Year 2 – Organic Synthesis and analysis

Q1. The reaction scheme below shows the conversion of epoxyethane into sodium
ethanedioate.

Compound X (COOH) 2 Na C O
2 2 4

(a) Identify compound X. State the reagents and conditions required to convert X into
ethanedioic acid. Draw the structure of the anion in sodium ethanedioate.
(4)

(b) The addition of sodium ethanedioate to an aqueous solution containing [Co(H O) ] 2 6

2+

ions results in the formation of a more stable complex ion. Draw the structure of the
complex ion formed and explain, in thermodynamic terms, why this substitution
reaction occurs.
(4)
(Total 8 marks)

Q2.(a) Compound C, H N(CH ) NH , can be synthesised from ethene in three steps as shown
2 2 4 2

below.

Step 1 Step 2 Step 3

Ethene Compound Compound Compound
addition A substitution B C
reaction reaction CHN 4 4 2 H N(CH ) NH
2 2 4 2

Name compound C and draw a structure for each of compounds A and B.

State the reagent(s) required for each step and name the type of reaction involved in
the conversion of B into C.
(7)

(b) Draw the repeating unit of the polyamide formed when C reacts with hexanedioic
acid. Discuss the interactions between the chains of the polyamide.
(4)

(c) Explain why polyamides are degraded by sodium hydroxide whereas polymers such
as poly(ethene) are not.
(3)

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 Year 2 – Organic Synthesis and analysis
(Total 14 marks)

Q3. The conversion of compound A into compound B can be achieved in two steps as
shown below.

The intermediate compound, X, has an absorption at 1650 cm in its infra-red spectrum.

–1

(a) Identify compound X. Explain your answer.

(2)

(b) For each step in this conversion, give the reagents and essential conditions required
and outline a mechanism.
(11)

(c) Show how the number of peaks in their proton n.m.r. spectra would enable you to
distinguish between compounds A and B.
(2)
(Total 15 marks)

Q4. A possible synthesis of 1,4-diaminobenzene is shown below.

Page 2
 Year 2 – Organic Synthesis and analysis

(a) Identify a suitable reagent or combination of reagents for Step 1. Name and outline
a mechanism for the reaction.
(6)

(b) Identify a suitable reagent or combination of reagents for Step 2. Name and outline
a mechanism for the reaction.
(6)

(c) Identify a suitable reagent or combination of reagents for Step 4. Draw the repeating
unit of the polymer formed by reaction of 1,4-diaminobenzene with pentanedioic
acid.
(3)
(Total 15 marks)

Q5. Use the data given on the back of the Periodic Table (PT) to help you answer this
question.
Compounds A to G are all isomers with the molecular formula C H O 6 12 2

(a) Isomer A, C H O , is a neutral compound and is formed by the reaction between

6 12 2

compounds X and Y in the presence of a small amount of concentrated sulphuric

acid.
X and Y can both be formed from propanal by different redox reactions.
X has an absorption in its infra-red spectrum at 1750 cm .
–1

Deduce the structural formulae of A, X and Y. Give suitable reagents, in each case,
for the formation of X and Y from propanal and state the role of concentrated

Page 3
 Year 2 – Organic Synthesis and analysis
sulphuric acid in the formation of A.
(7)

(b) Isomers B, C, D and E all react with aqueous sodium carbonate to produce carbon
dioxide.
Deduce the structural formulae of the three isomers that contain an asymmetric
carbon atom.
The fourth isomer has only three singlet peaks in its proton n.m.r. spectrum. Deduce
the structural formula of this isomer and label it E.
(4)

(c) Isomer F, C H O , has the structural formula shown below, on which some of the
6 12 2

protons have been labelled.

A proton n.m.r. spectrum is obtained for F. Using Table 1 at the back of the Periodic
Table (PT), predict a value of δ for the protons labelled a and also for those labelled
b. State and account for the splitting patterns of the peaks assigned to the protons a
and b.
(6)

(d) Isomer G, C H O , contains six carbon atoms in a ring. It has an absorption in its
6 12 2

infra-red spectrum at 3270 cm and shows only three different proton environments
–1

in its proton n.m.r. spectrum. Deduce a structural formula for G.

(2)
(Total 19 marks)

Q6. (a) Describe how propanal, CH CH CHO, and propanone, CH COCH , can be
3 2 3 3

distinguished using

(i) a chemical test and

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

(5)

Page 4
 Year 2 – Organic Synthesis and analysis
(b) Compound Z can be produced by the reaction of compound X with compound Y as
shown in the synthesis outlined below.

Identify compounds X and Y.

For each of the three steps in the synthesis, name the type of reaction involved and
give reagents and conditions. Equations are not required.

(10)
(Total 15 marks)

Q7. Two reactions of benzene are shown below.

(a) Name X and give the reagent and catalyst required for Reaction 1.
Write an equation for the formation of the reactive intermediate involved in this
reaction.
Name and outline a mechanism for the reaction of this reactive intermediate with
benzene to form X.
Page 5
 Year 2 – Organic Synthesis and analysis
(8)

(b) (i) Deduce the structure of Y and give the organic reagent needed for Reaction 2.

(ii) Give the reagent(s) needed for Reaction 3.

(3)
(Total 11 marks)

Q8. A possible synthesis of phenylethene (styrene) is outlined below.

(a) In Reaction 1, ethanoyl chloride and aluminium chloride are used to form a reactive
species which then reacts with benzene.
Write an equation to show the formation of the reactive species.
Name and outline the mechanism by which this reactive species reacts with
benzene.
(6)

(b) NaBH is a possible reagent for Reaction 2.

4

Name and outline the mechanism for the reaction with NaBH in Reaction 2.
4

Name the product of Reaction 2.

(6)

(c) Name the type of reaction involved in Reaction 3 and give a reagent for the reaction.
(2)
(Total 14 marks)

Page 6
 Year 2 – Organic Synthesis and analysis
Q9. A chemist has discovered that the labels have fallen off four bottles each of which
contains a different organic liquid. These liquids are known to be propan-2-ol, propanal,
hexene and 1-bromopropane.

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

Q10. Compound W can be formed via compounds H and S in the three-step synthesis
shown below.

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

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

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

Q11. Synthetic dyes can be manufactured starting from compounds such as 4-

nitrophenylamine.

A synthesis of 4-nitrophenylamine starting from phenylamine is shown below.

(a) An equation for formation of N-phenylethanamide in Step 1 of the synthesis is

Page 7
 Year 2 – Organic Synthesis and analysis
shown below.

2C H NH + CH COCl → C H NHCOCH
6 5 2 3 6 5 3 + C H NH Cl
6 5 3

N-phenylethanamide

(i) Calculate the % atom economy for the production of N-phenylethanamide

(M = 135.0).
r

(ii) In a process where 10.0 kg of phenylamine are used, the yield of N-

phenylethanamide obtained is 5.38 kg.

Calculate the percentage yield of N-phenylethanamide.

(iii) Comment on your answers to parts (i) and (ii) with reference to the
commercial viability of the process.
(7)

(b) Name and outline a mechanism for the reaction in Step 1.

(5)

(c) The mechanism of Step 2 involves attack by an electrophile. Write an equation

showing the formation of the electrophile. Outline a mechanism for the reaction of
this electrophile with benzene.
(4)
(Total 16 marks)

Q12. Atenolol is an example of the type of medicine called a beta blocker. These
medicines are used to lower blood pressure by slowing the heart rate. The structure of
atenolol is shown below.

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

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

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 Year 2 – Organic Synthesis and analysis
Functional group labelled K .........................................................................
(2)

(b) The H n.m.r. spectrum of atenolol was recorded.

1

One of the peaks in the H n.m.r. spectrum is produced by the CH group labelled p
1
2

in the structure of atenolol.

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

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

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

(2)

(c) N.m.r. spectra are recorded using samples in solution.

The H n.m.r. spectrum was recorded using a solution of atenolol in CDCl
1
3

(i) Suggest why CDCl and not CHCl was used as the solvent.
3 3

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

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

(ii) Suggest why CDCl is a more effective solvent than CCl for polar molecules
3 4

such as atenolol.

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

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

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

13

Use the structure of atenolol given to deduce the total number of peaks in the
C n.m.r. spectrum of atenolol.
13

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

(e) Part of the C n.m.r. spectrum of atenolol is shown below. Use this spectrum and
13

Table 3 on the Data Sheet, where appropriate, to answer the questions which
follow.

Page 9
 Year 2 – Organic Synthesis and analysis

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

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

(ii) One of the peaks in the C n.m.r. spectrum above is produced by the CH
13
3

group labelled q in the structure of atenolol.

Identify this peak in the spectrum by stating its δ value.

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

(iii) There are three CH groups in the structure of atenolol. One of these CH
2 2

groups produces the peak at δ = 71 in the C n.m.r. spectrum above. 13

Draw a circle around this CH group in the structure of atenolol shown below.
2

(1)

(f) Atenolol is produced industrially as a racemate (an equimolar mixture of two

enantiomers) by reduction of a ketone. Both enantiomers are able to lower blood
pressure. However, recent research has shown that one enantiomer is preferred in
medicines.

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

Page 10
 Year 2 – Organic Synthesis and analysis
.............................................................................................................
(1)

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

(1)

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

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

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

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

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

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

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

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

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

.............................................................................................................
(2)
(Total 16 marks)

Q13. A student used the infrared spectra of water vapour and of carbon dioxide to try to
find a link between infrared radiation and global warming.

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 Year 2 – Organic Synthesis and analysis

(i) Use information from the infrared spectra to deduce one reason why the student
concluded that water vapour is a more effective greenhouse gas than carbon
dioxide.

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

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

(ii) Use your knowledge of the bonds in CO to state why the infrared spectrum of
2

carbon dioxide is not as might be predicted from the data provided in Table 1 on the
Data Sheet.

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

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

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

.....................................................................................................................
(2)
(Total 3 marks)

Page 12
 Year 2 – Organic Synthesis and analysis

Q14. Organic chemists use a variety of methods to distinguish between compounds.

These methods include analytical and spectroscopic techniques.

(a) The following compounds can be distinguished by observing what happens in test-
tube reactions.

For each pair, suggest a suitable reagent or reagents that could be added
separately to each compound in order to distinguish them.

Describe what you would observe with each compound.

(i)

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

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

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

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

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

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

(ii)

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

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

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

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

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 Year 2 – Organic Synthesis and analysis
.............................................................................................................

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

(iii)

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

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

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

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

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

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

(b) Compounds J and K can also be distinguished using spectroscopic techniques

such as H n.m.r.
1

(i) Name compound J.

Give the total number of peaks in the H n.m.r. spectrum of J.

1

State the splitting pattern, if any, of the peak for the protons labelled a.

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

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

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

Page 14
 Year 2 – Organic Synthesis and analysis
.............................................................................................................

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

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

(ii) Name compound K.

Give the total number of peaks in the H n.m.r. spectrum of K.

1

State the splitting pattern, if any, of the peak for the protons labelled b.

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

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

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

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

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

.............................................................................................................
(3)
(Total 15 marks)

Q15.(a) A chemist discovered four unlabelled bottles of liquid, each of which contained a
different pure organic compound. The compounds were known to be propan-1-ol,
propanal, propanoic acid and 1-chloropropane.

Describe four different test-tube reactions, one for each compound, that could be
used to identify the four organic compounds.
Your answer should include the name of the organic compound, the reagent(s) used
and the expected observation for each test.

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

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

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

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

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

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

Page 15
 Year 2 – Organic Synthesis and analysis
........................................................................................................................

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

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

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

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

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

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

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

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

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

(b) A fifth bottle was discovered labelled propan-2-ol. The chemist showed, using
infrared spectroscopy, that the propan-2-ol was contaminated with propanone.

The chemist separated the two compounds using column chromatography. The
column contained silica gel, a polar stationary phase.

The contaminated propan-2-ol was dissolved in hexane and poured into the column.
Pure hexane was added slowly to the top of the column. Samples of the eluent (the
solution leaving the bottom of the column) were collected.

• Suggest the chemical process that would cause a sample of propan-2-ol to

become contaminated with propanone.

• State how the infrared spectrum showed the presence of propanone.

• Suggest why propanone was present in samples of the eluent collected first
(those with shorter retention times), whereas samples containing propan-2-ol
were collected later.

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

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

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

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

Page 16
 Year 2 – Organic Synthesis and analysis
........................................................................................................................

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

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

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

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

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

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

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

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

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

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

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

........................................................................................................................
(4)
(Total 12 marks)

Q16.Benzene reacts with ethanoyl chloride in a substitution reaction to form C H COCH . 6 5 3

This reaction is catalysed by aluminium chloride.

(a) Write equations to show the role of aluminium chloride as a catalyst in this reaction.

Outline a mechanism for the reaction of benzene.

Name the product, C H COCH . 6 5 3

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

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

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

Page 17
 Year 2 – Organic Synthesis and analysis
(6)

(b) The product of the substitution reaction (C H COCH ) was analysed by mass
6 5 3

spectrometry. The most abundant fragment ion gave a peak in the mass spectrum
with m/z = 105.
Draw the structure of this fragment ion.

(1)

(c) When methylbenzene reacts with ethanoyl chloride and aluminium chloride, a
similar substitution reaction occurs but the reaction is faster than the reaction of
benzene.
Suggest why the reaction of methylbenzene is faster.

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

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

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

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

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

........................................................................................................................
(2)
(Total 9 marks)

Q17.Acyl chlorides and acid anhydrides are important compounds in organic synthesis.

(a) Outline a mechanism for the reaction of CH CH COCl with CH OH and name the
3 2 3

organic product formed.

Mechanism

Page 18
 Year 2 – Organic Synthesis and analysis

Name of organic product ...............................................................................

(5)

(b) A polyester was produced by reacting a diol with a diacyl chloride. The repeating
unit of the polymer is shown below.

(i) Name the diol used.

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

(ii) Draw the displayed formula of the diacyl chloride used.

(1)

(iii) A shirt was made from this polyester. A student wearing the shirt accidentally
splashed aqueous sodium hydroxide on a sleeve. Holes later appeared in the
sleeve where the sodium hydroxide had been.

Name the type of reaction that occurred between the polyester and the
aqueous sodium hydroxide. Explain why the aqueous sodium hydroxide
reacted with the polyester.

Type of reaction ....................................................................................

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

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

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

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

(c) (i) Complete the following equation for the preparation of aspirin using ethanoic
Page 19
 Year 2 – Organic Synthesis and analysis
anhydride by writing the structural formula of the missing product.

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

(1)

(ii) Suggest a name for the mechanism for the reaction in part (c)(i).

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

(iii) Give two industrial advantages, other than cost, of using ethanoic anhydride
rather than ethanoyl chloride in the production of aspirin.

Advantage 1 ..........................................................................................

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

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

Advantage 2 ..........................................................................................

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

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

(d) Complete the following equation for the reaction of one molecule of benzene-1,2-
dicarboxylic anhydride (phthalic anhydride) with one molecule of methanol by
drawing the structural formula of the single product

(1)

(e) The indicator phenolphthalein is synthesised by reacting phthalic anhydride with

phenol as shown in the following equation.

Page 20
 Year 2 – Organic Synthesis and analysis

(i) Name the functional group ringed in the structure of phenolphthalein.

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

(ii) Deduce the number of peaks in the C n.m.r. spectrum of phenolphthalein.

13

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

(iii) One of the carbon atoms in the structure of phenolphthalein shown above is
labelled with an asterisk (*).
Use Table 3 on the Data Sheet to suggest a range of δ values for the peak
due to this carbon atom in the C n.m.r. spectrum of phenolphthalein.
13

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

(f) Phenolphthalein can be used as an indicator in some acid–alkali titrations.

The pH range for phenolphthalein is 8.3 – 10.0

(i) For each acid.alkali combination in the table below, put a tick ( ) in the box if
phenolphthalein could be used as an indicator.

Acid Alkali Tick

box ( )

sulfuric acid sodium hydroxide

hydrochloric acid ammonia

ethanoic acid potassium hydroxide

Page 21
 Year 2 – Organic Synthesis and analysis

nitric acid methylamine

(2)

(ii) In a titration, nitric acid is added from a burette to a solution of sodium

hydroxide containing a few drops of phenolphthalein indicator.
Give the colour change at the end-point.

...............................................................................................................
(1)
(Total 21 marks)

Q18.Describe how you could distinguish between the compounds in the following pairs using
one simple test-tube reaction in each case.

For each pair, identify a reagent and state what you would observe when both compounds
are tested separately with this reagent.

(a)

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

Observation with R.........................................................................................

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

Observation with S.........................................................................................

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

(b)

Page 22
 Year 2 – Organic Synthesis and analysis

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

Observation with T.........................................................................................

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

Observation with U.........................................................................................

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

(c)

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

Observation with V.........................................................................................

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

Observation with W........................................................................................

........................................................................................................................
(3)
(Total 9 marks)

Page 23
 Year 2 – Organic Synthesis and analysis

M1. (a) Identity of A;

ethane-1,2-diol or 1,2 dihydroxyethane or ethylene glycol or formula (1)
N.B. Do NOT allow OHCH CH OH unless a correct name is
2 2

also given

K Cr O / dilute H SO or dilute HCl or K Cr O / H

2 2 7 2 4 2 2 7
+

N.B. Oxidising agent must be a reagent

N.B. Do NOT allow concentrated H SO 2 4

Reflux or warm or heat (1)

Ignore temperature if given
N.B. If a temperature given on its own it must be at or below
200°C

Anion: (1)
N.B. Do NOT allow C O2 4
2–

N.B. Ignore lone pairs of electrons

4

(b) Structure :
correct co-ordination (1)
bonding through six correct oxygen (1)
Score 2 or zero
N.B. Not essential to show double bonds i.e. C=O in
structure

Explanation:
Substitution produces more molecules or particles or more disorder (1)
Entropy change is positive (1)
4
[8]

Page 24
 Year 2 – Organic Synthesis and analysis

M2.(a) 1, 4-diaminobutane or butane -1, 4-diamine (1)

A: BrCH2CH2Br or ClCH2CH2Cl (1)
B: NC CH2CH2CN
Step 1: Br2 or Cl2 (1) (ignore aq)
Step 2: KCN (1) (NOT HCN)
Step 3: H2 / Ni or LiAlH or Na / C2H5OH (1) (NOT NaBH4)
4

Hydrogenation only for H2 / Ni, or nucleophilic addition only for LiAlH4(1)

OR reduction or addition
7

(b)

QL hydrogen bonding (1)

Polarity of H-bonding shown or discussed (1)

4

(c) Polyamides / peptide link can be hydrolysed (1)

OR polyalkenes cannot be hydrolysed

QL OH– attacks peptide link or C (1)

+

poly(ethene) non-polar (1)

3
[14]

M3. (a) Identity of X; 2-methylpropene (1)

Absorption at 1650 cm indicates an alkene present (1)
–1

OR a chemical answer e.g. Br (aq) brown to colourless

2

(b) Reagents
Step 1 KOH (allow NaOH) (1) alcoholic (1) warm (1)
Only allow solvent and warm if reagent correct

Step 2 HBr (1)

Page 25
 Year 2 – Organic Synthesis and analysis
Mechanism: A→X

Or a carbocation mechanism

Mechanism X→B

11

(c) A gives three peaks (1)

B gives one peak (1)
Allow one for “A has more peaks than B” when no number of
peaks is given
2
[15]

M4. (a) CH COCl or (CH CO) O (1)

3 3 2

AlCl or H O or CH SO loses this mark

3 2 2 4

CH COOH loses reagent and M3, M4 = max 3

3

nucleophilic addition–elimination (1)

M3: structure
M4: 3 correct arrows
Allow M1 for attack on CH3- C =O +

Penalise Cl removing H
– +

Page 26
 Year 2 – Organic Synthesis and analysis
(b) Conc HNO (1) 3

Conc H SO (1)
2 4

HNO + 2 H SO → NO + H O + 2 HSO (2)

3 2 4 2
+
3
+
4
–

(or H SO ) 2(or H O + HSO )

4 2 4
–

HNO / H SO scores 1 3 2 4

Any 2

electrophilic substitution (1)

M2 structure
M3 arrow
6

(c) Sn (or Fe) / HCl or Ni / H (1) 2

NOT LiAlH NaBH 4 4

3
[15]

M5. (a) X contains > C=O (1)

if X and Y reversed lose this mark but allow remaining max
6/7

X is CH CH COOH (1)
3 2

Y is CH CH CH OH (1)
3 2 2

A is (1)

Page 27
 Year 2 – Organic Synthesis and analysis
Conc H SO : catalyst (1)
2 4

(b)

(c) 3.1 – 3.9 (1)

2.1 – 2.6 (1)

a: quartet (1) 3 adjacent H (1)

b: triplet (1) 2 adjacent H (1)

6

(d) 3269 cm –1
OH alcohol (1)

G is (1)
2

Notes

(a) first mark for C=O stated or shown in X

Ignore wrong names

Y CH CH CH OH
3 2 2

allow C H in A if Y correct or vice versa

3 7

Allow (1) for A if correct conseq to wrong X and Y

Page 28
 Year 2 – Organic Synthesis and analysis
other oxidising agents: acidified KMnO ; Tollens; Fehlings
4

other reducing agents: LiAlH ; Na/ethanol; Ni/H ; Zn or Sn or Fe/HCl

4 2

(b) give (1) for carboxylic acid stated or COOH shown in each suggestion
(1) for correct E
any 2 out of 3 for B, C or D
allow C H for either the B or D shown on the mark scheme
3 7

i.e. a correct structure labelled B, C or D or E will gain 2.

(c) protons a – quartet must be correct to score 3 adjacent H mark. Same for b

(d) allow (1) for any OH (alcohol) shown correctly in any structure – ignore extra
functional groups. Structure must be completely correct to gain second mark
[19]

Organic points

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

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

(2) Structures

penalise sticks (i.e. ) once per paper

Penalise once per paper

allow CH – or –CH or
3 3 or CH 3

Page 29
 Year 2 – Organic Synthesis and analysis
or H C– 3

M6. (a) (i)

Reagent Tollens Fehlings or Benedicts K2Cr2O7/H+ KMnO4/H+ I2/NaOH

or acidified

Propanal silver red ppt or goes red goes green goes colourless No
(mirror) (not red solution) reaction

Propanone no no reaction no reaction no reaction Yellow

reaction (ppt)

(penalise incomplete reagent e.g. K Cr O or Cr O /H then mark on)

2 2 7 2 7
2– +

(ii) propanal 3 peaks

ignore splitting even if wrong
1

propanone 1 peak
1

(b) X is CH CH COOH or propanoic acid if both name and formula given,

3 2

both must be correct, but

1

Y is CH CH(OH)CH or propan-2-ol
3 3 allow propanol with correct formula
1

Mark the type of reaction and reagent/condition independently.

The reagent must be correct or close to score condition

Step 1 Oxidation

K Cr O /H or other oxidation methods as above

2 2 7
+

allow Cr O H if penalised above (ecf)

2 7
2– +

reflux (not Tollens/Fehlings) or heat or warm

1

Step 2 reduction or nucleophilic reduction or reduction or 1

Page 30
 Year 2 – Organic Synthesis and analysis

addition nucleophilic addition hydrogenation

NaBH 4 LiAlH 4 H 2 1

in (m)ethanol or water or ether ether or dry Ni / Pt etc

1
or dry

Step 3 esterification or (nucleophilic) addition-elimination or condensation

1

(conc) H SO or HCl
2 4

warm (allow without acid reagent if X and Y given as reagents)

1

or reflux or heat
1
[15]

M7. (a) ethyl benzene

1

chloroethane or bromoethane (or ethene and hydrogen chloride/bromide)

1

aluminium chloride/bromide or iron(III) chloride /bromide or iron +

chorine/bromine
1

CH CH Cl + AlCl → CH CH + AlCl
3 2 3 3 2
+
4
–

electrophilic substitution
1

(b)

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 Year 2 – Organic Synthesis and analysis

CH CH COCl / propanoyl chloride or (CH CH CO) O / propanoic

3 2 3 2 2

anhydride
1

NaBH or LiAlH or H /Ni (not Sn/Fe with HCl)

4 4 2

1
[11]

M8. (a) CH COCl + AlCl → CH

3 3 3 O + AlCl
(1) equation (1)
2

penalise wrong alkyl group once at first error

position of + on electrophile can be on O or C or outside [ ]
penalise wrong curly arrow in the equation or lone pair on AlCl else ignore
3

Electrophilic substitution
NOT F/C acylation
1

horseshoe must not extend beyond C2 to C6 but can be

smaller
+ not too close to C1
M3 arrow into hexagon unless Kekule
allow M3 arrow independent of M2 structure

M1 arrow from within hexagon to C or to + on C

+ must be on C of
3

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 Year 2 – Organic Synthesis and analysis

(b) Nucleophilic addition

NOT reduction
1

M2 not allowed independent, but can allow M1 for attack of

H on C+ formed
–

1–phenylethan(–1–)ol or (1–hydroxyethyl)benzene
l

(c) dehydration or elimination

1

(conc) H SO or (conc) H PO
2 4 3 4

allow dilute and Al O 2 3

Do not allow iron oxides

1
[14]

M9. Acidified potassium dichromate(VI)

1
Turns green with propan-2-ol and propanal
1
No reaction with hexene and 1-bromopropane
1
Tollens with propan-2-ol and propanal
1
only propanal gives silver mirror
1
Bromine water
1
Decolourised by hexane
1

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 Year 2 – Organic Synthesis and analysis
No reaction with 1-bromopropane
1
Warm NaOH followed by acidified AgNO 3

1
White ppt with 1-bromopropane
1
[10]

M10. H CH CN or ethanenitrile
3

S CH CH NH or ethylamine 1Step 1 KCN

3 2 2

aq/alcoholic
1

Step 2 H 2

Ni
1

W secondary amine
1

nucleophilic substitution
1
[9]

M11.

Mark The marking scheme for this part of the question includes an overall

Page 34
 Year 2 – Organic Synthesis and analysis

assessment for the Quality of Written Communication (QWC). There

are no discrete marks for the assessment of QWC but the
candidates’ QWC in this answer will be one of the criteria used to
Range assign a level and award the marks for this part of the question
Descriptor
an answer will be expected to meet most of the criteria in the level
descriptor

4-5 – claims supported by an appropriate range of evidence

– good use of information or ideas about chemistry, going beyond
those given in the question
– argument well structured with minimal repetition or irrelevant
points
– accurate and clear expression of ideas with only minor errors of
grammar, punctuation and spelling

2-3 – claims partially supported by evidence

– good use of information or ideas about chemistry given in the
question but limited beyond this
– the argument shows some attempt at structure
– the ideas are expressed with reasonable clarity but with a few
errors of grammar, punctuation and spelling

0-1 – valid points but not clearly linked to an argument structure

– limited use of information or ideas about chemistry
– unstructured
– errors in spelling, punctuation and grammar or lack of fluency

(a) (i) M of C H NH = 93 M of CH COCl = 78.5

r 6 5 2 r 3

total M of reagents = 264.5

r

% atom economy = × 100 QWC

1

= × 100 = 51.0 %
1

(ii) expected yield = × 0.5 × 135 = 7.26 kg

1

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 Year 2 – Organic Synthesis and analysis

% yield = × 100 = 74.1 %

1

(iii) Although yield appears satisfactory (74%) % atom economy

is only 51% QWC
1

nearly half of the material produced is waste and must be

disposed of QWC
1

(b) (nucleophilic) addition-elimination

1

QWC (2)
4

(c) HNO + 2H SO → NO + H O + 2HSO

3 2 4 2
+
3
+
4
–

3
[16]

M12. (a) J (acid) amide

not peptide, not N-substituted amide
1

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 Year 2 – Organic Synthesis and analysis
K (secondary) amine or amino
penalise primary or tertiary
allow N-substituted amine
1

(b) (δ =) 3.1-3.9
1

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

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

OR CHCl has protons or has H or gives a peak

3

(ii) CDCl is polar OR CCl is non-polar

3 4

(d) 11 OR eleven
1

(e) (i) Si(CH ) OR SiC H

3 4 4 12

ignore TMS
1

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

penalise anything outside this range
1

(iii)

allow ring around the C only and also allow

Page 37
 Year 2 – Organic Synthesis and analysis

(f) (i) NaBH 4

ignore name if formula correct

ignore solvent
allow LiAlH Zn/HCl Sn/HCl
4 H /Ni
2 H /Pt
2

(ii)

allow ring around the C only

1

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

1

polarised light is not rotated or is unaffected

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

(iv) adv cheaper medicine due to cost or difficulty of separation or

both can lower blood pressure

OR more effective/beneficial with a reason

or no need to separate
1

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

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

Page 38
 Year 2 – Organic Synthesis and analysis
M13. (i) More absorption/less transmittance of infrared radiation
by it/water vapour

OR broader absorption by OH

OR less absorption/more transmittance of infrared radiation

by carbon dioxide
Must be comparative
This may be described and must not be contradictory
Credit answers which refer correctly to “transmittance”
(more absorption = less transmittance)
1

(ii) M1 CO contains C=O (stated like this or in words or strongly

2

implied) OR is O=C=O

M2 depends on correct M1

OR expected absorption/peak (for C=O) is missing

OR expected absorption/peak (for C=O) is shifted to 2300 (cm ) –1

OR asymmetric stretching is occurring (due to C=O)

If M1 and M2 not scored, give one mark for either
No absorption/peak at 1700 (cm )/1715 (cm )
–1 –1

OR no absorption in the range 1680 – 1750 (cm ) –1

Ignore “carbon-oxygen bonds”, “C-O bonds”

Ignore reference to other absorptions
For M2
Allow “dip” OR “spike” OR “low transmittance” as alternatives
for absorption.
2
[3]

M14. (a) (i) Single reagent

If wrong single reagent, CE = zero

Incomplete single reagent (e.g. carbonate) or wrong formula (e.g.NaCO ) loses

3

reagent mark, but mark on

For “no reaction” allow “nothing”

Different reagents

Page 39
 Year 2 – Organic Synthesis and analysis
If different tests on E and F; both reagents and any follow
on chemistry must be correct for first (reagent) mark.
Reagent must react: i.e. not allow Tollens on G (ketone) – no reaction.
Second and third marks are for correct observations.
i.e. for different tests on E and F, if one reagent is correct and one wrong, can
score max 1 for correct observation with correct reagent.

PCl PCl5 3

SOCl 2

E ester

Na CO /NaHCO named carbonate

2 3 3

metal e.g.Mg

no reaction

no reaction

named indicator

no effect

No reaction
1

F acid

Na CO /NaHCO named carbonate

2 3 3

Effervescence or CO 2

metal e.g.Mg

Effervescence or H 2

named indicator

acid colour
fumes
1

(ii) Single reagent

If wrong single reagent, CE = zero

Incomplete single reagent (e.g. carbonate) or wrong
formula (e.g.NaCO ) loses reagent mark, but mark on
3

Page 40
 Year 2 – Organic Synthesis and analysis
For “no reaction” allow “nothing”

Different reagents

If different tests on E and F; both reagents and any

follow on chemistry must be correct for first (reagent) mark.
Reagent must react: i.e. not allow Tollens on
G (ketone) – no reaction.
Second and third marks are for correct observations.
1

i.e. for different tests on E and F, if one reagent is correct

and one wrong, can score max 1 for correct observation
with correct reagent.

G ketone

AgNO 3

no reaction

Na CO /NaHCO named carbonate

2 3 3

water

no reaction

named indicator

no effect

Named alcohol

no reaction

Named amine or ammonia

no reaction
1

H Acyl chloride

AgNO 3

(white) ppt

Na CO /NaHCO named carbonate

2 3 3

Effervescence or CO or fumes or exothermic

2

water

fumes

Page 41
 Year 2 – Organic Synthesis and analysis
named indicator

acid colour

Named alcohol

Smell or fumes

Named amine or ammonia

fumes
1
Allow iodoform test or Brady’s reagent (2,4,dnph) test (both
positive for G)

(iii) Single reagent

If wrong single reagent, CE = zero

Incomplete single reagent (e.g. carbonate) or wrong
formula (e.g.NaCO ) loses reagent mark, but mark on
3

For “no reaction” allow “nothing”

Different reagents

If different tests on E and F; both reagents and any follow

on chemistry must be correct for first (reagent) mark.

Reagent must react: i.e. not allow Tollens on

G (ketone) – no reaction.

Second and third marks are for correct observations.

i.e. for different tests on E and F, if one reagent is correct

and one wrong, can score max 1 for correct observation
with correct reagent.
1

J Primary alcohol

K Cr O / H
2 2 7
+

goes green

KMnO / H 4
+

decolourised / goes brown

Lucas test (ZnCl /HCl)

2

Penalise missing H but mark on

+

Page 42
 Year 2 – Organic Synthesis and analysis

K Tertiary alcohol

K Cr O / H
2 2 7
+

No reaction

KMnO / H 4
+

no reaction

Lucas test (ZnCl /HCl)2

Rapid cloudiness
1
If uses subsequent tests e.g. Tollens/Fehlings, test must be
on product of oxidation

(b) (i) 3,3-dimethylbutan-1-ol

Allow 3,3-dimethyl-1-butanol
1

4
1

Triplet on three
1

(ii) 2-methylpentan-2-ol
Allow 2-methyl-2-pentanol
1

5
1

Singlet or one or no splitting

1
[15]

M15.(a) If 2 stage test for one compound, award no marks for that compound, eg no
mark for ROH or RX to alkene then Br2 test. If reagent is wrong or missing, no

Page 43
 Year 2 – Organic Synthesis and analysis
mark for that test; if wrong but close/incomplete, lose reagent mark but can
award for correct observation. In each test, penalise each example of wrong
chemistry, eg AgClr2

propan-1-ol

acidifiedpotassiumdichromate

sodium

Named acid + conc H2SO4

named acyl chloride

PCl5

M1
1

(orange) turns green

effervescence

Sweet smell

Sweet smell /misty fumes

Misty fumes

M2
1

propanal

add Tollens or Fehlings / Benedicts

acidifiedpotassiumdichromate

Bradys or 2,4-dnph
if dichromate used for alcohol cannot be used for aldehyde

M3
1

Tollens: silver mirror or Fehlings/ Benedicts: red ppt

(orange) turns green

Yellow or orange ppt

Page 44
 Year 2 – Organic Synthesis and analysis
M4
1

propanoic acid

Named carbonate/ hydrogencarbonate

water and UI (paper)

Named alcohol + conc H2SO4

sodium or magnesium

PCl5
if sodium used for alcohol cannot be used for acid

M5
1

effervescence

orange/red

Sweet smell

effervescence

Misty fumes
if PCl5 used for alcohol cannot be used for acid

M6
1

1-chloro propane

NaOH then acidified AgNO3

AgNO3
If acidification missed after NaOH,no mark here but allow
mark for observation

M7
1

white ppt

white ppt

Page 45
 Year 2 – Organic Synthesis and analysis
M8
1

(b) oxidation (of alcohol by oxygen in air)

M1
1

absorption at 1680 -1750 (due to C=O)

Must refer to the spectrum

M2
1

comparison of polarity of molecules or correct imf statement:propanone is less polar

OR propan-2-ol is more polarOR propanone has dipole-dipole forcesOR propan-2-ol
has hydrogen bonding

M3
1

about attraction to stationary phase or solubility in moving phasePropan-2-ol has

greater affinity for stationary phase or vice versaOR propanone is more soluble in
solvent/moving phase or vice versa

M4
1
[12]

M16.(a) CH COCl + AlCl

3 3 CH CO
3
+
+ AlCl 4
–

Allow RHS as
Allow + on C or O in equation but + must be on C in
mechanism below
Ignore curly arrows in equation even if wrong.
1

AlCl + H
4
– +
AlCl + HCl
3

Page 46
 Year 2 – Organic Synthesis and analysis

• M1 arrow from within hexagon

to C or to + on C
• + must be on C of RCO in mechanism
• + in intermediate not too close to C1
• gap in horseshoe must be centred approximately around
C1
• M3 arrow into hexagon unless Kekule
• allow M3 arrow independent of M2 structure
• ignore base removing H for M3
• NO mark for name of mechanism
3

Phenylethanone ignore 1 in name, penalise other numbers

Note: this is the sixth marking point in (a)
1

(b)
+ must be on C
But allow [C H CO]
6 5
+

(c) M1 about electrons

methyl group has (positive) inductive effect OR increases electron density on

benzene ring OR pushes electrons OR is electron releasing

Page 47
 Year 2 – Organic Synthesis and analysis
Ignore reference to delocalisation
1

M2 about attraction

electrophile attracted more

or benzene ring better nucleophile

Allow intermediate ion stabilised
M2 only awarded after correct or close M1
1
[9]

M17.(a)
• M2 not allowed independent of M1, but allow M1 for
correct attack on C+
• + rather than δ+ on C=O loses M2
• If Cl lost with C=O breaking, max1 for M1
• M3 for correct structure with charges but lp on
O is part of M4
• only allow M4 after correct/very close M3
• ignore Cl removing H
– +

(b) (i) pentane-1,5-diol

Second ‘e’ and numbers needed
Allow 1,5-pentanediol but this is not IUPAC name

Page 48
 Year 2 – Organic Synthesis and analysis

(ii)
Must show ALL bonds
1

(iii) All three marks are independent

M1 (base or alkaline) Hydrolysis (allow close spelling)

1

Allow (nucleophilic) addition-elimination or saponification

M2 δ+ C in polyester
1

M3 reacts with OH or hydroxide ion

–

Not reacts with NaOH

1

(c) (i)
Allow CH COOH or CH CO H
3 3 2

(ii) (nucleophilic) addition-elimination

Both addition and elimination needed and in that order

OR

(nucleophilic) addition followed by elimination

Do not allow electrophilic addition-elimination / esterification
Ignore acylation
1

(iii) any two from: ethanoic anhydride is

Page 49
 Year 2 – Organic Synthesis and analysis
• less corrosive

• less vulnerable to hydrolysis

• less dangerous to use,

• less violent/exothermic/vigorous reaction OR more controllable rxn

• does not produce toxic/corrosive/harmful fumes (of HCl) OR does not

produce HCl

• less volatile
NOT COST
List principle beyond two answers
2

(d)

(e) (i) ester

Do not allow ether
Ignore functional group/linkage/bond
1

(ii) 12 or twelve (peaks)

1

(iii) 160 – 185

Allow a number or range within these limits
Penalize extra ranges given
Ignore units
1

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 Year 2 – Organic Synthesis and analysis

(f) (i) sulfuric acid sodium hydroxide

hydrochloric acid ammonia X or blank

ethanoic acid potassium hydroxide

nitric acid methylamine X or blank

4 correct scores 2
3 correct scores 1
2 or 1 correct scores 0
2

(ii) Pink to colourless

Allow ‘red’ OR ‘purple’ OR ‘magenta’ instead of ‘pink’
Do not allow ‘clear’ instead of ‘colourless’
1
[21]

M18.In each section

• If wrong or no reagent given, no marks for any observations;

• Penalise incomplete reagent or incorrect formula – but mark observations

• Mark each observation independently

• Allow no reaction for no change / no observable reaction in all three parts, but
not none or nothing

• Q says one test. If two tests are given, score zero

(a)

Lucas test
K Cr O / H +
KMnO / H +

(ZnCl / HCl)
2 2 7 4
2

R (Orange) goes (purple) goes No

Page 51
 Year 2 – Organic Synthesis and analysis

green Penalise colourless /

Primary alcohol wrong starting decolourises allow cloudiness
colour goes brown

S no change / no
no change / no Rapid
observable
Tertiary alcohol observable reaction cloudiness
reaction

1
Allow acidified potassium manganate and acidified
potassium dichromate without oxidation numbers

(b)

Na CO / NaHCO
metal eg Mg named indicator
2 3 3

named carbonate

PCl 5PCl 3

SOCl 2

Named alcohol + HCl / H SO 2 4

T no change / no no change / no
no effect
ester observable reaction observable reaction

no change / no observable reaction

1

U Effervescence or Effervescence or (H )
acid colour
2

Acid (CO ) gas formed

2 gas formed

Fumes / (HCl) gas formed

Page 52
 Year 2 – Organic Synthesis and analysis
Sweet smell
1

(c)

Fehling’s / Tollens’ / [Ag(NH )2]

3
+
K Cr O /
2 2 7

Benedict’s H +

I / NaOH
2

no change / no change /
V no change / no
no no observable
observable
Ketone observable reaction
reaction
reaction

Yellow ppt
1

(Orange)
W goes green
Red ppt Silver mirror Penalise
aldehyde wrong starting
colour

no change / no observable reaction

1
[9]

Page 53