2016 HYDROXY COMPOUNDS (ALCOHOLS AND PHENOLS)

H1 / H2
Summary of Reactions

Complete the following table.

Starting Compound

(CH3)2CHCH(OH)CH3

Reaction Type

Reagents and
Conditions

Organic Product(s) [if any]

redox
or acid-metal

Na @
room temp.

(CH3)2CHCH(O-Na+)CH3

neutralisation
or acid-base
neutralisation
or acid-base
nucleophilic
substitution
[H1: substn]
nucleophilic
substitution
[H1: substn]

NaOH
room temp.

no reaction
[alcohol is neutral to litmus]
no reaction
[alcohol is neutral to litmus]

Oxidation

Na2CO3
room temp.
HBr (or PBr3)
reflux
SOCl2 (or conc
HCl, ZnCl2 cat)
reflux
K2Cr2O7 / H+ #
reflux

(CH3)2CHCHBrCH3

(CH3)2CHCHClCH3
(CH3)2CHCOCH3

Elimination

excess conc.
H2SO4
170C

(CH3)2C=CHCH3 (major)
(CH3)2CHCH=CH2 (minor)

nucleophilic
substitution
[H1: substn]

CH3CH2CO2H
conc. H2SO4
reflux

(CH3)2CHCH(CH3)OCOCH2CH3

nucleophilic
substitution
[H1: substn]

CH3COCl
room temp.

(CH3)2CHCH(CH3)OCOCH3

oxidative
cleavage

I2 / NaOH(aq) *
warm (<70C)

(CH3)2CHCO2-Na+
CHI3

Remarks:
@ Na is used to identify OH group in alcohol, phenol and carb acid
# K2Cr2O7 / H+ is used to identify 1 alcohol, 2 alcohol and aldehyde
* Alkaline aqueous I2 is used to identify CH3CH(OH) or CH3CO
structural unit in organic compounds
1

Level 1 and 2
Section A
1

Which pair of reagents cannot be used to prepare CH3CH2Cl?

A
B
C
D

CH2==CHCl
CH3CH2OH
CH3CH2OH
CH3CH2OH

+
+
+
+

H2
HCl
PCl5
Cl2
N97/III/27

Ans: D
2

What is the structural formula of the compound formed when

CH2CHCH2CHO reacts with NaBH4?
A

CH2CHCH2CO2H

CH2CHCH2CH2OH

CH3CH2CH2CHO

CH3CH2CH2CH2OH

H2 N15/I/23
Ans: B [NaBH4 only reduces aldehyde to 1 alcohol but not
alkene to alkane]
3

Which compound reacts with its own oxidation product (an

oxidation which involves no loss of carbon) to give a sweet
smelling liquid?
A
B
C
D

propanal
propanoic acid
propanone
propan-1-ol
J95/IV/26

[O]
CH3CH2CHO

CH3CH2CO2H

no reaction

CH3CH2CO2H

[O]

no reaction

CH3COCH3
[O]
CH3CH2CH2OH

CH3CH2CO2H

CH3CH2CO2CH2CH2CH3
ester
Ans: D
4

Which of the following isomers of C5H11OH gives, on

dehydration, the greatest number of different alkenes?
A

CH3 CH2 CH CH2OH

CH3

CH3 CH2 CH2 CH CH3

OH

CH3 CH2 CH CH2 CH3

OH

D
J93/IV/26

CH3 CH2 CH CH2OH

CH3
CH3 CH2 CH2 CH CH3
OH

CH3 CH2 CH CH2 CH3

OH

CH3 CH2 CH CH2

CH3
CH3 CH2 CH C CH3
H
CH3 CH2 CH2 C CH2
H
CH3 CH CH CH2 CH3

Ans: B
5

All the isomeric alcohols with the molecular formula C5H12O are
added separately to warm alkaline aqueous iodine.
How many of the isomers will give a pale yellow precipitate?
(Ignore stereoisomers.)
A 0

B 1

C 2

D 3
H2 N07/I/26

Ans: C [CH3CH(OH)CH2CH2CH3; CH3CH(OH)CH(CH3)2]

Section B
6

Bacteria have been suggested as a possible means of cleaning

up oil spillages. Some bacteria contain enzymes that can insert
one or more oxygen atoms into any carbon-hydrogen bond in
an alkane. This converts a water-insoluble alkane into a watersoluble alcohol, e.g.
CH3CH3 CH3CH2OH
Which of the following alcohols could be obtained by this
process from (CH3)2CHCH2CH3?
1
2
3

(CH3)2C(OH)CH(OH)CH3
CH3CH(OH)CH(CH3)2
CH3CH2CH(CH2OH)2
4

Ans: A (all)
N95/IV/39
Section C
7

Alcohol B has esters which are responsible for the flavours of

various fruits and has the molecular formula C5H12O. Reaction
of B with acidified potassium dichromate(VI) produces a
compound C, C5H10O2. Heating B over Al2O3 produces D,
C5H10. Vigorous oxidation of D forms 2-methylpropanoic acid
as one of the products.
Suggest structures for B, C and D and explain the reactions
involved.
B being an alcohol, undergoes elimnation (loss of H2O)
when heated with Al2O3 to give an alkene, D. Oxidising D
loses a carbon suggests that D is a terminal alkene. From
the formula of 2-methylpropanoic acid, D is therefore 3methylbut-1-ene.

CH3 CH CH
CH3
D

CH2

[O]

CH3 CH COOH
CH3
+ CO2 + H2O

From the dehydration reaction, B is either

CH3 CH CH2 CH2OH

or
CH3

CH3 CH CH CH3
CH3 OH
.

However, oxidation of B to C gives an additional oxygen in

the product C, suggests that C is a carboxylic acid and
hence B is a primary alcohol, i.e.

CH3 CH CH2 CH2OH [O] CH3 CH CH2 CO2H

CH3
CH3
B
C
J94/I/10

8(a) (i)

Calculate the oxidation number of carbon in methanol,

CH3OH.
-2

(ii)

(iii)

Using only the elements C, H and O, draw the structural

formulae of three compounds, A, B and C, each
containing a single carbon atom with an oxidation number
of zero, +2 and +4 respectively.
A:

HCHO

(0)

B:

HCO2H

(+2)

C:

CO2

(+4)

Suggest reagents and conditions for converting methanol

into each of the three compounds A, B and C.
CH3OH HCHO

K2Cr2O7 / dil H2SO4; distil

CH3OH HCO2H

K2Cr2O7 / dil H2SO4; reflux

CH3OH CO2

KMnO4 / dil H2SO4 (OR excess O2;

heat)
H2 N09/III/2(a)

Suggest synthetic routes to the following dicarboxylic acids

starting from 1,2-dibromoethane.
(a)

BrCH2CH2Br HO2CCO2H
BrCH2CH2Br HOCH2CH2OH HO2CCO2H
NaOH(aq)
reflux

K2Cr2O7 / H2SO4(aq)
reflux

Note: KMnO4 is not acceptable as it will further

oxidise (CO2H)2 to CO2.
(b)

BrCH2CH2Br HO2C(CH2)2CO2H
BrCH2CH2Br NCCH2CH2CN HO2C(CH2)2CO2H
KCN(alc)
reflux

H2SO4(aq)
reflux
H2 N11/III/2(d)

H2 Only
Section A
10

Which of the following could be a correct synthesis of aspirin

CO2H
OCOCH3 ?

CO2CH3
NaOH (aq)
OCOCH3
under reflux
CO2H
OH

CH3COCl (aq)

CO2Na+
H+ (aq)
OCOCH3

CO2H
OCOCH3

CO2H
OCOCH3 + HCl

room temperature

CN

OCOCH3

NaOH (aq)

CO2Na+
H+ (aq)
OCOCH3

CO2H
OCOCH3

under reflux
CO2H
conc. H2SO4
OH + CH CO H
3
2
under reflux

CO2H
OCOCH3 + H O
2

N90/I/29
Ans: B
Section C
11(a) The antiseptic TCP contains 2,4,6-trichlorophenol.
(i)

Which laboratory reagent and conditions would you use

to convert phenol into 2,4,6-trichlorophenol?
Excess aqueous chlorine, Cl2(aq), room temperature

(ii)

Suggest whether 2,4,6-trichlorophenol is more or less

acidic than phenol. Explain your answer.
More acidic
Cl is electronegative and hence exerts electron
withdrawing inductive effect. When TCP ionises to form
the phenoxide anion, the negative charge is further
dispersed by the 3 Cl atoms and the anion is stabilised.
Hence, TCP has a higher tendency to ionise to give H+
7

(i.e. equilibrium lies more to the right) and is therefore

more acidic than phenol.

OH
Cl

Cl

Cl

Cl
+ H+

Cl
(b)

Cl

Suggest structural formulae for the organic products of the

reactions of phenylmethanol with
(i)

HBr

CH2Br

(ii)

Cr2O72 / H+

CO2H

(c)

Suggest why phenol does not undergo a similar reaction with

that in (b)(ii).
Absence of hydrogen atom at the carbon atom (the
carbon) carrying the OH group.
J99/I/7

Level 3
Section D
12

Alcohol J, CxHyOH, is a volatile fungal metabolite whose

presence when detected in air can indicate hidden fungal attack
on the timbers of a house.
When 0.10 cm3 of liquid J was dissolved in an inert solvent and
an excess of sodium metal added, 10.9 cm3 of gas (measured
at 298 K) was produced.
When 0.10 cm3 of liquid J was combusted in an excess of
oxygen in an enclosed vessel, the volume of gas (measured at
298 K) was reduced by 54.4 cm3. The addition of an excess of
NaOH(aq) caused a further reduction in gas volume of 109 cm3
(measured at 298 K).
(i) Use these data to calculate values for x and y in the
molecular formula CxHyOH for J.
nhydrogen gas = 10.9 / (24x103) = 4.54 x 10-4 mol
2ROH + 2Na 2RO-Na+ + H2
No. of mol of alc = 2 x 4.54 x 10-4 mol = 9.08 x 10-4 mol
Since CO2 reacts with NaOH to give a further
contraction of 109 cm3,
no. of mol of CO2 prod = 109 / (24 x 103) = 4.54 x 10-3 mol
CxHyOH(l) + (x+(y+1)/4-)O2(g) xCO2(g) + (y/2+)H2O(l)
9.08 x 10-4 mol
4.54 x 10-3 mol
1 mol
:
5 mol
Therefore, x = 5
Since there is an initial contraction of 54.4 cm3,
(VO2 reacted + Vexcess O2) (VCO2 + Vexcess O2) = 54.4
VO2 reacted 109 = 54.4
VO2 reacted = 163.4 cm3
No. of mol of O2 reacted = 163.4 / (24 x 103) = 6.81 x 10-3
C5HyOH(l) + (5+(y+1)/4-)O2(g) 5CO2(g) + (y/2+)H2O(l)
9.08 x 10-4 mol 6.81 x 10-3 mol
1 mol
:
7.5 mol
5 + (y+1)/4 = 7.5
y = 11
Therefore, formula is C5H11OH.
9

Alcohol J reacts with acidified K2Cr2O7, and can be dehydrated

to alkene K. On treating K with an excess of hot acidified
concentrated KMnO4, an equimolar mixture of ethanoic acid
and propanone is produced.
(ii)

Use this information to deduce the structural formulae for

J and K, explaining your reasoning.

Since CH3COOH and CH3COCH3 are obtained in a 1:1 mole

ratio on oxidative cleavage of alkene K,
K must be

J must be a secondary alcohol (not a tertiary alcohol) since it

can be oxidized by K2Cr2O7/H+.
Hence J must be

(iii)

Suggest suitable reagents and conditions for the

conversion of J into K.
Excess concentrated H2SO4, 170C

(iv)

Explain whether K can show geometrical isomerism.

K cannot show geometrical isomerism as one of the
carbon atoms of the double bond has 2 identical CH3
groups attached to it.
[8]
H2 N10/III/3(d)

10

SUPPLEMENTARY QUESTIONS
Topic 10.4 (FBP Topical TYS)
H1 / H2
1.

MCQ

Sect A

N04/I/24

A
A: CH3CH2OH(l) CH2=CH2(g) + H2O(l)
B: CH3CO2H(l) + CH3CH2OH(l) CH3CO2CH2CH3(l) + H2O(l)
C: CH3CH2OH(l) + 2[O] CH3CO2H(l) + H2O(l)
D: CH3CH2OH(l) + HBr(g) CH3CH2Br(l) + H2O(l)
2.

MCQ

Sect A

N09/I/1

A
Based on the given info, the structural formula of sugar is
CH2(OH)CH(OH)CH(OH)CH(OH)CH(OH)CHO
which has 5 OH groups and thus will react with 5 mol of Na
to produce 2.5 mol of H2 gas as shown:
2ROH + 2Na 2RO-Na+ + H2
3.

Essay

Paper 3

N05/III/8(a)

(a) PBr3, reflux

(b) Acidified potassium dichromate(VI), distil
(c) Excess concentrated H2SO4, 170oC
H2 Only
4.

MCQ

Sect A

N10/I/27

B
Alcohol is neutral to litmus and thus does not react with
basic NaOH whereas phenol and carboxylic acid groups
are acidic and will thus react with NaOH to give phenoxide
and carboxylate respectively

11

5.

MCQ

Sect B

N05/I/39

D (only 1)
1: Nucleophilic substitution to form ester
2: Phenol cannot be oxidized in the same way as 1 & 2
alcohols
3: Partial double bond character for C-O bond in phenol
makes the bond too strong to be substituted
6.

MCQ

Sect B

N07/I/38

B (1 & 2 only)
1: Phenol is a weak acid and thus dissociates partially to
produce H+ resulting in an acidic solution
2: Dinoseb contains a chiral centre and thus exists in
optically active forms
3: Phenol reacts with acyl chloride (not alcohol) to
produce ester
7.

Structured

Paper 2

N05/II/4

(a) Cl2 in CCl4 (use less polar medium provided by CCl4

instead of aqueous medium to effect mono-substitution)
Room temperature
(b)It is to form O- anion which is a stronger nucleophile
than uncharged phenol molecule for the nucleophilic
substitution reaction to take place at a higher rate.
(c) HCl(aq) or H2SO4(aq)
(d)ortho to OH group in the ring
(e) (i) Acidified KMnO4, Heat
(ii) Purple KMnO4 would be decolorized and a white
ppt would be observed for MCPA but not for 2,4-D.
(iii) Replace CH3 group in MCPA with COOH.

12