................................................. [4]
(d) The compounds E, F and G react at different rates with nucleophilic reagents. Draw
structures for the products of each compound with the following reagents.
If no reaction occurs, write “no reaction” in the box.
Page 28 of 231
25. Chemists use skeletal or partial-skeletal formulae to represent larger structures. For
example the structure
may also be represented as follows.
Oestradiol is one of the hormones that controls the reproductive cycle in female mammals.
(a) (i) On the above structure of oestradiol, circle one chiral centre.
(ii) What is the total number of chiral centres in the oestradiol molecule? ..................... [2]
(b) Complete the following part-structures (which have the -OH groups removed) to show
the products obtained when oestradiol (above) is reacted with the stated reagents.
(i) sodium metal
(ii) Br2(aq)
Page 29 of 231
(iii) NaOH(aq)
(iv) CH3COCl
(v) hot acidified K2Cr2O7
[7]
[Total: 9]
26. The phenol 1-naphthol is a starting point for the manufacture of carbaryl, an insecticide and a
plant growth inhibitor.
(a) (i) Suggest a structure for the intermediate C and draw it in the box above.
(ii) Name the functional groups in carbaryl.
..................................................................................................................................
..................................................................................................................................
(iii) Suggest structures for the three products formed when carbaryl is hydrolysed.
(iv) What reagents and conditions would you use for this hydrolysis?
.................................................................................................................................. [7]
Page 30 of 231
(b) Suggest reagents and conditions for converting 1-naphthol into each of the following
compounds.
(c) Compound D is an isomer of 4-nitro-1-naphthol. D is formed as a by-product during the

reaction in b(ii). It can be converted into 2-amino-1-naphthol, E.
(i) Suggest the structural formula of the isomer D.
(ii) Suggest reagents needed for reaction I.
..................................................................................................................................
(iii) Suggest the structural formula of the compound formed when compound E reacts
with an excess of CH3COCl.
[3]
(d) When an alkaline solution of compound E is added to a solution containing Cu2+(aq)

ions, a pale green-blue precipitate F forms. Analysis of F shows that its formula is
Cu(C10H8NO)2(H2O)2.
(i) Complete the following structural formula of F.
When an excess of concentrated NH3(aq) is added to F, the precipitate dissolves to

form a deep blue solution.
(ii) State the formula of the ion responsible for the deep blue colour.
..................................................................................................................................
(iii) What type of reaction is occurring here?
.............................................................................................................................. [3]
[Total: 15]
Page 31 of 231
27. The nitration of benzene occurs in the following steps.
(a) What reagents and conditions are needed for this reaction?
...................................................................................................................................... [2]
(b) Write an equation showing how the electrophile NO+2 is formed from the reagents.
...................................................................................................................................... [1]
(c) The nitration of methylbenzene produces mainly 2-nitromethylbenzene, whereas the

nitration of benzoic acid produces mainly 3-nitrobenzoic acid.
Use this information to suggest suitable intermediates G and H in the following two
2-stage syntheses of chlorobenzoic acids, and suggest suitable reagents for reactions
I to IV.
reagents:
reaction I ................................................ reaction II ................................................
reaction III .............................................. reaction IV ............................................... [4]

[Total: 7]
28. Recently much interest has been shown in the production of the fuel biodiesel from algae.
Up to 55% of the mass of the dried algae is composed of lipids, the majority of which are
triglycerides.
To convert triglycerides into biodiesel, the following processes are carried out.
Page 32 of 231
(a) Name the functional group present in triglycerides.
.................................................................................................................................... [1]
(b) Suggest reactants and conditions for
reaction I,
..........................................................................................................................................
reaction II.
.......................................................................................................................................... [4]
(c) Suggest the structural formula of the compound formed when glycerol is reacted with
(i) an excess of HBr(aq),
..................................................................................................................................
(ii) an excess of hot acidified K2Cr2O7(aq).
.................................................................................................................................. [2]
(d) Calculate the mass of biodiesel that can be produced from 1000 kg of dried algae,
assuming that 50% of the algal mass is triglycerides.
mass = ........................................... kg [2]
(e) (i) Construct an equation for the complete combustion of biodiesel.
..................................................................................................................................
(ii) Use your equation to calculate the mass of CO2 produced when 10 kg of biodiesel
is burned.
..................................................................................................................................
.................................................................................................................................. [3]
(f) The production of biodiesel is at present an expensive process.
Suggest a reason why the development of biodiesel as an alternative to fossil fuels is

important.
.................................................................................................................................... [1]
[Total: 13]
29. Both ethene and benzene react with bromine, but the mechanisms and the types of
products of the two reactions are different.
Page 33 of 231
(a) State the type of reaction undergone in each of reactions I and II.
reaction I
..........................................................................................................................................
reaction II
.......................................................................................................................................... [2]
(b) In each of reactions I and II, the intermediate is a bromine-containing cation. In each
of the following boxes, draw the intermediate and use curly arrows to show how it is
converted into the product.
(c) Why do ethene and benzene differ in their reaction with bromine?
..........................................................................................................................................
.................................................................................................................................... [1]
[Total: 7]
30. The substituted benzene compound can be further substituted.
If Y is an electron-withdrawing group, the next substitution will be in position 3.

If Y is an electron-releasing group, the next substitution will be mostly in position 4.
The following table lists some electron-withdrawing and electron-releasing substituents.

Page 34 of 231
Use the above information to draw relevant structural formulae in the boxes in the
schemes below.
31. Each of the following structures is an 8-atom segment of the chain of a commercial
polymer.
For each structure,
• decide whether it is part of a condensation or an addition polymer, and

• draw the structural formulae of the monomer(s) from which the polymer is made.
Page 35 of 231
32. (4-aminophenyl)ethanoic acid (4-APEA) and its derivatives are being investigated as
possible drugs to treat chronic inflammation of the intestines.
The synthesis of 4-APEA from methylbenzene is shown in the following scheme.
(a) Draw the structures of the compounds G and H in the boxes above. [2]
(b) Suggest reagents and conditions for the following steps.
• step II
..........................................................................................................................................
• step III
..........................................................................................................................................
• step V
......................................................................................................................................... [3]
[Total: 5]
33. Suggest a test or simple reaction you could carry out on each of the following pairs of
compounds to enable them to be distinguished.
(i) description of test or reaction
..................................................................................................................................
..................................................................................................................................
(ii) observation with compound J
..................................................................................................................................
(iii) observation with compound K
.................................................................................................................................. [2]
Page 36 of 231
..................................................................................................................................
..................................................................................................................................
(ii) observation with compound L
..................................................................................................................................
(iii) observation with compound M
.................................................................................................................................. [2]
..................................................................................................................................
..................................................................................................................................
(ii) observation with compound N
..................................................................................................................................
(iii) observation with compound P
.................................................................................................................................. [2]
..................................................................................................................................
..................................................................................................................................
(ii) observation with compound Q
..................................................................................................................................
(iii) observation with compound R
.................................................................................................................................. [2]
[Total: 8]
34. (a) Explain briefly what is meant by the word protein.
..........................................................................................................................................
.................................................................................................................................... [1]
Page 37 of 231
(b) Describe how peptide bonds are formed between amino acids during the formation of a
tripeptide. Include diagrams and displayed formulae in your answer.
.................................................................................................................................... [3]
(c) Describe how proteins can be broken down into amino acids in the laboratory without
the aid of enzymes.
.................................................................................................................................... [2]
(d) When a small polypeptide S was broken down in this way, three different amino acids
were produced according to the following reaction.
(i) How many peptide bonds were broken during this reaction?
..................................................................................................................................
(ii) Calculate the Mr of the polypeptide S.
Mr = ..................................................... [3]
[Total: 9]
35. (a) In the following boxes draw the structural formulae of three alcohols having straight
(i.e. unbranched) chains, with the molecular formula C5H12O.
Use the letters A, B or C as appropriate when answering the following questions. Each
letter may be used once, more than once or not at all.
(b) Which of the alcohols are chiral? .................................................................................. [1]
(c) (i) Which of these alcohols react with alkaline aqueous iodine? ...................................
(ii) Describe the observation you would make during this reaction.
..................................................................................................................................
(iii) Draw the structural formulae of the products of this reaction.
[4]
Page 38 of 231
(d) Draw the structural formula of the product obtained when each of the alcohols A, B and
C is heated with an excess of acidified K2Cr2O7(aq).
(e) One of the many suggestions for converting biomass into liquid fuel for motor transport
is the pyrolysis (i.e. heating in the absence of air) of cellulose waste, followed by the
synthesis of alkanes.
(i) In the first reaction, cellulose, (C6H10O5)n, is converted into a mixture of carbon
monoxide and hydrogen. Some carbon is also produced.
Complete and balance the equation for this reaction.
(ii) The second reaction involves the combination of CO and H2 to produce alkanes
such as heptane.
Using the value of 1080 kJ mol-1 as the value for the bond energy in CO,
and other relevant bond energies from the Data Booklet, calculate the for this
reaction.
= ......................................... kJ mol-1
[5]
[Total: 15]
36. Phenol and chlorobenzene are less reactive towards certain reagents than similar non-
aromatic compounds.
Thus hexan-1-ol can be converted into hexylamine by the following two reactions,
whereas neither of the following two reactions takes place.

Page 39 of 231
(a) (i) Suggest reagents and conditions for
reaction I, ...............................................................................................................
reaction II. ...............................................................................................................
(ii) What type of reaction is reaction II? ..........................................................................
(iii) Suggest a reason why chlorobenzene is much less reactive than 1-chlorohexane.
.................................................................................................................................. [4]
(b) Phenylamine can be made from benzene by the following two reactions.
(i) Suggest reagents and conditions for
reaction III, ..............................................................................................................
reaction IV. ..............................................................................................................
(ii) State the type of reaction for
reaction III, ..............................................................................................................
reaction IV. .............................................................................................................. [5]
(c) Suggest a reagent that could be used to distinguish phenylamine from hexylamine.
reagent and conditions ....................................................................................................
observation with phenylamine ..........................................................................................
observation with hexylamine ............................................................................................. [2]
(d) Phenylamine is used to make azo dyes. In the following boxes draw the structural
formula of the intermediate D and of the azo dye E.
[2]
[Total: 13]
Page 40 of 231
37. Cyclohexanol and phenol are both solids with low melting points that are fairly soluble in
water.
(a) Explain why these compounds are more soluble in water than their parent hydrocarbons
cyclohexane and benzene.
..........................................................................................................................................
..................................................................................................................................... [2]
(b) Explain why phenol is more acidic than cyclohexanol.
..........................................................................................................................................
..................................................................................................................................... [2]
(c) For each of the following reagents, draw the structural formula of the product obtained
for each of the two compounds. If no reaction occurs write no reaction in the box.
(d) Choose one of the above five reagents that could be used to distinguish between
cyclohexanol and phenol. Describe the observations you would make with each compound.
reagent ........................................................................................
observation with cyclohexanol ........................................................................................
observation with phenol ........................................................................................ [2]

[Total: 13]
Page 41 of 231
38. Kevlar is a tough polyamide used in bullet-proof vests and high-specification bicycle tyres.
It can be manufactured by the following process.
(a) (i) Suggest reagents and conditions for
reaction I, .............................................................................................................
reaction II. .............................................................................................................
(ii) Draw the structural formula of one repeat unit of Kevlar in the box above. [4]
(b) The di-acid chloride C reacts with a variety of reagents. Suggest the structural formulae
of the products of the reaction of C with
(i) CH3NH2,
(ii) HOCH2CH2OH.
[3]
(c) The diamine D also reacts with a variety of reagents. Suggest the structural formulae of
the products of the reaction of D with
(i) HCl (aq),
(ii) Br2(aq).
[3]
(d) 4-aminobenzoic acid, E, is a useful intermediate for making dyes.
Suggest reagents and conditions for
reaction III, .....................................................................................................................
reaction IV. ..................................................................................................................... [4]

Page 42 of 231
(e) 4-aminobenzoic acid, E, forms a zwitterion.
(i) What is meant by the term zwitterion?
..................................................................................................................................
..................................................................................................................................
(ii) Draw the structural formula of the zwitterion formed from 4-aminobenzoic acid.
[2]
[Total: 16]
39. (a) All the carbon atoms in benzene lie in the same plane. This means that they are coplanar, but
this is not the case with cyclohexane.
By rotating the molecule around its several C–C bonds, all the carbon atoms in butane
can be made to lie in the same plane, but this is not the case with methylpropane.
By considering the 3-dimensional geometry of the following five molecules, and allowing
rotations around C–C bonds, decide whether or not the carbon atoms in each molecule
can be arranged in a coplanar fashion. Then place a tick in the appropriate column in
the table below.
Page 43 of 231
(b) Methylbenzene can react with chlorine under different conditions to give the monochloro
derivatives F and G.
Suggest reagents and conditions for each reaction.
reaction I
..........................................................................................................................................
reaction II
...................................................................................................................................... [2]
(c) Benzyl benzoate is a constituent of many perfumery products, and has also been
used in the treatment of the skin condition known as scabies. It can be made from
methylbenzene by the following route, which uses one of the chlorination reactions
from (b).
(i) Draw the structural formula of the intermediate H in the box above.
(ii) Suggest reagents and conditions for each reaction.
reaction Ill
..................................................................................................................................
reaction V
..................................................................................................................................
reaction VI
..................................................................................................................................
Page 44 of 231
(iii) State the type of reaction occurring during
reaction Ill,
..................................................................................................................................
reaction V.
.................................................................................................................................. [6]
[Total: 11]
40. Compounds J and K are isomers with the molecular formula C5H11NO, and they contain the
same functional group.
They may both be obtained from ethanol by the following routes.
(a) Draw the structural formulae of the lettered compounds J to Q in the boxes above. [7]
(b) Suggest reagents and conditions for the following.
reaction I
..........................................................................................................................................
reaction Il
..........................................................................................................................................
Page 45 of 231
reaction IV
...................................................................................................................................... [3]
(c) What type of reaction is occurring in
reaction IV,
..........................................................................................................................................
reaction VI?
...................................................................................................................................... [2]
(d) (i) Name the functional group that is common to compounds J and K.
..................................................................................................................................
(ii) Name the functional group that is common to compounds N and P.
.............................................................................................................................. [2]
[Total: 14]
41. Ethanolamine and phenylamine are two organic bases that are industrially important.
Ethanolamine is a useful solvent with basic properties, whilst phenylamine is an important
starting material in the manufacture of dyes and pharmaceuticals.
The following table lists some of their properties, together with those of propylamine.
(a) Suggest why the boiling point of ethanolamine is much higher than that of propylamine.
Draw a diagram to illustrate your answer.
..........................................................................................................................................
..........................................................................................................................................
[2]
(b) Describe and explain the relative basicities of propylamine and phenylamine.
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [2]
(c) Write an equation showing ethanolamine acting as a Brønsted-Lowry base.
...................................................................................................................................... [1]
Page 46 of 231
(d) Propylamine can be synthesised from bromoethane by the following route.
(i) Draw the structure of the intermediate compound X in the box above.
step 1 ........................................................................................................................
step 2 ........................................................................................................................ [3]
(e) Apart from their relative basicities, ethanolamine and phenylamine differ in many of their
reactions.
For each of these two compounds, describe one test that would give a positive result
with the stated compound, but a negative result with the other.
ethanolamine
test ...................................................................................................................................
observation ......................................................................................................................
phenylamine
test ...................................................................................................................................
observation ...................................................................................................................... [4]

[Total: 12]
42. Acyl chlorides are useful intermediates in organic syntheses.
(a) (i) State a suitable reagent for converting carboxylic acids into acyl chlorides.
..................................................................................................................................
(ii) Construct an equation for the reaction between ethanoic acid, CH3CO2H, and the
reagent you have stated in (i).
.................................................................................................................................. [2]
(b) (i) In the boxes provided draw the structures of the compounds formed when benzoyl
chloride undergoes the following reactions.
(ii) Name the functional group in
• compound A ..................................................................
• compound B .................................................................
Page 47 of 231
(iii) What type of reaction is reaction II?
.................................................................................................................................. [5]
(c) (i) Suggest suitable acyl chlorides to use in the following reaction. Draw their structures
in the boxes provided.
Compound E dissolves in, but does not react with, cold water.
(ii) Suggest the major type of intermolecular interaction that occurs between E and
water.
..................................................................................................................................
(iii) A solution of the diamine H2NCH2CH2NH2 in water has pH = 11 but a solution of E

in water has pH = 7. Suggest why this is the case.
..................................................................................................................................
(iv) What type of polymer is compound F?
.................................................................................................................................. [5]
[Total: 12]
43. Predict the products of the following reactions and draw their structures in the boxes
provided.
Note that the molecular formula of the final product is given in each case.
[6]
[Total: 6]
Page 48 of 231
44. (a) Complete the electronic structures of the Cr3+ and Mn2+ ions.
Cr3+ 1s22s22p6 .............
Mn2+ 1s22s22p6 .............

[2]
(b) (i) Describe what observations you would make when dilute KMnO4(aq) is added
slowly and with shaking to an acidified solution of FeSO4(aq) until the KMnO4 is in
a large excess.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(ii) Construct an ionic equation for the reaction that occurs.
.................................................................................................................................. [4]
(c) By selecting relevant data from the Data Booklet explain why acidified solutions of
Fe2+(aq) are relatively stable to oxidation by air, whereas a freshly prepared precipitate of
Fe(OH)2 is readily oxidised to Fe(OH)3 under alkaline conditions.
relevant values and half equations
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
explanation
..........................................................................................................................................
.......................................................................................................................................... [4]
(d) Predict the organic products of the following reactions and draw their structures in the
boxes below. You may use structural or skeletal formulae as you wish.
Page 49 of 231
(e) KMnO4 and K2Cr2O7 are the reagents that can be used to carry out the following
transformation.
(i) Draw the structure of intermediate E in the box above.
(ii) Suggest reagents and conditions for the following.
reaction I ...................................................................................................................
reaction II .................................................................................................................. [3]

[Total: 17]
45. (a) (i) Briefly explain why the benzene molecule is planar.
..................................................................................................................................
..................................................................................................................................
(ii) Briefly explain why all the carbon-carbon bonds in benzene are the same length.
..................................................................................................................................
..................................................................................................................................
.................................................................................................................................. [2]
(b) Benzene can be nitrated by warming it with a mixture of concentrated sulfuric and
nitric acids.
(i) By means of an equation, illustrate the initial role of the sulfuric acid in this
reaction.
..................................................................................................................................
(ii) Name the type of reaction and describe the mechanism for the nitration reaction,
including curly arrows showing the movement of electrons and all charges.
type of reaction .........................................................................................................
mechanism
[4]
Page 50 of 231
(c) State the reagents and conditions needed to convert benzene into chlorobenzene.
...................................................................................................................................... [1]
(d) Nitrobenzene undergoes further substitution considerably more slowly than

chlorobenzene. In nitrobenzene the incoming group joins to the benzene ring in the
3-position, whereas in chlorobenzene the incoming group joins to the benzene ring in the
4-position.
(i) Use these ideas to suggest the structures of the intermediate compounds Y and Z
in the following synthesis of 4-chlorophenylamine.
(ii) Suggest the reagents and conditions needed for reaction III in the above
synthesis.
..................................................................................................................................
(iii) Suggest the structural formulae of the products A, B, C and D of the following
reactions. If no reaction occurs write “no reaction” in the relevant box.
[8]
[Total: 15]
46. (a) Compound G can be synthesised from benzene by the route shown below.
(i) Name the functional group formed in step 5.
..................................................................................................................................
Page 51 of 231
(ii) Draw the structures of the intermediates H and J in the boxes above.
(iii) Suggest reagents and conditions for the following.
step 2 ........................................................................................................................
step 3 ........................................................................................................................
step 4 ........................................................................................................................
step 5 ........................................................................................................................ [7]
(b) In a reaction discovered just over 100 years ago by the German chemist Karl Fries,
compound G is converted into compound K when it is heated with AlCl3.Compound K is a
structural isomer of G.
Compound K is a 1,4-disubstituted benzene derivative. It is insoluble in water, but

dissolves in NaOH(aq). It gives a white precipitate with Br2(aq), and a yellow precipitate
with alkaline aqueous iodine.
(i) What is meant by the term structural isomerism?
..................................................................................................................................
..................................................................................................................................
(ii) Use the information given above to name two functional groups in compound K.
..................................................................................................................................
..................................................................................................................................
(iii) Suggest the structural formula of K, and draw it in the box above.
(iv) Suggest structures for the aromatic products of the following reactions.
Page 52 of 231
47. Menthone, C10H18O, is a cyclic ketone that occurs in oil of peppermint.
(a) Use asterisks (*) on the formula above to identify any chiral centres in the molecule of
menthone. [2]
(b) Menthone can be reduced to menthol, which can be dehydrated to a mixture of two
alkenes, L and M.
(i) Suggest reagents for
step 1, ......................................................................................................................
step 2. .......................................................................................................................
(ii) Suggest structures for L and M and draw them in the boxes above. [4]
(c) When heated with concentrated, acidified KMnO4(aq), one of the two alkenes L or M
produces the dicarboxylic acid N.
(i) Give the letter of the alkene that produced N by this reaction.
..................................................................................................................................
(ii) Suggest the structure of the product, P, of the reaction between the other alkene
you have drawn and hot concentrated acidified KMnO4.
Page 53 of 231
(iii) Suggest one chemical test that would enable you to distinguish between N and P.
reagent(s) ..................................................................................................................
observation ................................................................................................................ [3]
(d) Chlorocyclohexane can be prepared by bubbling HCl(g) through a solution of

cyclohexene.
Suggest the mechanism of this 2-stage reaction by means of a diagram. Include all whole or
partial charges, and represent the movements of electron pairs by curly arrows.
[3]
[Total: 12]
48. Menthol and menthone, the main constituents of oil of peppermint, can be made synthetically
from thymol by the following route.
(a) State the type of reaction of
• reaction I, ..........................................................................................................
• reaction II. ......................................................................................................... [2]
(b) Suggest one test for each of the three compounds that would give a positive result with
the stated compound but a negative result with both the other two compounds.
thymol
test ...................................................................................................................................
observation ......................................................................................................................
menthol
test ...................................................................................................................................
observation ......................................................................................................................
menthone
test ...................................................................................................................................
observation .................................................................................................................. [6]

[Total: 8]
Page 54 of 231
49. The following chart shows some reactions of ethylbenzene and compounds produced from it.
(i) Draw the structure of compound X in the box provided in the chart above.
(ii) Suggest reagents and conditions for each of the reactions, writing them in the spaces
below.
reaction I ......................................................................................................................
reaction II ......................................................................................................................
reaction III ......................................................................................................................
reaction IV ......................................................................................................................
reaction V ......................................................................................................................
reaction VI ......................................................................................................................
reaction VII ......................................................................................................................

[Total: 8]
Page 55 of 231
50. The following scheme outlines the production of some compounds from ethene.
(a) (i) Suggest the reagent and conditions for reaction I.
..................................................................................................................................
(ii) Describe the mechanism of reaction I by means of a diagram. Include all whole,
partial and induced charges, and represent the movements of electron pairs by
curly arrows.
[3]
(b) Suggest the identities of compounds B, C and E, and draw their structures in the boxes
opposite. [3]
(c) Suggest reagents and conditions for
reaction II,
..........................................................................................................................................
reaction III.
...................................................................................................................................... [2]
(d) During reaction II the nitrogen atoms are lost from the organic molecule. Suggest the
identity of the nitrogen-containing ion produced during this reaction.
...................................................................................................................................... [1]
(e) Compounds E and F react together to give a polymer and an inorganic product.
(i) Draw one repeat unit of this polymer.

Page 56 of 231
(ii) Identify the inorganic product.
.............................................................................................................................. [2]
(f) A 0.100 mol dm–3 solution of compound D has a pH of 2.60.
(i) Calculate the [H+] in this solution.
(ii) Hence calculate the value of Ka of compound D.
[2]
[Total: 13]
51. (a) There are several ways of introducing chlorine atoms into organic molecules. State the
reagents and conditions necessary to carry out the following transformations.
(b) (i) When treated with concentrated HNO3 + H2SO4 at 55 °C, benzene produces
nitrobenzene.
Outline the mechanism of this reaction. You should include all charges, and use
curly arrows to represent the movement of electron pairs.
In aromatic substitution of monosubstituted benzenes, the orientation of an incoming

group depends on the nature of the group already attached to the ring.
For example, using the same reagents and conditions as in (i), methylbenzene and
benzoic acid produce the following nitro compounds.
Page 57 of 231
(ii) Using this information as an aid, suggest a structure for compound C in the following
synthesis of 3-bromobenzoic acid.
(iii) Suggest reagents and conditions for steps 1 and 2.
[6]
[Total: 12]
52. (a) The reaction producing tri-iodomethane (iodoform) can be used as a test for the
presence of certain groups within a molecule.
(i) State the reagents and conditions used for this reaction.
..................................................................................................................................
(ii) Write the structural formula of one functional group that would give a positive result
with this iodoform reaction.
..................................................................................................................................
(iii) What do you observe in a positive test?
..................................................................................................................................
..................................................................................................................................
(iv) In the following table place a tick (✓) in the column against each compound that
would give a positive result with this test, and a cross (✗) against each compound
that would give a negative result.
[6]
Page 58 of 231
(b) The iodoform test can be used, along with other reactions, to work out the structures of
unknown compounds.
Use the information in the table below to deduce the structures of the compounds in the
following scheme, and draw these structures in the boxes provided.
Results of tests (✓indicates a positive result; ✗indicates a negative result)
(c) Treatment of compound F with NaBH4 gives compound G, C4H8O3. Heating G with
Al2O3 gives a mixture of three isomeric unsaturated carboxylic acids H, J and K,
C4H6O2, two of which are stereoisomers of each other.
Suggest structures for G, H, J, and K, and name the type of stereoisomerism shown.
type of stereoisomerism ............................................................................................... [5]

[Total: 14]
3. (a) Polyvinyl acetate, PVA, is a useful adhesive for gluing together articles made from wood,
paper or cardboard. The monomer of PVA is ethenyl ethanoate, B.
PVA is formed from B by the process of addition polymerisation.

(i) Draw a section of the PVA molecule containing at least 2 monomer molecules, and
identify clearly the repeat unit.
Page 59 of 231
The ester B can be hydrolysed in the usual way, according to the following
equation.
(ii) Use this information to suggest a possible structure for C and draw it in the box
above.
When substance C is extracted from the product mixture, it is found that it does not
decolourise Br2(aq), but it does form a pale yellow precipitate with alkaline aqueous
iodine.
(iii) Suggest a structure for C that fits this new information
(iv) Suggest a confirmatory test for the functional group in the structure you have drawn
in (iii). Your answer should include the reagent you would use and the observation
you would make.
..................................................................................................................................
.................................................................................................................................. [6]
(b) The following diagram represents a section of another polymer.
(i) On the above formula draw brackets, [ ], around the atoms that make up the repeat
unit of this polymer.
(ii) Name the functional group in polymer D.
..................................................................................................................................
(iii) Suggest and draw the structure of the monomer, E, that could form this polymer.
(iv) What type of polymerisation is involved in making polymer D from its monomer?
..................................................................................................................................
(v) What is the relationship between the repeat unit of polymer D and the repeat unit of
PVA?
.................................................................................................................................. [5]
Page 60 of 231
(c) Monomer E exists as two stereoisomers. Heating either isomer with Al2O3 gives a
mixture of two unsaturated carboxylic acids F and G, which are stereoisomers of each
other.
(i) Name the type of stereoisomerism shown by compound E.
..................................................................................................................................
(ii) Suggest structures for F and G, and name the type of stereoisomerism they show.
type of isomerism ...................................................................................................... [4]

[Total: 15]
54. (a) Describe and explain how the acidities of ethanol and phenol compare to that of water.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
...................................................................................................................................... [4]
(b) Complete the following equations showing all the products of each of these reactions of
phenol. Include reaction conditions where appropriate in the boxes over the arrows. If no
reaction occurs write no reaction in the products box.
[5]
Page 61 of 231
(c) The analgesic drug paracetamol can be synthesised from phenol by the following route.
Suggest reagents and conditions for the each of three steps, and suggest the structure
of the intermediate H. Write your answers in the boxes provided.
[4]
[Total: 13]
55. (a) (i) Write the equation for a reaction in which ethylamine, C2H5NH2, acts as a
Brønsted-Lowry base.
..................................................................................................................................
(ii) Ammonia, ethylamine and phenylamine, C6H5NH2, are three nitrogen-containing

bases.
Place these three compounds in order of basicity, with the most basic first.
(iii) Explain why you have placed the three compounds in this order.
..................................................................................................................................
..................................................................................................................................
.................................................................................................................................. [4]
Page 62 of 231
(b) (i) Write an equation for a reaction in which phenol, C6H5OH, acts as a Brønsted-Lowry
acid.
..................................................................................................................................
The pKa values for phenol, 4-nitrophenol and the phenylammonium ion are given in
the table.
(ii) Suggest an explanation for the difference in the pKa values of phenol and nitrophenol.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iii) Using the information in the table opposite, predict which of the following pKa values
is the most likely for the 4-nitrophenylammonium ion.
Place a tick (✓) in the box beside the value you have chosen.
(iv) Explain your answer to part (iii).
..................................................................................................................................
.................................................................................................................................. [5]
(c) Phenylamine can be converted to 4-nitrophenol by the following steps.
(i) Suggest the identity of intermediate B by drawing its structure in the box above.
Page 63 of 231
(ii) Suggest reagents and conditions for the three steps in the above scheme.
[5]
[Total: 14]
56. Compound C has the molecular formula C7H14O. Treating C with hot concentrated
acidified KMnO4(aq) produces two compounds, D, C4H8O, and E, C3H4O3. The results
of four tests carried out on these three compounds are shown in the following table.
(a) State the functional groups which the above four reagents test for.
(i) Br2(aq)
..................................................................................................................................
(ii) Na(s)
..................................................................................................................................
(iii) I2(aq) + OH–(aq)
..................................................................................................................................
(iv) 2,4-dinitrophenylhydrazine
.................................................................................................................................. [4]
(b) Based upon the results of the above tests, suggest structures for compounds D and E.
D, C4H8O E, C3H4O3
[2]
Page 64 of 231
(c) Compound C exists as two stereoisomers.
Draw the structural formula of each of the two isomers, and state the type of
stereoisomerism involved.
type of stereoisomerism ....................................................... [3]

[Total: 9]
57. (a) Amino acids such as alanine are essential building blocks for making proteins. They can
be synthesised by a general reaction of which the following is an example.
(i) Suggest the structure of the intermediate compound E by drawing its structural
formula in the box above.
(ii) Suggest, in the box below, the structural formula of the starting material needed to
synthesise phenylalanine by the above general reaction.
(b) (i) What is a protein?
..................................................................................................................................
(ii) Using alanine as an example, draw a diagram to show how proteins are formed
from amino acids. Show two repeat units in your answer.
[3]
(c) The hydrolysis of compound F produces two compounds G and H.
(i) State the reagents and conditions needed for this hydrolysis.
..................................................................................................................................
(ii) Draw the structures of the two products G and H in the boxes above. [3]
Page 65 of 231
(d) (i) Draw the zwitterionic structure of alanine.
(ii) Suggest the structural formulae of the zwitterions that could be formed from the
following compounds.
[4]
58. Alkanes are generally considered to be unreactive compounds, showing an inertness to

common reagents such as NaOH, H2SO4, and K2Cr2O7.
(a) Suggest a reason why these reagents do not attack an alkane such as CH4.
.......................................................................................................................................... [1]
(b) When a mixture of chlorine and ethane gas is exposed to strong sunlight, an explosion
can occur due to the fast exothermic reaction.
Under more controlled conditions, however, the following reaction occurs.
(i) What is the name of this type of reaction?
..................................................................................................................................
(ii) Use equations to describe the mechanism of this reaction, naming the steps
involved.
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
..................................................................................................................................
(iii) This reaction can produce organic by-products, in addition to C2H5Cl.
Draw the structural formulae of three possible organic by-products. Two of your
by-products should contain 4 carbon atoms per molecule.
Briefly describe how each by-product could be formed.
Page 66 of 231
(iv) It is found by experiment that, during this type of reaction, primary, secondary and
tertiary hydrogen atoms are replaced by chlorine atoms at different rates, as shown
in the following table.
Using this information, and considering the number of hydrogen atoms of each type
(primary, secondary or tertiary) within the molecule, predict the relative ratio of the
two possible products J and K from the chlorination of 2-methylpropane. Explain
your answer.
ratio J / K = .....................................................
explanation:
..................................................................................................................................
.................................................................................................................................. [10]
(c) In the boxes below draw the skeletal formulae of four different structural isomers of
C5H11Cl that could be obtained from the chlorination of 2-methylbutane. Indicate any
chiral centres in your structures by an asterisk (*).
[5]
[Total: 16]
Page 67 of 231
59. Indigo is the dye used in blue jeans. Although originally extracted from plants of the type
indigofera, it is now almost entirely made artificially.
Indigo is insoluble in water but this disadvantage can be overcome by converting it into the
water-soluble colourless leuco-indigo. If cloth soaked in a solution of leuco-indigo is left to dry
in the air, the leuco-indigo is converted into the insoluble blue indigo, which is precipitated out
onto the fibres of the cloth.
(a) (i) Give the molecular formula of indigo.
....................................................................................................................................
(ii) Name three functional groups in indigo.
............................................................................................................................ [3]
(b) (i) What type of reaction is the conversion of indigo into leuco-indigo?
....................................................................................................................................
(ii) Suggest a laboratory reagent for this reaction.
.................................................................................................................................... [2]
(c) Suggest two chemical tests that could be used to distinguish between indigo and
leuco-indigo. Write your answers in the following table.
[5]
(d) When indigo is heated with hydrogen and a nickel catalyst, compound A, C16H28N2O2, is
formed.
(i) Suggest a structure for A.

Page 68 of 231
(ii) Calculate the volume of hydrogen, measured at room temperature and pressure,
that would have been absorbed if 2.50 g of indigo had undergone this reaction.
volume = ...........................dm3
[3]
(e) Suggest the structure of the product formed when indigo reacts with an excess of Br2(aq).
[3]
[Total: 16]
60. (a) Methoxybenzene reacts with Br2(aq) in a similar manner to phenol.
(i) Draw the structural formula of the product of the reaction between methoxybenzene
and an excess of bromine.
(ii) Suggest a chemical reaction you could use to distinguish between methoxybenzene
and phenol. State the reagent, describe the observations you would make, and give
an equation for the reaction.
reagent ......................................................................................................................
.
observation .................................................................................................................
equation [4]
Page 69 of 231
(b) Phenol can be synthesised from benzene by the following route.
(i) Suggest structures for compounds D and E and draw them in the boxes above.
step 2, .........................................................................................................................
step 4. ........................................................................................................................ [4]
(c) The following chart shows some reactions of compound F which is a neutral compound.
G forms a salt with dilute H2SO4, whereas H forms a salt with NaOH(aq).
Both G and H can be obtained from compound J by separate one-step reactions (reaction
1 and reaction 2 below).
All four compounds F, G, H and J form a yellow precipitate with alkaline aqueous iodine.
(i) Suggest structures for F, G, H and J, and draw them in the boxes above.
Page 70 of 231
(ii) Suggest reactants and conditions for
reaction 1, ..................................................................................................................
reaction 2. .................................................................................................................. [6]

[Total: 14]
61. (a) Describe and explain how the acidities of CHCl2CO2H and CH2ClCO2H compare to each
other, and to the acidity of ethanoic acid.
..........................................................................................................................................
..........................................................................................................................................
..........................................................................................................................................
.......................................................................................................................................... [3]
(b) For each of the following pairs of compounds, suggest one chemical test (reagents and
conditions) that would distinguish between them.
State the observations you would make with each compound, writing ‘none’ if appropriate.
[7]
(c) The following diagram shows a section (not a repeat unit) of a polymer, G, that can be
made from the two monomers E and F.
(i) What type of polymerisation made this polymer?
...................................................................................................................................
Page 71 of 231
(ii) Draw the structures of the two monomers E and F.
(iii) Suggest the conditions needed to make polymer G from E and F in the laboratory.
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(iv) One of the monomers, E or F, could be changed to make a more rigid polymer of a
similar chemical type to G.
Suggest which of your two monomers could be changed, and suggest a structure for
the new monomer.
Monomer to be changed (E or F) ...........................
Structural formula of the new monomer
[6]
[Total: 16]
Page 72 of 231
62. The compound responsible for the hot taste of chilli peppers is capsaicin. Its molecular
structure can be deduced by the following reaction scheme.
Compounds C, D and E all react with Na2CO3(aq).
Answer the following questions.
(a) Suggest reagents and conditions for reaction 3.
.................................................................................................................................... [1]
(b) What type of reaction is reaction 4?
.................................................................................................................................... [1]
(c) Suggest reagents and conditions for reaction 5.
.................................................................................................................................... [1]
Page 73 of 231
(d) Name the functional group in C that has reacted with hot concentrated acidified KMnO4.
.................................................................................................................................... [1]
(e) Suggest the name of the functional group in capsaicin that has reacted in reaction 1.
.................................................................................................................................... [1]
(f) Work out structures for compounds C–F and capsaicin, and draw their structural formulae
in the boxes opposite. [5]
[Total: 10]
63. Compound G is a naturally occurring aromatic compound that is present in raspberries.
(a) Identify the functional groups present in compound G.
..........................................................................................................................................
.................................................................................................................................... [2]
(b) Complete the following table with information about the reactions of the three stated
reagents with compound G.
[8]
Page 74 of 231
(c) The dye H can be made from compound G by the route shown below.
(i) Draw the structures of the amine J and the intermediate K in the boxes above.
step 1, ........................................................................................................................
step 2. ........................................................................................................................ [5]
(d) Suggest a reaction scheme by which compound G and propanoic acid could be converted
into compound L.
[3]
[Total: 18]
Page 75 of 231
64. The compound responsible for the yellow colour of the spice turmeric is curcumin. Its
molecular structure can be deduced from the following series of reactions. The CH3O– group
that is present in curcumin may be regarded as unreactive.
Curcumin and compounds A and D all react with 2,4-dinitrophenylhydrazine reagent.
Compounds A and B effervesce with Na2CO3(aq), but curcumin, and compounds C and D,
do not.
Curcumin reacts with Br2(aq) and with cold dilute acidified KMnO4
(a) (i) Name the functional group common to curcumin and compounds A and D.
...................................................................................................................................
(ii) Name the functional group common to compounds A and B.
................................................................................................................................... [2]
(b) (i) Suggest the structures of compounds B, C and D, and draw their structural formulae
in the relevant boxes opposite.
(ii) Suggest suitable reagents and conditions for reaction 4.
................................................................................................................................... [4]
Page 76 of 231
(c) (i) Name the type of reaction for reaction 2.
...................................................................................................................................
(ii) Suggest a reagent for reaction 2.
...................................................................................................................................
(iii) Suggest the structure of compound A, and draw its structural formula in the relevant
box opposite. [3]
(d) (i) Name the functional group in curcumin that reacts with cold dilute acidified KMnO4.
...................................................................................................................................
(ii) Name two functional groups in curcumin that react with Br2(aq).
................................................................................................................................... [2]
(e) Suggest a structure for curcumin and draw its structural formula in the relevant box
opposite. [2]
[Total: 13]
65. (a) (i) Explain why ethylamine is basic.
...................................................................................................................................
...................................................................................................................................
(ii) Write an equation showing ethylamine acting as
a base, .......................................................................................................................
a nucleophile. ............................................................................................................
(iii) Why is phenylamine less basic than ethylamine?
...................................................................................................................................
...................................................................................................................................
...................................................................................................................................
(a) (i) Explain why ethylamine is basic.
...................................................................................................................................
...................................................................................................................................
(ii) Write an equation showing ethylamine acting as
a base, .......................................................................................................................
a nucleophile. ............................................................................................................
(iii) Why is phenylamine less basic than ethylamine?
...................................................................................................................................
...................................................................................................................................
Page 77 of 231
Alkaloids are naturally-occurring compounds that act as bases.
(iv) Suggest the structure of the product, E, of the reaction between the alkaloid nicotine
and an excess of HCl (aq).
[6]
(b) Phenylamine, and substituted phenylamines, are used to make cloth dyes and food
colourants.
The first step in this process is the production of a diazonium salt.
(i) State the reagents and conditions necessary for this reaction.
...................................................................................................................................
The diazonium salt is then reacted with a phenol or an aryl amine in alkaline solution.
Page 78 of 231
(ii) Suggest the starting materials needed to synthesise the following dyes.
Draw their structures in the boxes provided.
(iii) Suggest what effect the NaO3S– group in methyl orange has on its properties. This
group has no effect on the colour of the compound.
................................................................................................................................... [7]
[Total: 13]
Page 79 of 231
66. Because of the lack of reactivity of the nitrogen molecule, extreme conditions need to be used
to synthesise ammonia from nitrogen in the Haber process.
(a) Suggest an explanation for the lack of reactivity of the nitrogen molecule, N2.
...........................................................................................................................................
........................................................................................................................................... [1]
(b) Under conditions of high temperature, nitrogen and oxygen react together to give oxides
of nitrogen.
(i) Write an equation for a possible reaction between nitrogen and oxygen.
....................................................................................................................................
(ii) State two situations, one natural and one as a result of human activities, in which
nitrogen and oxygen react together.
....................................................................................................................................
....................................................................................................................................
(iii) What is the main environmental effect of the presence of nitrogen oxides in the
atmosphere?
.................................................................................................................................... [4]
(c) Describe and explain how the basicities of ethylamine and phenylamine compare to that
of ammonia.
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
...........................................................................................................................................
........................................................................................................................................... [4]
Page 80 of 231
(d) Compound X is a useful intermediate in the synthesis of pharmaceuticals.

X can be synthesised from chloromethylbenzene according to the following scheme.
(i) What type of reaction is each of the following?
step 1 .........................................................................................................................
step 2 .........................................................................................................................
step 1, ........................................................................................................................
step 2. ........................................................................................................................
(iii) Draw the structures of the intermediates T and W in the boxes above. [6]
[Total: 15]
Page 81 of 231
67. (a) A series of experiments is carried out in which the reagent shown at the top of the column
of the table is mixed, in turn, with each of the reagents at the side.
Complete the following table by writing in each box the formula of any gas produced.
Write x in the box if no gas is produced.
The first column has been completed as an illustration.
[5]
(b) Compound C is responsible for the pleasant aroma of apples. It can be prepared from
phenol by the following 3-step synthesis.
(i) The only by-product of step 1 is HCl. Suggest the reagent that was used to react
with phenol to produce compound A.
....................................................................................................................................
(ii) What type of reaction is occurring in step 2?
....................................................................................................................................
(iii) What reagents and conditions are required for step 3?
....................................................................................................................................
(iv) State the reagent and conditions needed to convert C back to B, the reverse of
step 3.
.................................................................................................................................... [5]
Page 82 of 231
(c) (i) Either compound A or compound B, or both, react with the following reagents.
For each reagent draw the structure of the organic product formed with A, and with
B. If no reaction occurs, write ‘no reaction’ in the relevant box.
(ii) Choose one of the above reactions to enable you to distinguish between A and B.
State below the observations you would make with each compound.
[7]
[Total: 17]
June 2013/41
Page 83 of 231
68. (a) Describe the reagents and conditions required to form a nitro compound from the
following.
[3]
(b) Draw the structure of the intermediate organic ion formed during the nitration of benzene.
[1]
(c) In the box over the arrow below, write the reagents needed to convert nitrobenzene into
phenylamine.
[1]
(d) Phenylamine can be converted into the organic compounds A and B.
(i) Suggest the structural formulae of A and B in the boxes below.
(ii) Suggest suitable reagents and conditions for step 1, and write them in the box over
the arrow.
[3]
Page 84 of 231
(e) When phenylamine is treated with propanoyl chloride a white crystalline compound, C,
C9H11NO, is formed.
(i) Name the functional group formed in this reaction. ...................................................
(ii) Calculate the percentage by mass of nitrogen in C.
percentage = ........................ %
(iii) Draw the structural formula of C.
[3]
[Total: 11]
69. Coffee beans contain chlorogenic acid.
(a) (i) Draw circles around any chiral centres in the above structure.
(ii) Write down the molecular formula of chlorogenic acid.
....................................................................................................................................
(iii) How many moles of H2(g) will be evolved when 1 mol of chlorogenic acid reacts with
an excess of sodium metal?
....................................................................................................................................
(iv) How many moles of NaOH(aq) will react with 1 mol of chlorogenic acid under each
of the following conditions?
in the cold ...............................................
on heating ............................................... [6]

Page 85 of 231
(b) On heating with dilute aqueous acid, chlorogenic acid produces two compounds, D and
E.
(i) What type of reaction is chlorogenic acid undergoing when D and E are formed?
....................................................................................................................................
When compound D is heated with concentrated H2SO4, compound F, C7H6O3, is formed.
Compound F evolves CO2(g) when treated with Na2CO3(aq), and decolourises Br2(aq),
giving a white precipitate. It does not, however, decolourise cold dilute acidified KMnO4.
When compound E is treated with an excess of Br2(aq), compound G is produced.
(ii) If the test with cold dilute acidified KMnO4 had been positive, which functional group
would this have shown to be present in F?
....................................................................................................................................
(iii) Name the functional groups in compound F that would react with the following.
Na2CO3(aq) ................................................. Br2(aq) .................................................
(iv) Suggest structures for compounds F and G and draw them in the relevant boxes
above.
Page 86 of 231
(v) Compound E is one of a pair of stereoisomers.
What type of stereoisomerism is shown by compound E?
....................................................................................................................................
(vi) Draw the structure of the other stereoisomer in the box below.
[8]
(c) Calculate the volume of 0.1 mol dm–3 NaOH that is needed to react completely with 0.1 g
of compound E.
volume = ....................... cm3

[3]
[Total: 17]
June 2013/42
70. Super-absorbent polymers have the ability to absorb 200-300 times their own mass of water.
They are classified as hydrogels and they are widely used in personal disposable hygiene
products such as babies’ nappies (diapers).
These polymers are commonly made by the polymerisation of compound K mixed with
sodium hydroxide in the presence of an initiator.
(a) (i) Explain what is meant by the term polymerisation.
....................................................................................................................................
....................................................................................................................................
(ii) What type of polymerisation is involved in the formation of hydrogels?
....................................................................................................................................
Page 87 of 231
(iii) Describe the changes in chemical bonding that occur during the polymerisation of K.
....................................................................................................................................
.................................................................................................................................... [3]
(b) Acrylic acid is the common name for compound K.

Suggest the systematic (chemical) name of K.
........................................................................................................................................... [1]
(c) (i) Draw the structure of at least two repeat units of the polymer formed by the above
method from acrylic acid, K, when mixed with NaOH.
(ii) The C–C–C bond angle in compound K changes when the polymer is formed.
State and explain how the C–C–C bond angle differs between a molecule of K and
the polymer.
angle changes from ............................................ to .................................................
explanation ................................................................................................................
.................................................................................................................................... [4]
(d) (i) Draw a detailed diagram of a portion of the polymer you have drawn in (c)(i) to
explain how it can absorb a large volume of water.
(ii) A student added 0.10 g of the polymer to 10 cm3 of aqueous copper(II) sulfate
solution.
Predict, with a reason, what you expect to observe.
....................................................................................................................................
.................................................................................................................................... [4]
(e) Compound L, CH2=CHCONH2, can also be polymerised to form a super-absorbent

polymer.
(i) Name the two functional groups in compound L.
....................................................................................................................................
....................................................................................................................................
Page 88 of 231
Compound K can be converted into compound L by the following two-step route.
(ii) Suggest a reagent for step 1.
....................................................................................................................................
(iii) What other product is formed in step 2?
....................................................................................................................................
(iv) State the reagents and conditions necessary to re-form K from L.
.................................................................................................................................... [5]
[Total: 17]
Nov 2013/41
71. (a) Bromine reacts with a variety of organic compounds.

For each of the following reactions,
● complete and balance the equation, including the structural formula of the organic
product,
● state the specific conditions (if any) under which the reaction takes place and the
type of reaction that occurs.
reaction conditions .....................................................................................................
type of reaction ..........................................................................................................
type of reaction ..........................................................................................................

Page 89 of 231
type of reaction .......................................................................................................... [10]
(b) When hydrocarbon B is heated with concentrated manganate(VII) ions, three organic
compounds, C, D and E, are formed.
(i) Suggest the identities of compounds C, D and E, drawing their structures in the
boxes above.
(ii) Use the relevant letter, C, D or E, to identify which of your compounds will react with
each of the following reagents.
Each reagent may react with more than one of C, D and E, in which case state all
the compounds that may react with each reagent.
● 2,4-dinitrophenylhydrazine ..............................
● alkaline aqueous iodine ...................................
● aqueous sodium hydroxide .............................. [6]

[Total: 16]
Page 90 of 231
72. Naturally-occurring α-amino acids, RCH(NH2)CO2H, can be classified as amphiprotic

substances. An amphiprotic substance is one which can act as both a Brønsted-Lowry acid
and base.
(a) What is the Brønsted-Lowry definition of an acid?
...........................................................................................................................................
........................................................................................................................................... [1]
(b) (i) All α-amino acids are soluble in water since they can form hydrogen bonds with
water molecules and can also exist as zwitterions.
Draw diagrams to show how the carboxylic acid and amino groups of alanine can
form hydrogen bonds with water molecules.
(ii) Draw the structure of the zwitterionic form of glycine.
[5]
Page 91 of 231
(c) The amino acid alanine can be formed by the reaction of CH3CHClCO2H with an excess
of ammonia.
Outline a mechanism for this reaction using curly arrows.
[3]
(d) Amino acids can form different ions at different pH values.

Suggest the structures of the ions formed from the α-amino acids below at the respective
pH value.
[2]
(e) (i) How many different dipeptides is it possible to synthesise, each containing two of
the three amino acids alanine, serine and lysine?
......................................
(ii) Write the structural formula of one of these dipeptides incorporating serine and
alanine.
[3]
(f) Most naturally-occurring amino acids have a chiral centre and exhibit stereoisomerism.
(i) Define the term stereoisomerism.
....................................................................................................................................
....................................................................................................................................
Page 92 of 231
There are four optical isomers of threonine.
Some of these optical isomers are drawn below.
When answering this question, remember that completely free rotation about a C–C
single bond occurs in these compounds.
(ii) Which of the structures G, H or J is identical to structure F? ....................................
(iii) The other two of the structures G, H or J represent two of the three other possible
optical isomers of threonine.
Complete the following partial structure of the fourth optical isomer.
[3]
[Total: 17]
Nov 2013/43
73. Noradrenaline is a hormone and neurotransmitter, which is released during stress to stimulate the
heart and increase blood pressure.
(a) State the names of three functional groups in the noradrenaline molecule.
....................................................................................................................................................
.................................................................................................................................................... [3]
Page 93 of 231
(b) (i) Consider the following two-stage synthesis of noradrenaline from dihydroxybenzaldehyde.
● Draw the structure of the intermediate Z in the box.
● Suggest reagents for steps 1 and 2.
step 1 ..................................................................................................................................
step 2 ..................................................................................................................................
(ii) Dihydroxybenzaldehyde reacts with Br2(aq).
● Describe what you would see during this reaction.
......................................................................................................................................
● Draw the structure of the product.
[5]
(c) Draw the structures of the products when noradrenaline is reacted with
(i) dilute NaOH(aq),
(ii) dilute HCl (aq),
(iii) an excess of ethanoyl chloride, CH3COCl.
[4]
(d) Name the new functional groups formed in the reaction in (c)(iii).
....................................................................................................................................................
.............................................................................................................................................. [2]
[Total: 14]
Page 94 of 231
74. The two compounds V and W are isomers with the molecular formula C4H8O, and show the
following properties and reactions.
● Both compounds react with sodium metal, and both decolourise bromine water.
● Compound V forms a yellow precipitate with alkaline aqueous iodine, whereas compound
W does not.
● When reacted with cold KMnO4(aq), both V and W produce the same neutral compound
X, C4H10O3.
● Both V and W exist as pairs of stereoisomers.
(a) Suggest which functional groups are responsible for the reactions with
(i) sodium,
.............................................................................................................................................
(ii) bromine water,
.............................................................................................................................................
(iii) alkaline aqueous iodine.
............................................................................................................................................. [3]
(b) Suggest structures for V and W.
[2]
(c) State the type of stereoisomerism shown by compound V and draw the structures of the
stereoisomers.
type of stereoisomerism .............................................................................................................
structures of stereoisomers
[2]
Page 95 of 231
(d) Suggest the structure of the neutral compound X.
[1]
[Total: 8]
June 2014/41
75. Both ethene and benzene react with bromine.
(a) What type of reaction is the reaction of bromine with
(i) ethene,
.............................................................................................................................................
(ii) benzene?
............................................................................................................................................. [1]
(b) Write an equation to show the formation of the electrophile during the reaction between bromine
and benzene.
.............................................................................................................................................. [1]
(c) Each of these reactions involves an intermediate.
(i) Draw the structure of the intermediate in each reaction.

Page 96 of 231
(ii) Suggest why the product of the reaction between bromine and benzene, bromobenzene,
is still unsaturated.
............................................................................................................................................. [3]
(d) When methylbenzene is nitrated, 4-nitromethylbenzene is formed, but when benzoic acid is
nitrated, 3-nitrobenzoic acid is produced.
Consider the following synthesis of 3-chlorobenzoic acid, F, from methylbenzene.

Use the information given above to suggest
● the structure of the intermediate E,

● the reagents and conditions needed for reactions 1 and 2.
reagents and conditions for reaction 1
....................................................................................................................................................
reagents and conditions for reaction 2
....................................................................................................................................................[3]
(e) Consider the following synthesis of 3-chlorophenylmethylamine, H, from F.

Suggest
● the structure of the intermediate G,

● the reagents for reactions 3 and 4.
reagents for reaction 3
....................................................................................................................................................
reagents for reaction 4
....................................................................................................................................................[3]
[Total: 11]
Page 97 of 231
76. Although now remembered for his music, the Russian composer Alexander Borodin was a
chemist. He is credited with the discovery of the aldol reaction, a product of which is compound
J.
J shows the following properties:
● its molecular formula is C4H8O2,

● it is neutral,
● it reacts with sodium metal,
● it reacts with Fehling's solution,
● it does not react with aqueous bromine.
(a) Suggest which functional groups are responsible for the reactions with
(i) sodium,
.............................................................................................................................................
(ii) Fehling's solution.
............................................................................................................................................. [2]
(b) The result of the bromine test shows a functional group is absent from compound J.
Suggest the identity of this functional group.
.............................................................................................................................................. [1]
(c) In the boxes below, draw three possible straight-chain structures for J that fit the above
results, and that are structural isomers of each other.
[3]
(d) Compound J reacts with alkaline aqueous iodine to give a pale yellow precipitate.
(i) Which functional group does this reaction show that J contains?
.............................................................................................................................................
(ii) Which of your three structures K, L or M contains this group and is therefore J?
............................................................................................................................................. [2]
Page 98 of 231
(e) Compound J exists as stereoisomers.
(i) Name the type of stereoisomerism shown by J.
.............................................................................................................................................
(ii) Draw two structures of J to illustrate this stereoisomerism.
[2]
[Total: 10]
June 2014/42
77. (a) Methylbenzene undergoes electrophilic substitution with nitronium ions, NO2+.
Nitronium ions are generated by the reaction between concentrated sulfuric acid and
concentrated nitric acid.
(i) Construct an equation for the formation of nitronium ions, NO2+, by this method.
.............................................................................................................................................
(ii) Complete the scheme to show the mechanism for this reaction. Use curly arrows to show
the movement of electron pairs.
(b) (i) Describe and explain the relative acidities of chloroethanoic acid and ethanoic acid.
.............................................................................................................................................
.............................................................................................................................................
.............................................................................................................................................
(ii) Describe and explain the relative acidities of phenol and ethanol.
.............................................................................................................................................
.............................................................................................................................................
............................................................................................................................................. [3]
Page 99 of 231
(c) Phenyl 2-hydroxybenzoate is an antiseptic.
Complete the following table about the reactions of phenyl 2-hydroxybenzoate with the three
reagents.
[6]
[Total: 13]
78. (a) Organohalogen compounds can undergo hydrolysis.
State the relative rates of hydrolysis of the following compounds.
Explain your answer.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
.............................................................................................................................................. [3]
Page 100 of 231
(b) Aminolaevulinic acid is involved in the synthesis of haemoglobin and chlorophyll.
Name the three functional groups in aminolaevulinic acid.
............................................................................................................................................. [2]
(c) Aminolaevulinic acid reacts readily with bromoethane.
(i) Show the mechanism of the first step of this reaction on the diagram. Include all necessary
curly arrows, lone pairs and relevant dipoles.
(ii) Name the mechanism in (c)(i).
.............................................................................................................................................
(iii) Identify the non-organic product formed in this reaction.
............................................................................................................................................. [5]
Page 101 of 231
(d) Three reactions of aminolaevulinic acid are shown. Draw the structures of the products W, X
and Y in the boxes below.
[3]
(e) Aminolaevulinic acid can undergo polymerisation.
Draw the structure of the polymer showing two repeat units. The linkages between the
monomer units should be shown fully displayed.
[2]
[Total: 15]
Nov 2014/41
Page 102 of 231
79. L-DOPA is used in the treatment of Parkinson's disease. It can be prepared from vanillin.
(a) L-DOPA and vanillin each contain an aromatic benzene ring.
Describe, with the aid of a diagram, the bonding and shape of a molecule of benzene, C6H6.
....................................................................................................................................................
....................................................................................................................................................
....................................................................................................................................................
........................................................................................................................................... [5]
(b) A student carried out some reactions with samples of L-DOPA and vanillin using reagents X, Y
and Z.
● Reagent X reacted with L-DOPA and with vanillin.

● Reagent Y reacted with L-DOPA but not with vanillin.
● Reagent Z reacted with vanillin but not with L-DOPA.
Assume that the CH3O– group in vanillin does not react.

Suggest possible identities of reagents X, Y and Z and give the structures of the organic
products that were formed.
Reagent X ..................................................................................................................................
Reagent Y ..................................................................................................................................
Page 103 of 231
Reagent Z ..................................................................................................................................
[7]
[Total: 12]
80. Methoxetamine is a derivative of the pharmaceutical drug, ketamine.
(a) (i) What is the molecular formula of methoxetamine?
.............................................................................................................................................
(ii) On the diagram above, circle any chiral centres that are present in methoxetamine.
(iii) Name two functional groups in methoxetamine, in addition to the aryl group.
........................................................................................................................................ [4]
Page 104 of 231
(b) In the table, complete the structure of each of the compounds formed when methoxetamine is
reacted with the following reagents.
State the type of reaction in each case.
[6]
[Total: 10]
Nov 2014/43
81. (a) Both chloroalkanes and acyl chlorides react with water, but only acyl chlorides fume in moist
air.
(i) State which product causes the fumes in this reaction.
....................................................................................................................................... [1]
(ii) Explain why the reactivities of chloroalkanes and acyl chlorides differ.
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [1]
Page 105 of 231
(b) Compound R is a useful intermediate in the synthesis of pharmaceutical compounds. It can be

made from compound P by the following route.
(i) Suggest structures for the starting material P and the intermediate Q. [2]
(ii) Suggest reagents and conditions for the following steps in the above scheme.
step 1 ..................................................................................................................................
step 2 ..................................................................................................................................
step 4 .................................................................................................................................. [3]

[Total: 7]
82. 1,3-dimethylbenzene is a useful starting material for several commercially important compounds.
(a) The artificial ‘musk ketone’, A, is a perfume agent added to many cosmetics and detergents. It
is made from 1,3-dimethylbenzene by the following route.
(i) The only by-product of step 2 is HCl.
Suggest the reagent that was used in this step.
....................................................................................................................................... [1]
(ii) Suggest the type of reaction that is occurring during both step 2 and step 3.
....................................................................................................................................... [1]
(iii) State the reagents and conditions needed for step 3.
....................................................................................................................................... [1]
Page 106 of 231
(iv) Suggest the structures of the two products formed when A is reacted with alkaline aqueous
iodine.
[2]
(b) 1,3-dimethylbenzene is also a starting material for the synthesis of the polymer Nomex, used
in fireproof protective clothing worn by firefighters, military pilots and racing car drivers. The
polymer is made from 1,3-dimethylbenzene and 1,3-dinitrobenzene by the following route.
(i) Draw the structure of one repeat unit of Nomex in the box above. [1]
(ii) What type of polymer is Nomex?
....................................................................................................................................... [1]
(iii) Suggest the by-product formed during step 3.
....................................................................................................................................... [1]
(iv) Suggest reagents and conditions for step 2.
....................................................................................................................................... [1]
Page 107 of 231
(v) Suggest how and why the properties of the polymer might change if some of the diamine
monomer were replaced with 1,3,5-triaminobenzene.
.............................................................................................................................................
....................................................................................................................................... [1]
[Total: 10]
83. (a) Long chain alkanes such as 4-methylheptane can be ‘cracked’ to produce shorter chain
hydrocarbons.
(i) State the conditions necessary for this reaction to take place.
....................................................................................................................................... [1]
(ii) Suggest the structure of B.
[1]
(iii) Compounds C, D and E are isomers with the molecular formula C5H10.
On heating with concentrated acidified KMnO4,
● compound C gives CO2 and compound F (C4H8O2),

● D and E each give a 1 : 1 mixture of compounds G (C2H4O2) and H (C3H6O2).
Suggest structures for compounds C - H.
[3]
Page 108 of 231
(iv) Name the type of isomerism shown between D and E.
....................................................................................................................................... [1]
(b) Propene, CH3CH=CH2, reacts with bromine to give 1,2-dibromopropane.
(i) How is this reaction usually carried out?
....................................................................................................................................... [1]
(ii) State the type of reaction that is occurring here.
....................................................................................................................................... [1]
(iii) Draw the mechanism of this reaction, including the structures of any intermediates, and
any dipoles, lone pairs and curly arrows to show the movements of electrons.
[2]
[Total: 10]
84. (a) Compound B is a component of several perfumes and flavourings. It can be obtained by the
hydrogenation of compound A.
During the reaction, the hydrogen atoms all add onto the same side of the benzene ring.
(i) Suggest reagents and conditions for this reaction.
....................................................................................................................................... [1]
(ii) Circle all the chiral atoms on the structure of B above. [1]
(iii) How many possible optical isomers are there with the same structural formula as B?
....................................................................................................................................... [1]
(iv) Complete the following part-structure to show the structure of one of the isomers of B that
would be formed during the above reaction.
[1]
Page 109 of 231
(b) Compound A can be obtained from propan-2-ylbenzene by the following route.
(i) Suggest the structure of the intermediate cation C and draw it in the box above. [1]
(ii) Suggest reagents and conditions for the following steps.
step 1 ..................................................................................................................................
step 2 ..................................................................................................................................
step 3 .................................................................................................................................. [4]
(c) Suggest the structures of the organic products of the reactions between each of the compounds
A and B and the following reagents. If no reaction occurs write ‘no reaction’ in the relevant box.
[5]
[Total: 14]
Page 110 of 231
85. (a) Carboxylic acids can be converted into primary amines by the following sequence of reactions.
(i) Suggest the identity of intermediate D and write its structure in the box above. [1]
(ii) Suggest the reagents for
step 1 ..................................................................................................................................
step 2 ..................................................................................................................................
step 3 .................................................................................................................................. [2]
(b) Four compounds, E, F, G and H, are isomers of each other.

Each compound contains an aromatic ring and two functional groups from the following list.
• alcohol
• amide
• amine
• carboxylic acid
• ester
• phenol
(i) Which of these functional groups react readily with cold HCl (aq)?
....................................................................................................................................... [1]
(ii) Which of these functional groups react readily with cold NaOH(aq)?
....................................................................................................................................... [1]
The molecular formula of the four isomers, E, F, G and H, is C8H9NO2. All four compounds
are insoluble in water. Table 1 shows their solubilities in acid or alkali.
Page 111 of 231
(iii) Use this information to suggest the two functional groups, taken from the list on page,
that each compound contains.
[4]
(iv) Suggest a structure for each compound.
[4]
[Total: 13]
June 2015/41/42
86. Boron forms many useful compounds.
(a) The compound diborane, B2H6, can be used as a rocket fuel.

It can be prepared by the reaction of boron trifluoride, BF3, with sodium borohydride, NaBH4.
Balance this equation.

Page 112 of 231
(b) Primary and secondary alcohols can be formed by the reaction of carbonyl compounds with
NaBH4, which is a source of hydride ions, H–.
Complete the mechanism for the reaction of butanone with hydride ions, H–, and draw the
intermediate in the box. Include all necessary curly arrows and relevant dipoles.
[3]
(c) Borane, BH3, is used to synthesise alcohols from alkenes.
The reaction occurs in two steps.

The BH2 group from BH3 bonds to the least substituted carbon atom of the double bond, and
the remaining H from BH3 bonds to the other carbon.
(i) Suggest the type of reaction in step 1.
........................................................................................................................................ [1]
(ii) The diol Y can be prepared by the same method.
Draw the structure of the diene which could be used to prepare diol Y.
[1]
Page 113 of 231
(d) Benzene, C6H6, and borazine, B3N3H6, have planar, cyclic structures.
(i) Describe the structure of and bonding in benzene, C6H6.
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
..............................................................................................................................................
........................................................................................................................................ [3]
(ii) In borazine, B3N3H6, the boron and nitrogen atoms alternate around the ring. Each ring
atom has a single hydrogen atom bonded to it.
All boron-nitrogen bonds in borazine are 0.144 nm in length, whereas in simple compounds
B–N and B=N bond lengths are 0.154 nm and 0.136 nm respectively.
Suggest and draw the structure of borazine.
[1]
[Total: 10]
Page 114 of 231
87. Sunset Yellow is a yellow colouring agent used in food and drinks, which can be made by the
following route.
In step 3 of this synthesis, a phenol-like compound, S, reacts with intermediate T made from
amine R.
Assume that the –SO3– Na+ group does not react.
(i) Suggest structures for compounds R, S and T and draw them in the boxes above. [3]
step 1, ..................................................................................................................................
step 2. .................................................................................................................................. [3]
(iii) What type of organic salt is formed in step 2?
........................................................................................................................................ [1]
Page 115 of 231
(b) Compound W has the following structure.
(i) How many σ and π bonds are present in a molecule of W?
σ bonds ....................... π bonds ....................... [2]
(ii) The products of the reactions of W with cold HCl and with CH3CH2Br are soluble in water
but not in organic solvents.
Complete the table for these reactions of W.
[3]
[Total: 12]
88. (a) A student carries out some reactions with separate samples of butanal and butanone.
The following results are obtained with reagents L, M and N.
(i) Suggest a possible identity for each reagent L, M and N.
L ..........................................................................................................................................
M ..........................................................................................................................................
N ..................................................................................................................................... [3]
Page 116 of 231
(ii) Give the structure of the organic product formed when M reacts with butanal.
[1]
(iii) What is observed when N reacts with butanone?
........................................................................................................................................ [1]
(iv) What type of reaction is occurring when N reacts with butanone?
........................................................................................................................................ [1]
(b) The organolithium compound methyl lithium, CH3Li, can act as a source of CH3– ions.
The CH3– ion can act as a nucleophile.

The reaction between methyl lithium and carbonyl compounds can be used to make alcohols.
(i) Suggest a mechanism for the reaction of butanal with CH3– ions. Include all necessary
curly arrows, lone pairs and relevant dipoles.
(ii) A chemist decides to prepare the following organic compound G from butanal.
Draw the structure of the organolithium reagent which could be used to prepare G from
butanal.
[1]
[Total: 10]
Page 117 of 231
89. 4-nitrophenol can be converted into a range of useful organic products.
(a) 4-nitrophenol can react with three different reagents.

Complete the table by:
• drawing the structures of the organic products formed,

• identifying the non-organic products formed.
[4]
Page 118 of 231
(b) 4-nitrophenol can also be used in the synthesis of the dye Mordant Brown by the following
route.
In step 2 of this synthesis, 4-nitrophenol reacts with intermediate F made from amine E.
Assume that the –SO3– Na+ group does not react.
(i) Suggest structures for compounds E and F and draw them in the boxes above. [2]
step 1, ..................................................................................................................................
step 2. .................................................................................................................................. [3]

[Total: 9]
Nov 2015/42/43
Page 119 of 231
90 The anti-inflammatory drug ketoprofen can be synthesised from benzene via the following five
steps.
step 1 step 2
T, (C15H14O)
O step 3
Br
step 4
step 5 CO2H
U ketoprofen
(a) Suggest the structures of compounds T and U and draw them in the boxes above.

[2]
(b) Suggest reagents and conditions for steps 1-5.

step 1 .........................................................................................................................................
.
step 2 .........................................................................................................................................
.
step 3 .........................................................................................................................................
.
step 4 .........................................................................................................................................
.
step 5 .........................................................................................................................................
.
[5]
(c) What types of reaction are steps 1 and 5?

step 1 .........................................................................................................................................
.
step 5 .........................................................................................................................................
.
[2]
[Total: 9]
Page 120 of 231
91 (a) 2-bromopropane can be used to synthesise methylethylamine and 2-methylpropylamine.
NH2
reaction 1 methylethylamine
Br
2-bromopropane
reaction 2 reaction 3
NH2
X 2-methylpropylamine
(i) Draw the structure of the intermediate X in the box above. [1]


• reaction 1, ....................................................................................................................
.
• reaction 2, ....................................................................................................................
.
• reaction 3. ....................................................................................................................
.
[3]
(b) (i) Write an equation showing why aqueous solutions of ethylamine are alkaline.

....................................................................................................................................... [1]
.
(ii) Compare the basicities of ethylamine and ammonia. Explain your answer.

.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
....................................................................................................................................... [2]
.
Page 121 of 231
(c) Solutions containing mixtures of amines and their salts are buffer solutions.

(i) Explain what is meant by the term buffer solution.

.............................................................................................................................................
.
....................................................................................................................................... [1]
.
(ii) Write two equations to show how a solution containing a mixture of CH3NH2 and CH3NH3Cl

acts as a buffer.
.............................................................................................................................................
.
....................................................................................................................................... [2]
.
[Total: 10]
Page 122 of 231
92 The anti-inflammatory drug ibuprofen can be synthesised from benzene via the following six steps.
step 1 step 2
OH step 3
CN
step 4
CO2H CO2H
step 5 step 6
J
ibuprofen
(a) Draw circles around any chiral carbon atoms in the above five formulae. [1]

(b) Suggest the structures of compounds H and J and draw them in the boxes above. [2]

(c) Suggest reagents and conditions for steps 1-6.

step 1 .........................................................................................................................................
.
step 2 .........................................................................................................................................
.
step 3 .........................................................................................................................................
.
step 4 .........................................................................................................................................
.
step 5 .........................................................................................................................................
.
step 6 .........................................................................................................................................
.
[6]
(d) Name the mechanism of step 1 and state the type of reaction for step 6.

step 1 .........................................................................................................................................
.
step 6 .........................................................................................................................................
.
[2]
[Total: 11]
Page 123 of 231
93 Oleocanthal, Q, is a natural compound found in olive oil. It has antioxidant and anti-in
flammatory
properties and is thought to have a protective effect against Alzheimer’s disease.
O
HO
O
Q
(a) Q shows optical and cis-trans isomerism.
On the structure of Q above, circle the functional group that shows cis-trans isomerism and
indicate with an asterisk (*) the chiral carbon atom. [1]
(b) Q can be isolated from olive oil by partitioning between two solvents.
(i) Explain what is meant by the term partition coefficient.
.............................................................................................................................................
.............................................................................................................................................
....................................................................................................................................... [2]
(ii) When 40.0 cm3 of hexane was shaken with 10.0 cm3 of a solution containing 0.25 g of Q in
10.0 cm3 of methanol, it was found that 0.060 g of Q was extracted into the hexane.
Calculate the partition coefficient, Kpartition, of Q between hexane and methanol.
Kpartition = ............................. [2]

Page 124 of 231
(c) Complete the following table to show the structures of the products formed when Q reacts with
the three reagents.
reagent structure of product(s) type of reaction
excess
Br2(aq)
NaBH4
excess hot
NaOH(aq)
[6]
(d) When a sample of Q synthesised in a laboratory was compared to a natural sample from olive
oil, it was found that the therapeutic activity of the synthetic sample was lower.
Suggest a reason for this.
....................................................................................................................................................
.............................................................................................................................................. [1]
[Total: 12]
Page 125 of 231
94 (a) Bromobenzene can be prepared from benzene as shown.
Br2
Br
Al Br3
(i) Name the mechanism of this reaction.
....................................................................................................................................... [1]
(ii) Draw the mechanism of this reaction. Include all relevant curly arrows, any dipoles and
charges.
[4]
(b) Two isomeric aromatic compounds, V and W, each contain three functional groups, two of
which are shown in the table.
O
Br Br NH
O
NH
CH3
CH3
V W
Complete the table with the other functional groups present in V and W.
substance functional groups present
V bromo group aryl (benzene) group ............................
W bromo group aryl (benzene) group ............................

[1]
Page 126 of 231
(c) Compounds V and W can be synthesised from bromobenzene by the following routes.
step 2 PCl 5
Br CH3
R S
step 1 CH3NH2
O
Br Br
NH
CH3
step 3 V
step 4 CH3COCl
Br NO2 Br NH
O
T CH3
W
(i) Suggest reagents for each of the steps 1– 4.
step 1 ..................................................................................................................................
step 2 ..................................................................................................................................
step 3 ..................................................................................................................................
step 4 ..................................................................................................................................
[4]
(ii) Deduce structures for R, S and T and draw their structural formulae in the boxes. [3]
(d) (i) Draw the structures of the two organic products from the reaction of V and W with LiAl H4.
product from V product from W

[2]
Page 127 of 231
(ii) Name the type of reaction occurring between LiAl H4 and V or W.
....................................................................................................................................... [1]
(e) V and W can be hydrolysed using hot HCl (aq).
(i) Draw the structures of the two organic products of the hydrolysis of W.
Br NH
O HCl (aq)
+
heat
CH3
W
[2]
(ii) The products formed from the hydrolysis of W are soluble in aqueous acid, whereas a
precipitate, X, is formed on hydrolysing V.
Draw the structure of compound X.
X
[1]
(iii) Suggest why X is insoluble in water.
.............................................................................................................................................
....................................................................................................................................... [1]
[Total: 20]
Page 128 of 231
95 Ibuprofen and paracetamol are pain-relief drugs.
O O
OH
N OH
H
ibuprofen paracetamol
(a) Ibuprofen and paracetamol both contain the aryl (benzene) functional group.

Name the other functional groups present in each molecule.

ibuprofen ....................................................................................................................................

.
paracetamol ...............................................................................................................................

.
[2]
(b) Ibuprofen contains a chiral centre and shows stereoisomerism.

(i) State what is meant by the term chiral centre.

.............................................................................................................................................
.
....................................................................................................................................... [1]
.
(ii) Draw the two stereoisomers of ibuprofen.

C C
[2]
Page 129 of 231
(c) Draw the structures of the organic products when ibuprofen and paracetamol react separately

with LiAl H4.
product with ibuprofen product with paracetamol

[2]
(d) A student carried out some reactions with solutions of ibuprofen and paracetamol using

reagents D and E and the following results were obtained.
( means a reaction took place.)
reagent ibuprofen paracetamol

D  
E  
(i) Suggest a possible identity for each reagent D and E.

D .............................................
E .............................................
[2]
(ii) Give the structure of the organic product formed when reagent D reacted with ibuprofen.

product with ibuprofen
[1]
(iii) Give the structure of the organic product formed when reagent E reacted with paracetamol.

product with paracetamol
[1]
Page 130 of 231
(e) One of the steps in the manufacture of ibuprofen is shown.

CH3COCl
Al Cl 3
O
X Y
(i) Write an equation for the reaction between CH3COCl and Al Cl 3.

....................................................................................................................................... [1]
.
(ii) Complete the mechanism for the conversion of X into Y. Include all necessary curly arrows,

any relevant dipoles and charges.
[3]
(iii) Name the mechanism in (ii).

....................................................................................................................................... [1]
.
[Total: 16]
Page 131 of 231
96 Compounds J, K, L and M are isomers of each other with the molecular formula C9H11NO.
All four isomers contain a benzene ring.

Two of the isomers contain a chiral centre.

The results of six tests carried out on J, K, L and M are shown in the table.

observations with each isomer

test
J K L M
1 add cold HCl (aq) soluble soluble soluble insoluble
2 add 2,4-DNPH reagent orange ppt. orange ppt. orange ppt. no reaction
3 add NaOH(aq) + I2(aq) pale yellow ppt. no reaction pale yellow ppt. no reaction
4 warm with Fehling’s no reaction red ppt. no reaction no reaction
solution
5 heat with NaOH(aq) no reaction no reaction no reaction P(C6H7N) and
Q(C3H5O2Na)
produced
6 diazotization and no dye orange dye no dye no dye
addition of alkaline produced produced produced produced
phenol
(a) Use the experimental results in the table above to determine the group(s), in addition to the

benzene ring, present in each of the four isomers J, K, L and M.
Complete the table below, identifying the group(s) present in each isomer.

group(s) in compound
J K L M
...................................... ...................................... ...................................... ......................................
...................................... ...................................... ...................................... ......................................
...................................... ..................................... ..................................... .....................................
[5]
Page 132 of 231
(b) (i) Name the type of reaction occurring in test 5 that converts M into P + Q.

....................................................................................................................................... [1]
.
(ii) Suggest structures for compounds P and Q.

P (C6H7N) Q (C3H5O2Na)
[2]
(c) Isomers J, K, L and M all have the molecular formula C9H11NO.

Use the information in (a) to suggest a structure for each of these isomers and draw these in

the boxes. Draw circles around all chiral centres in K and L.
J K
L M
[5]
(d) Compound N is another isomer which has the same molecular formula C9H11NO and also

contains a benzene ring.

N contains the same functional group as M.

When heated with NaOH(aq), N produces ethylamine and a sodium salt W.

Suggest the structure of W.

W
[1]
[Total: 14]
Page 133 of 231
97 Carvone occurs in spearmint and a stereoisomer of carvone occurs in caraway seeds. Treating
either isomer with hydrogen over a nickel catalyst produces a mixture of isomers with the structural
formula X.
O OH
H2 + Ni
carvone X
(a) (i) State the type of stereoisomerism carvone can show. Explain your answer.

.............................................................................................................................................
.
....................................................................................................................................... [1]
.
(ii) Write an equation, using molecular formulae, for this conversion of carvone to X.

....................................................................................................................................... [2]
.
X can be synthesised from methylbenzene by the following route.
NO2 NH2
step 1 step 2 step 3
methylbenzene
step 4
OH OH N2+Cl –
step 6 step 5
X
Page 134 of 231
(b) (i) Name the mechanism in step 1.

. ....................................................................................................................................... [1]
(ii) What type of reaction is occuring in the following steps?

step 3 ..................................................................................................................................
.
step 5 ..................................................................................................................................
.
[2]
(iii) Suggest reagents and conditions for each of the following steps.

step 1 ..................................................................................................................................
.
step 2 ..................................................................................................................................
.
step 3 ..................................................................................................................................
.
step 4 ..................................................................................................................................
.
[6]
(c) During step 6, hydrogen is added to the benzene ring to produce the cyclohexane ring in X.

The six hydrogen atoms are all added to the same side of the benzene ring.
(i) State the reagents and conditions needed for this reaction.

....................................................................................................................................... [1]
.
(ii) Complete the part structure to show the structure of the isomer of X that would most likely

be obtained during this reaction.
[2]
[Total: 15]
Page 135 of 231
98 Compounds W, X, Y and Z are isomers of each other with the molecular formula C8H7Cl O.
All four isomers contain a benzene ring.

Only one of the isomers contains a chiral centre.

The results of six tests carried out on W, X, Y and Z are shown in the table.

observations with each isomer

test
W X Y Z
1 add cold AgNO3(aq) white ppt. forms none white ppt. forms none
immediately very slowly
2 heat with NaOH(aq),
then add dilute white ppt. none white ppt. none
HNO3 + AgNO3(aq)
3 add NaOH(aq) + I2(aq) none pale yellow ppt. none none
4 warm with Fehling’s
none none red ppt. none
solution
5 add cold, dilute, no change no change no change decolourises
acidified KMnO4(aq)
6 add Br2(aq) no change no change no change decolourises
and forms white
ppt.
(a) Use the experimental results in the table above to determine the group(s), in addition to the

benzene ring, present in the four isomers W, X, Y and Z.
Complete the table below, identifying the group(s) present in each isomer.

group(s) in compound
W X Y Z
...................................... ...................................... ...................................... ......................................
...................................... ...................................... ...................................... ......................................
...................................... ...................................... ...................................... ......................................
[5]
Page 136 of 231
(b) Isomers W, X, Y and Z all have the molecular formula C8H7Cl O.

(i) Use the information in (a) to suggest a structure for each of these isomers and draw these

in the boxes.
W X
Y Z
[4]
(ii) Draw a circle around the chiral centre in one of the above structures.
[1]
[Total: 10]
Page 137 of 231
99 (a) The amino acid tyrosine can be synthesised from phenol by the route shown.
OH
step 1 CHO step 2
CN
HO HO HO
phenol
step 3
NH2 Cl OH
step 5 step 4
CO2H CO2H 1. PCl 5 CO2H

HO HO 2. H2O HO
tyrosine
(i) Name the mechanism occurring in the following steps.

step 1 ..................................................................................................................................
.
step 2 ..................................................................................................................................
.
[2]
(ii) What type of reaction is occurring in step 3?

. ....................................................................................................................................... [1]
(iii) Suggest reagents and conditions for each of the following steps.

step 1 ..................................................................................................................................
.
step 2 ..................................................................................................................................
.
step 3 ..................................................................................................................................
.
step 5 ..................................................................................................................................
.
[5]
Page 138 of 231
(iv) Draw the structures of the products of the reactions of tyrosine with an excess of each of

the following reagents.
with NaOH(aq)
with HCl (aq)
with Br2(aq)
[4]
Question continues on the next page.

Page 139 of 231
(b) The dipeptide phe-tyr has the following structure.

H
N CO2H
H2N
O
OH
A mixture of this dipeptide (phe-tyr) and its two constituent amino acids (phe and tyr) was

subjected to electrophoresis in a buffer at pH 12. At the end of the experiment the following
results were seen. Spots R and S remained very close together.
mixture applied here
+ –
P R S
The three spots are due to the three species phe, tyr and phe-tyr.

(i) Which species is responsible for spot P? Explain your answer.

.............................................................................................................................................
.
....................................................................................................................................... [2]
.
(ii) Suggest why the other two species give spots R and S that are so close together.

..............................................................................................................................................
........................................................................................................................................ [1]
[Total: 15]
Page 140 of 231
100 Compound P contains several functional groups.
Cl H CN
C C
CN
(a) Name the functional groups present in P.

. ....................................................................................................................................................
. .............................................................................................................................................. [2]
(b) Compound P can be polymerised.

Draw a section of the polymer of P showing two repeat units.

Name the type of polymerisation.

type of polymerisation ................................................................................................................

.
[2]
Page 141 of 231
(c) Complete the following table to show the structures of the products formed and the

type of organic reaction when P reacts with the four reagents.
type of
reagent structure(s) of product(s)
organic reaction
excess Br2(aq)
excess hot,
concentrated,
acidified MnO4–(aq)
excess hot HCl (aq)
excess H2 / Pt catalyst
[8]
[Total: 12]
Page 142 of 231
101 (a) Calcium carbide, CaC2, reacts readily with water, forming ethyne, C2H2, and a sparingly soluble
white ionic compound.
(i) Write an equation for the reaction of CaC2 with water.

....................................................................................................................................... [1]
.
(ii) Draw a ‘dot-and-cross’ diagram for the carbide ion, C22–. Show outer electrons only.

[1]
(b) Ethyne is the simplest member of the alkyne homologous series.

H C C H
ethyne
Propyne, C3H4, and butyne, C4H6, are the next two members of the series.

Deduce the general formula for the alkynes.

. .............................................................................................................................................. [1]
(c) Ethyne can be polymerised into poly(acetylene), which is a conducting polymer.

C C
H n
poly(acetylene)
(i) Suggest why this polymer conducts electricity.

. .............................................................................................................................................
. ....................................................................................................................................... [1]
(ii) State the empirical formula of poly(acetylene).

. ....................................................................................................................................... [1]
(iii) By reference to a physical or chemical property, suggest one advantage of a conducting

polymer when compared with metals.
. ....................................................................................................................................... [1]
Page 143 of 231
(d) Alkynes can react with carbonyl compounds under basic conditions as shown in reaction 1.

C R'
R' R''
R C C H R C C C R'' reaction 1
small amount
of base OH
(i) The first step of the mechanism of reaction 1 involves the alkyne anion reacting with the

carbonyl compound.
Complete the first step of the mechanism and draw the intermediate for this reaction.

Include all relevant dipoles, charges and curly arrows.
O R'
C R C C C R''
R' R''
OH
R C C–
intermediate
[3]
(ii) Suggest the name of the mechanism in reaction 1.

....................................................................................................................................... [1]
.
Page 144 of 231
(iii) An alkyne, Q, and a carbonyl compound, R, react together to form compound P as shown.

OH
CH3
C2H5C C C
2Q + R CH2
C2H5C C C
CH3
OH
P
Use reaction 1 to suggest the structures of Q and R.

Q R
[2]
(e) A series of twelve separate experiments is carried out as shown in the table.

Complete the table by writing in each box a tick () if a reaction occurs, or a cross () if no

reaction occurs.
CH3CHO HCO2H CH3COCH3 HO2CCO2H
hot, acidified MnO4–(aq)
alkaline I2(aq)
warm Tollens’ reagent

[4]
[Total: 16]
Page 145 of 231
102 (a) Benzene reacts with D in the presence of a suitable catalyst to give cumene and non-organic
product E. This is an electrophilic substitution reaction.
catalyst
+ D + E
cumene
(i) Name the reactant D and the non-organic product E.

D ....................................................
E ....................................................
[2]
(ii) Give the name of the type of aromatic electrophilic substitution reaction taking place.

....................................................................................................................................... [1]
.
(b) Cumene undergoes substitution reactions with chlorine to give several different isomeric

products with the formula C9H11Cl. The substitution can occur in the aromatic ring or in the
side chain of cumene.
‑
(i) Describe the conditions that are used to ensure substitution takes place only in the

aromatic ring.
....................................................................................................................................... [1]
.
(ii) Draw the structures of the two major isomeric products of the reaction, formula C9H11Cl,

when substitution takes place in the aromatic ring.
[1]
Page 146 of 231
(iii) Describe the conditions that are used to ensure substitution takes place only in the

side‑chain.
....................................................................................................................................... [1]
.
(iv) Draw the structures of two isomeric products of the reaction, formula C9H11Cl, when

substitution takes place in the side chain. ‑
[1]
(c) Complete the following table to show the structures of the organic products formed when

cumene reacts with each reagent.
reagent structure of organic product
hot KMnO4(aq)
H2 + Ni, high pressure
[2]
Page 147 of 231
(d) Cumene can be nitrated using a mixture of concentrated nitric and sulfuric acids. The

mechanism for this reaction is similar to the mechanism for the nitration of benzene.
Complete the mechanism for this reaction.

● Include all relevant charges and curly arrows showing the movement of electron pairs.

● Draw the structure of the intermediate.

● You do not need to draw the products.

products
cumene intermediate
[4]
[Total: 13]
Page 148 of 231
103 Abscisic acid, C15H20O4, is a plant hormone.
OH
O O OH
abscisic acid, C15H20O4
(a) On the diagram of abscisic acid, use an asterisk (*) to label each chiral carbon atom.
[1]
(b) Abscisic acid is reacted with an excess of NaBH4.

Give the molecular formula of the organic product formed.

............................................................................................................................................... [1]
(c) If abscisic acid is treated with an excess of hot, concentrated, acidified KMnO4, three different

carbon containing products are formed.

‑
(i) Draw the skeletal formula of the carbon-containing product with the largest molecular

mass.
[1]
(ii) Identify the carbon containing product with the smallest molecular mass. Explain how this
‑
product arises.
.............................................................................................................................................
.
.............................................................................................................................................
.
....................................................................................................................................... [2]
.
(iii) Identify the third carbon-containing product of this reaction by giving its displayed or

structural formula.
[1]
[Total: 6]
Page 149 of 231
104 Noradrenaline is a hormone found in humans.
OH
HO NH2
HO
noradrenaline
(a) Give the molecular formula of noradrenaline.

. .............................................................................................................................................. [1]
(b) State whether or not noradrenaline shows stereoisomerism. Explain your answer.

. ....................................................................................................................................................
. .............................................................................................................................................. [1]
(c) HNO2(aq) is reacted at 5 °C with separate samples of noradrenaline and phenylamine.

The reaction with phenylamine produces a stable diazonium ion.

The reaction with noradrenaline produces an unstable diazonium ion.

(i) Suggest why the diazonium ion produced with phenylamine is stable.

.............................................................................................................................................
.
....................................................................................................................................... [1]
.
(ii) When one noradrenaline molecule reacts with one HNO2 molecule, the products are

one water molecule, one molecule of an unreactive gas, and one molecule of an organic
compound made up of carbon, hydrogen and oxygen only.
Complete the chemical equation for this reaction.

OH
HO NH2
+ HNO2 + ............ + H2O
HO
[2]
[Total: 5]
Page 150 of 231
105 Phenol is an important industrial chemical used in the manufacture of dyestuff and other substances.
(a) Suggest two different substances that react with phenol to produce potassium phenoxide,

C6H5O– K+. Identify the second product formed in each case.
substance ................................................... second product ...................................................

.
substance ................................................... second product ...................................................

.
[3]
(b)
OH
2-naphthol
2 naphthol can show similar properties to phenol. It can be used to produce Sudan I, an
-
orange coloured dyestuff.
N
N
OH
Sudan I
(i) On the diagram of Sudan I above circle the bond or bonds that make this substance a

dyestuff. [1]
(ii) Describe how Sudan I can be made using phenylamine and 2 naphthol as the organic
-
starting materials.
.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
.............................................................................................................................................
.
....................................................................................................................................... [3]
.
Page 151 of 231
(c) Phenol can be used to make 2 nitrophenol.

-
OH
NO2
2-nitrophenol
The nitration reaction of phenol to form 2‑nitrophenol shows that phenol is more reactive than

benzene.
(i) Describe the conditions used for the nitration of phenol.

Explain how these conditions show phenol to be more reactive than benzene.

conditions ...........................................................................................................................
.
explanation .........................................................................................................................
.
. .............................................................................................................................................
. .............................................................................................................................................
[2]
(ii) Suggest why phenol is more reactive than benzene.

. .............................................................................................................................................
. .............................................................................................................................................
. ....................................................................................................................................... [1]
(iii) Complete the mechanism for the nitration of phenol to form 2 nitrophenol. You should
-
assume that the mechanism is the same as that for the nitration of benzene.
● Include all relevant charges and curly arrows to show the movement of electron pairs.

● Draw the structure of the intermediate.

● You do not need to draw the products.

OH
NO2
+
products
phenol intermediate
[3]
(iv) Name the isomer of 2‑nitrophenol which is also a major product of this reaction.

....................................................................................................................................... [1]
.
[Total: 14]
Page 152 of 231
106 Asparagine and valine are two naturally occurring amino acids.
O O
O
OH OH
NH2 NH2 NH2
asparagine valine
(a) Give the molecular formula of asparagine.

. .............................................................................................................................................. [1]
(b) Name all of the functional groups in an asparagine molecule.

. .............................................................................................................................................. [2]
(c) Draw the structure of the dipeptide formed by valine and asparagine.

The peptide bond should be shown displayed and should be clearly labelled.

[2]
(d) A solution of valine in water acts as a buffer solution.

(i) Explain what is meant by a buffer solution.

. .............................................................................................................................................
. .............................................................................................................................................
. ....................................................................................................................................... [2]
(ii) Write two equations to explain how valine can act as a buffer. Use the formula H2NCHRCO2H

for valine in your equations.
. .............................................................................................................................................
. .............................................................................................................................................
[2]
Page 153 of 231
(e) Each valine molecule has one chiral carbon atom.

Draw three dimensional diagrams to show the two optical isomers of valine.
-
The (CH3)2CH group can be represented as R.

[2]
(f) Asparagine is hydrolysed when heated with aqueous sulfuric acid.

Write an equation for this reaction.

. .............................................................................................................................................. [2]
[Total: 13]
Page 154 of 231
107 (a) Polyhydroxyamide is a fire-resistant polyamide which is formed from the two monomers, F and
G.
HO2C CO2H H2N NH2
OH
F G
(i) Predict the number of peaks that will be seen in the carbon-13 NMR spectra of F and G.

number of peaks
G
[2]
(ii) Draw the repeat unit of polyhydroxyamide. The amide bond should be shown displayed.

[2]
(b) When poly(ethene) is formed from ethene, many bonds are broken and formed.

Place one tick () in each row of the table to indicate the types of bonds broken and formed

in this process.
σ-bonds only π-bonds only both σ- and π-bonds
bonds broken
bonds formed
[2]
Page 155 of 231
(c) Addition polymers can be classified into two types.

● homopolymer - a polymer made up of the same monomer unit

● copolymer - a polymer made up of two or more different monomer units

The reaction of propene, CH3CH=CH2, with phenylethene, C6H5CH=CH2, gives a copolymer.

Draw a length of the chain of this copolymer that contains one molecule of each monomer.

[2]
(d) (i) Polyalkenes biodegrade very slowly.

Explain why by referring to the structures of the polymers.

. .............................................................................................................................................
. .............................................................................................................................................
. ....................................................................................................................................... [1]
(ii) Some polymers will degrade in the environment.

Describe two processes by which this occurs.

1 ..........................................................................................................................................
.
2 ..........................................................................................................................................
.
[2]
[Total: 11]
Page 156 of 231
108 (a) Chlorobenzene and phenol both show a lack of reactivity towards reactants that cause the
breaking of the C–X bond (X = Cl or OH).
Explain why.

. ....................................................................................................................................................
. ....................................................................................................................................................
. ....................................................................................................................................................
. ....................................................................................................................................................
. .............................................................................................................................................. [3]
(b) When phenol is reacted with bromine dissolved in an inert solvent, two isomeric bromophenols,

C6H4BrOH, are formed.
Suggest structures for these products. Name each compound.

name: ..................................................................
name: ..................................................................
[2]
Page 157 of 231
(c) A student suggested that phenol can be prepared from benzene by the method shown.

NO2 NH2
step 1 step 2
step 3
NaNO2(aq) / HCl (aq)
5 °C
OH
step 4
phenol
K
(i) Suggest reagents and conditions for each of the following steps.

step 1 ..................................................................................................................................
.
step 2 ..................................................................................................................................
.
step 4 ..................................................................................................................................
.
[3]
(ii) Deduce the structure for K and draw its structural formula in the box.
[1]
(iii) Name the mechanism for step 1.

....................................................................................................................................... [1]
.
(iv) Write an equation for step 2. Use [H] for the reducing agent in this equation.

[1]
[Total: 11]
Page 158 of 231
Marks scheme for Organic Chemistry A2
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Page 217 of 231
Organic Chemistry AS
1. Hydrocarbons
(a)Nomenclature (I.U.P.A.C)
(b)Functional Group: Alkane, Alkene, Alkyne, Alkyl, Alcohol, Alkyl Halides(Halageno Alkanes),
Aldehyde & Ketone(Carbonyl), Carboxylic Acid, Acyl, Ester, Ether, Amine and Amides.
(c) Representation of chain
(i) Structure:
(ii) Condensed:
OR CH3(CH2)2CH3
(iii) Molecular:
C5H10O3
(iv) Skeletal:
* Aliphatic Compounds = Organic compounds with open chains of carbon atoms which may be branched or
unbranched
*Alicyclic Compounds = Organic compounds with closed rings of carbon atoms
* Aromatic compounds (Arene) = Organic compounds that contain at least one Benzene ring (A2 Syllabus)
* = Bond in the plane of paper
* = Bond going back into paper away from you
* = Bond coming out of paper towards you
* Electrons sufficient species are called Nucleophile ( NU)
* Electrons deficient species are called Electrophile (E+)
* Atom or Group of atoms having an unpaired electron is called Free Radical
* A substance formed during a reaction and can be isolated from reaction mixture called Intermediate
* A substance formed during a reaction and cannot be isolated is called Transition State
* An organic molecule in which Carbon is positively charged is called Carbonium or Carbocation
* An organic molecule in which Carbon is negatively charged is called carbanion

Page 218 of 231
(d) Isomerism
Structure Chain C-C-C -C / C-C-C
Position C=C-C-C/C-C=C-C
Functional Group alcohol ether
Isomerism carboxylic Ester
aldehyde ketone
Ring - Chain C=C-C /
Stereo Geometrical (cis trans)
 2n Isomers
 Probability (Double bonds at same position at both side
of chain)
 2n Isomers
 Chiral centre / Chiral Carbon
Optical  Optical Activity
 Enantiomers
 Super and Non-super impossible
 Dextro and Levo rotatory
2. Alkane CnH2n+2
(a) Cracking: Source of Alkane, Alkene and Hydrogen
Conditions: Catalyst Al2O3 or SiO2 (Thermal and Catalytic)

Temperature 400 ⁰C - 500 ⁰C
Absence of Oxygen
(b) Combustion: Complete, CO2 , H2O

(Energy Source)
Incomplete, C, CO, H2O
(c) Free Radical Substitution: Initiation Cl - Cl Cl● + Cl●
Propagation Cl● + CH4 CH3● + HCl
Termination CH3● + CH3● C2 H6
Initiation = Only halogen free radicals formed

Propagation = A free radical substitutes a substance into a free radical
Termination = Two free radicals combine to form a substance
* Homolytic Fission results free radicals while Homolytic Fission results ions
* shows the movement of single electron
* shows the movement of an electron pair

Page 219 of 231
3. Alkene CnH2n
Dehydration / Elimination CH3 - CH2 - OH CH2 = CH2 + H2O
(Condition: Conc. H2SO4 + 170 ⁰C OR Al2O3(s) + 300 ⁰C)
Preparations Dehydrogenation
C2H6 C2H4 + H2
Cracking
OH- Alcohol
Elimination CH3 - CH2 - X CH2 = CH2 + H2O + X-
reflux
Ni + 150⁰C
Hydrogenation CH2 = CH2 + H2 CH3 - CH3
Cone. H3 PO4 + 300⁰C + 70atm

Hydration CH2 = CH2 + H2 O CH3 - CH2 - OH
CCl4
Reactions Bromination (a) CH2 = CH2 + Br2 CH2 - CH2
(With Electrophilic
addition Mechanism) Br Br
(b) CH2 = CH2 + Br2 (aq) CH2 - CH2 + CH2 - CH2
Br Br Br OH
r.t.p
Hydrohalogenation CH3 - CH = CH2 + HBr(g) CH3 - CH2 - CH2-Br
(With Markonioves Rule) (20%)
+
CH3 - CH - CH3
Br (80%)
(i) Cold dil. KMnO4
MnO4- / OH-
Oxidation CH2 = CH2 + [O] + H2O CH2 - CH2
r.t.p
OH OH (Diol)
{Observation: Purple to Colourless and Brown ppt (MnO2)}
O
MnO4- / H+
(ii) Hot Cone. KMnO4 CH2 = CH-R + [O] CO2 + H2O + R - C -OH
Heat
R R
MnO4- / H+
R - C = CH2 + [O] R - C = O + CO2 + H2O
Heat
* used to find out position of C=C in alkenes.
* If the double bonded carbon attached to one carbon directly, Carboxylic acid produces
* If the double bonded carbon attached to two more carbons directly, Ketone produces
* If the double bonded carbon attached to no more carbon, Carbon dioxide and water produce
Page 220 of 231
4. Alcohols CnH2n+1OH
Primary (1⁰) C - C - OH
Types Secondary (2⁰) C - C - OH
C
C
Tertiary (3⁰) C - C - OH
Hydration of alkene
Preparation Fermentation C6 H12 O6 2C2 H5OH + 2CO2

(Condition: yeast, 18⁰C - 40⁰C, Absence of Oxygen)
Reduction of Carboxylic acid
With Na, CH3 - CH2 - OH + Na CH3 - CH2 - O-Na+ + 1�2H2

(use to find no. of OH group) (Basic solution) Bubbles/Fizzing)
SN reaction R - OH R - X + HX (Steamy fumes)

(Conditions PCl5 or PCl3 + Heat or SOCl2 or I2 + P4 + Heat)
with HBr R - OH R - Br + H2O

(Conditions HBr(g) or NaBr + Cone. H2SO4 + Heat)
Reactions Dehydration
1⁰ mild
Oxidation CH3 - CH2 - OH + [O] CH3 - CHO
Oxidation
(Conditions: H+ / K2Cr2O7 + Heat or H+ / KMnO4 + Heat)
O
1⁰ Oxidation
CH3 - CH2 - OH + [O] CH3 - C - OH
(Conditions: H+ / K2Cr2O7 + reflux or H+ / KMnO4 + reflux)
CH3 CH3
2⁰ Oxidation
CH3 - CH - OH CH3 - C = O
Esterification RCOOH + ROH RCOOR + H2O
(Condition: Heat + Any one Conc. HCl or Conc. H2SO4)
* 3⁰ do not oxidise
5. Halogeno alkane, R-X, Alkyl Halides CnH2n+1X
Alkane (free radial substitution)
Preparation Alkene (Electrophilic addition)
Alcohol (SN reaction)

Page 221 of 231
Hydrolysis CH3 - CH2 - X CH3 - CH2 - OH + HX

(Conditions: Aq NaOH + reflux)
(Nucleophilic substitution)
CH3 - CH2 - X CH3 - CH2 - CN + X-

Reaction (Conditions: KCN or NaCN in Alcohol + reflux)
Elimination CH3 - CH2 - X CH2 = CH2 + H2O + X-

(Conditions: Alcoholic NaOH + reflux)
Amine formation, R-X R - NH2 + HCl
(Conditions: Conc. NH3 in ethanol + Heat)
* Primary Alkyl halides undergo SN 2 reactions
* Secondary Alkyl halides undergo both SN 1 and SN 2 reaction
* Tertiary Alkyl halides undergo SN 1 reaction
* Higher temperature, Higher concentration of Nucleophile and Ethanol as a solvent will favour
Elimination reaction
* Lower temperature, Dil solution of nucleophile and Water as a solvent will favour Substitution reaction
* SN mechanism with ease of hydrolysis depending on C - Hal bond length.
6. Carboxylic Acid CnH2n+1COOH
[O]
Preparation Oxidation 1⁰ alcohol R-CH2 - OH R - COOH
[O]
aldehyde R - CHO R - COOH
H+ + reflux
Hydrolysis R - CN R - COOH + NH4+
(Oxidation of Nitriles) (Acidic Hydrolysis)
OH- + reflux
R - CN R - COO- + NH3
(Alkaline Hydrolysis)
* After alkaline hydrolysis Acidifying with any strong acid will produce carboxylic acid again
* Reduction of Nitriles will produce amine
r.t.p
Reactions With NaOH: RCOOH + NaOH RCOO-Na+ + H2O
r.t.p
With NaHCO3 / Na2CO3 RCOOH + Na2CO3 RCOO-Na+ + H2O + CO2
r.t.p
With Na: RCOOH + Na RCOO-Na+ + 1�2H2
(used to identify COOH Groups)
warm
With SOCl2 , RCOOH + SOCl2 ROCl + SO2 + HCl
warm
With PCl5 , RCOOH + PCl5 RCOCl + POCl3 + HCl
dry ether/r.t.p
With LiAlH4 , RCOOH R - CH2 - OH
Esterification can be done both with Alcohol and Acyl halides
* For Reduction of carboxylic acid Sodium boron hydride cannot be used

* Ni + H2 can be used to reduce carboxylic acid industrially
Page 222 of 231
7. Aldehydes and Ketones / Carbonyl
Test for Carbonyl: Condensation reaction
NO2 NO2
Test for Aldehyde
(i) Tollen's Reagent
O O O O
Heat
R - C - H + 2Ag(NH3)2OH R - C - OH or R - C - O- or R - C - O-NH4+ + 2Ag(s) + 3NH3 + H2O
colourless (Silver ppt)
(ii) Fehling's Solution
O O O O
Heat
R - C - H + 2Cu(OH)2 + NaOH R - C - OH or R - C - O- or R - C - O-Na+ + Cu2O(s) + 3H2O
Blue Solution (Brick red ppt)
* Both are redox reaction

* Ketones and Bezaldehyde do not react with Fehling's solution
(Iodo form test) / Triiodomethane test / Test for methyl ketones
*Test for methyl ketone, Ethanal, Ethanol, and 2⁰ alcohol with CH3 - CH Group
OH
O O
warm
CH3 - C - CH3 + NaOH + 3I2 CH3 - C - O- + CHI3(s) + 3H2O + 3NaI
(Yellow ppt)
Preparations Alcohols (done)
Alkenes (done)
O (10 0C - 20 0C)/ KCN OH
Reaction Cyanohydrin R - C - + HCN(g) R - C - CN
(with Nucleophilic addition mechanism)
Oxidation of aldehyde (done)
* Ketones don't oxidise.
*The carbonyl compounds can be converted back into alcohols by reduction
*Hydrogen cyanide dissociate in water to form the cyanide ion, CN-, which is nucleophile. However, HCN is weak
acid and thus a poor source of cyanide ions, a trace of sodium or potassium cyanide is added in order to accelerate
the reaction:
Page 223 of 231
8. Polymerisation
Addition Polyethene, Poly propene, PVC, PTFE etc.

Page 224 of 231
1. BENZENE C6H6
 Hexagonal, planar, 120⁰ bond angle with 6 Sp2 - Hybridized carbon.
 not saturated nor unsaturated but aromatic (Arene)
 because of delocalization of 𝜋𝜋 - electrons, all C-C bond lengths are equal, gives stability to benzene, does not
undergo reactions like alkenes.
 Colourless Poisonous liquid, Insoluble in polar but soluble in non-polar.
ELECTROPHILIC SUBSTITUTION REACTION
A. HALOGENATION
(For bromination Br2 and FeBr3 is used)
MECHANISM
B. NITRATION
MECHANISM
Further reaction is possible if the temperature is above 60 ⁰C. 1,3 - dinitrobenzene is formed.
C. FRIEDEL CRAFT REACTION
1. ALKYLATION
Benzene undergoes Friedel-Crafts reaction with chloromethane in the following reaction.
[ more than 2 carbon, stability of carbonium factor is involved ]

Page 225 of 231
2. ACYLATION
Benzene undergoes Friedel-Crafts reaction with ethanoyl chloride in the following reaction.
ADDITION REACTION
 For addition of Halogen, no catalyst and Hydrogenation Ni/150°C
2. ORIENTATION
 Where directors direct incoming electrophile at ortho, meta or para.
O, P – Directors (2,4,6 – Directors)
• Electron donating (Electron pushing)

• Activating
• Saturated Groups
m – Directors (3,5 – Directors)
• Electron withdrawing
• Deactivating
• Unsaturated
3. TOLUENE / METHYL BENZENE (C6H5 – CH3)

 Colourless liquid, non-polar, B.P slightly higher than Benzene.
 More reactive than Benzene b/c of methyl activating e- pushing Group.
A. HALOGENATION
Page 226 of 231
B. NITRATION
 This temperature is lower than that used in the nitration of benzene as methylbenzene reacts more readily
with electrophile.
 At higher temperatures, two and three nitro groups can be substituted in the benzene ring.
C. ALKYLATION
SIDE CHAIN REACTION

A. OXIDATION
 Methylbenzene undergoes oxidation with acidified potassium permanganate solution to form benzoic acid.
The purple acidified potassium permanganate solution is decolourised and a white precipitate of benzoic
acid is produced.
B. HALOGENATION
Page 227 of 231
4. PHENOLS (C6H5 OH)

 Colourless crystalline solid with higher m.p than Benzene and Toluene because of Hydrogen bonding.
 Weak acid, slightly soluble in water.
ACIDIC BEHAVIOR
Na NaOH Na2CO3
C2H5OH  X X
  X
CH3COOH   
resonance stabilization
 Stronger than water and alcohols but weaker acid than carboxylic acid.
 Electron donating decreases the acidity of phenol by increasing e- density on oxygen, hence it accept H+ ions
more rapidly.
 Electron withdrawing increases the acidity of phenol, hence phenoxide ion delocalises its oxygen e- charge
density over aromatic ring.
 Carboxylate ion stabilized by resonance.
A. HALOGENATION
B. NITRATION
Page 228 of 231
REACTION WITH ‘OH’ GROUP
5. AMINE & AMIDES

 Derivatives of ammonia, they may be 1°, 2° and 3° amines
 Amines are basic b/c of lone pair of e- of nitrogen makes it able to accept proton (lewis base).
 Basicity of amine increases by electron donating group

 3° amines are less basic than 1° and 2° b/c of steric hindrance.
 Aryl amines are least basic than NH3 b/c lone pair of Nitrogen is delocalized over benzene ring.
PREPARATION
REACTIONS
Page 229 of 231
COUPLING OR DIAZOTISATION
6. CARBONYL COMPOUNDS
TEST FOR CARONYL GROUP
TEST FOR ALDEHYDE
(a) Tollens’ Test
(b) Fehling’s Test
IODOFORM TEST
* Details of these reactions have been discussed in AS level

Page 230 of 231
7. CARBOXYLIC ACID
 They may be prepared from alkene, Nitriles, 1° alcohols and aldehydes.
 Stronger acid than phenols.
 Electron withdrawing groups increases the acidity of carboxylic acid.
8. ARYL HALIDES
Comparison of alkyl halide with aryl halides
 Aryl halides do not undergo similar reaction like alkyl halides because of carbon-halide bond is strengthen
by over lapping p-orbital of ‘Cl’ with 𝜋𝜋 orbital of Benzene.
9. POLYMERIZATION
 A process in which monomers form polymer.
Addition (monomers Polymer only)
Polymer
Condensation (monomers Polymer + H2O or HCl or NH3)

(Biodegradable polymers PLA)
ADDITION
(a) Homopolymer (contain one type of repeat unit)

Page 231 of 231
(b) Copolymer (contain at least 2 different repeat units)
(c) Thermoplastics
 Soft and formable when heated [Recycled plastics]

 Rigid when cooled
 Can be re-heated and reformed into different shapes
(d) Thermosetting
 Initially form a X – Linked solid with by heating
(e) Elastomers
* They stretch when pulled but return to their original shape when force is released
* In the unstretched state, the chains coil up randomly. These chains straighten out when stretch.
* Cross-linking is present between chains so that they can return to their original length after the force is
released.
(f) Conducting polymer
Condensation
* Kevlar, Poly lactic acid( PLA), Nylon 6, Nylon 6,6, Lactomers etc.

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Organic worksheet for A2 Level

1. The common analgesic drug paracetamol has the following structure.

(a) Name the two functional groups in the paracetamol molecule

.............................................................. and ........................................................... [2]

(ii) NaOH(aq) in the cold,

(iii) NaOH(aq) under reflux.

(c) Paracetamol can be synthesised by reacting 4-aminophenol with compound X.

(i) Suggest a possible identity of X.

(a) State the condition needed for

(ii) reaction II..

3. Phenylamine is an important intermediate compound for the production of dyes.

reagent + conditions for step I .........................................................................................

reagent + conditions for step II ........................................................................................ [4]

(b) Phenylamine is a weak base.

(i) Write an equation showing phenylamine acting as a base.

(iii) Explain the reasoning for your answer in (ii).

(ii) What reagent is the phenol dissolved in for step IV to be effective?

4. Benzene can be converted into nitrobenzene by a nitration reaction.

(b) What type of reaction mechanism is this?

(c) The reaction proceeds via two steps:

(i) Draw the structure of the intermediate Y in the box.

(ii) Identify the cation X+..................................................................................................

(iii) Identify the cation Z+..................................................................................................

(iv) Write an equation to show how X+ is produced from the reagents.

(a) What type of reaction mechanism is this?

(ii) State the reagents and conditions for step I.

(iii) State the reagents and conditions for step II.

(i) What type of polymerisation produces Kevlar?

(a) Suggest reagents and conditions for step I.

(f) Residues of CN can be destroyed by hydrolysis with an aqueous alkali.

Compounds G and H are isomers of compound D.

(ii) Explain the reasoning behind your choice.

(i) Suggest a reagent for step I.

When the diacyl chloride of L is reacted with HOCH2CH2OH, a polymer is formed.

(i) What type of polymerisation is occurring here?

(c) The following formula represents a section of another polymer.

(i) What type of polymer is this?

8. Ethyl 4-hydroxybenzoate, E, is a permitted food preservative.

(a) Name two functional groups in E.

(i) sodium metal,

(ii) NaOH(aq) under reflux,

(c) Compounds F and G are isomers of E.

(i) Suggest the order of acid strength of E, F and G.

distinguished from each other by the use of NaOH(aq) and Na2CO3(aq).

observation with H ............................................................................................................

observation with L ........................................................................................................ [2]

(c) Alanine reacts with both acids and bases.

(e) Alanine is one of about 20 amino acids that make up proteins.

(i) What type of bond joins amino acids together in proteins?

10. This question is about the reactions of some functional groups.

formula you drew in part (i).

(i) Identify the cation A+. ...............................................................................................

(ii) Draw the structure of the intermediate B in the box. [2]

(i) the reaction between alanine and HCl(aq),

(ii) the reaction between serine and NaOH(aq).

(d) What type of polymer is silk protein?

number of residues = ................................... [3]

13. This question is concerned with organochlorine compounds.

(i) conditions for reaction I