Suggested solutions

1 B 2 B 3 B 4 D 5 B

Section A: Multiple Choice Questions (5 marks)

1 Why does hydrogen cyanide add to propanone but not to propene?

A The addition product formed with propene would not be stable.

B Propanone is more susceptible to nucleophilic attack than propene.
C Propanone is more susceptible to electrophilic attack than propene.
D Propanone is more susceptible to free radical attack than propene.
( B )

Unlike propene in which C=C bond is electron rich, C in the C=O bond of propanone
is electron deficient as it is bonded to an electronegative O atom. Hence, C in the C=O
bond will be attacked by nucleophile, which is CN– in this case.

2 How many structural isomers with molecular formula C4H8O can reduce a solution containing
Ag(NH3)2+ ions?

A 1 B 2 C 3 D 4
( B )
C4H8O can represent both ketone and aldehyde functional groups.

However, only aldehyde can be oxidised by Ag(NH3)2+. They are CH3CH2CH2CHO,

(CH3)2CHCHO.

3 Aldehydes and ketones are produced industrially by the catalytic oxidation of alkenes, e.g.,
ethanal is manufactured from ethene as shown below.

H2C=CH2 + ½ O2 → CH3CHO

The process is also used industrially with but–2–ene.

Which compound would be produced from but–2–ene?

A CH3CH2CHO C (CH3)2CHCHO
B CH3COCH2CH3 D CH3CH2CH2CHO
( B )

Identify the pattern for the reaction:

1 2
H2C=CH2 + ½ O2 → CH3CHO

In forming the product, one H from C2 is shifted to C1 and one O is added to C2.

2 3
For but-2-end, CH3CH=CHCH3, one H from C3 is shifted to C2 and one O is added to C3
to form CH3CH2COCH3, which is identical to CH3COCH2CH3 in option (B).

1
4 The first stage in the synthesis of Antipyrine, a drug used in reducing fever, is the
reaction between compound P and phenylhydrazine.

CH3COCH2CO2CH2CH3 +

What will be the product Q of this first stage?

( D )

Condensation reaction occurs between the C=O group and phenylhydrazine, where the
O from C=O (in P) and 2 H atoms bonded to the first N atom (in phenylhydrazine) are
removed in the form of a H2O molecule.

CH3 C CH2CO2CH2CH3
CH3 C CH2CO2CH2CH3 + N N H →
N N
O H H
H

+ H2O

2
5 When the apparatus below was used with compound Q, an orange precipitate was formed in
the right-hand test-tube.

Which could be compound Q?

1 CH3CH2CH2OH
2 CH3CH(OH)CH3
3 (CH3)3COH

A 1, 2 and 3 C 1 only
B 1 and 2 only D 2 and 3 only
( B )

Q must be a primary (option 1) or secondary (option 2) alcohol which will be oxidised

by acidified K2Cr2O7 to form aldehyde and ketone respectively. Both aldehyde and
ketone contain C=O group which will react with 2,4–DNPH to form the orange ppt via
condensation reaction. In this case, option 3 cannot be Q as it is a tertiary alcohol.

Section B: Structured Questions (15 marks)

6 For each pair of isomers below, propose a simple chemical test to distinguish between the
two compounds.

In each case, you should give the reagents and conditions of the test, and describe what you
would observe.

(a) CH3(CH2)3CHO and CH3CH2COCH2CH3 [2]

[1] Ammonical soln of [Ag(NH3)2]+ (Tollen’s reagent), heat

[½] Silver mirror formed with CH3(CH2)3CHO
[½] No silver mirror CH3CH2COCH2CH3
OR
[1] Alkaline soln of Cu2+ complex (Fehling’s solution), heat
[½] Brick-red ppt of Cu2O with CH3(CH2)3CHO,
[½] No brick-red ppt with CH3CH2COCH2CH3
OR
[1] KMnO4(aq) and H2SO4(aq), ✓heat
[½] Decolorisation of purple KMnO4 by CH3(CH2)3CHO
[½] Purple solution remains for CH3CH2COCH2CH3
3
 (b) CH3CO(CH2)2CH3 and CH3CH2COCH2CH3 [2]

[1] NaOH(aq) and I2, warm

[½] Yellow ppt (of CHI3) formed with CH3CO(CH2)2CH3
[½] No yellow ppt with CH3CH2COCH2CH3
[Total: 4]

7 (a) Chloral hydrate (2, 2, 2–trichloroethane–1, 1–diol) is a sedative drug that can be made by
adding trichloroethanal to water, as shown:

This reaction is a nucleophilic addition reaction. It can be catalysed by small amounts of

hydroxide ions, OH–.

Complete the diagram to suggest a mechanism to show how chloral hydrate is formed.
Show all charges and relevant lone pairs and show the movement of electron pairs by
using curly arrows. [3]

[½] Lone pair on hydroxide

[½] partial charges on C=O bond
[½] Pair of curly arrows
[½]Correct intermediate structure

[1]Balanced eqn showing regeneration of OH– catalyst

(b) The yield of chloral hydrate is lower in the presence of higher concentrations of hydroxide
ions.
An alkaline aqueous solution of trichloroethanal will undergo a different reaction to form
methanoate ions, HCO2–, and a liquid that is immiscible with water.

Suggest an equation for this reaction. [1]

[1]CCl3CHO + OH– → HCO2– + CHCl3
[Total: 4]

4
8 (a) Consider the following reaction scheme:

HO CHO Stage 1 Stage 2

Compound A Norepinephrine

HO

(i) Suggest a structure for compound A. [1]

[1]

(ii) State the reagents and conditions used for Stage 1 and Stage 2. [2]

Stage 1: HCN with trace amt of NaCN, r.t [1]

OR HCN with trace amt of NaOH, r.t [1]

Stage 2: LiAlH4 in dry ether, r.t [1]

OR H2, Ni, heat [1]
OR H2, Pt, r.t [1]

(iii) State the name of the reactions for Stage 1 and Stage 2. [2]

Stage 1: nucleophilic addition [1]

Stage 2: reduction [1]

(b) Menthol is a major constituent of peppermint oil. Menthol is made commercially from
piperitone, which occurs in eucalyptus oils.
CH3
H CH3

H
OH O
H CH(CH3)2 H CH(CH3)2
Menthol Piperitone

(i) What type of reaction is required to convert piperitone to menthol? [1]

Reduction [1]

(ii) Suggest reagents and conditions for the conversion of piperitone to menthol. [1]

H2, Ni, heat [1]

OR H2 , Pt, r.t [1]

[Note: LiAlH4 should not be used for reduction of an alkene generally.]

[Total: 7]