Name:

CG:

Class:

SERANGOON JUNIOR COLLEGE

H2 9647 CHEMISTRY
2015 JC2
Hydroxyl Compounds
Tutorial 6
Compulsory Questions
[To be discussed during tutorial. Do all questions on foolscap paper. Show all relevant
workings.]
1. Using the table below to compare and contrast the reactions of ethanol and phenol
with each of the following reagents. Include in your answer, the type of reaction,
balanced equations and all products formed.

Reagents

a
.

Sodium

b
.

Aqueous
potassium
hydroxide

OH

CH3CH2OH

Redox
CH3CH2O-Na+ + H2

Redox

No reaction

Neutralisation

O-Na+ + 1/2H2

O-K+
+ H2O

c. Phosphorus
pentachloride
d
.

Aqueous
bromine

Nucleophilic
substitution
CH3CH2Cl + POCl3 + HCl
No reaction

No reaction

Electrophilic
substitution

Br
Br

OH
Br

e
.

Conc H2SO4
with ethanoic
acid, reflux

esterification/
nucleophilic
substitution of
CH3COOH
CH3COOCH2CH3 + H2O

HBr
No reaction

Comments (Any
differences in
reactions?
Reasons for
reaction /
no reaction)
1 mol of ethanol or
phenol produced
only mol of H2
Alcohols are
weaker acids than
water

considered to be
neutral.
Strong C-O bond in
phenol, no
nucleophilic sub.
-OH group is a
strong activating
group (2,4,6-)
Question: What is
the difference in
product if liquid
bromine is used?
Phenol
requires
acyl chloride to
form ester.

f.

Acidified hot
Potassium
manganate(VII)
/ potassium
dichromate(VI)

Oxidation

no reaction as oxidation
will result in destruction
of
the
aromatic
character

CH3COOH + H2O

2. Identify all the five functional groups present in the compound below. State the type of
reaction and draw the organic product when the structure below reacts with:

Functional Groups:

OH

1.
2.
3.
4.
5.

H
ClCH2

CH CHCH2OH

OH

2(a)

1o alcohol
2o alcohol
Phenol
Alkene
Halogenoalkane

sodium, rtp;

Reagent

Type of reaction(s)
Product
(Circle the functional group(s)
involved in the reactions)

(a) Sodium, rtp

O-Na+

OH
H
ClCH2

CH CHCH2OH

ClCH2

OH

1. Redox
/
acid
displacement
(b) aqueous
sodium
hydroxide,
heat;

CH CHCH2O-Na+

C
O-Na+

metal

O-Na+

OH
H
ClCH2

CH CHCH2OH

OH

HOCH2

CH=CHCH2OH

OH

1. Nucleophilic substitution
2. Neutralisation
(c) thionyl
chloride,
SOCl2

OH

OH

H
ClCH2

CH CHCH2OH

OH

1. Nucleophilic substitution

H
ClCH2

C
Cl

CH CHCH2Cl

(d) ethanoic
acid, conc.
H2SO4,
reflux

OH

OH
H

H
ClCH2

CH CHCH2OH

ClCH2

CH CHCH2O CCH3

O CCH3

OH

O
1. Nucleophilic substitution /
esterification
Note: Phenol doesnt react
carboxylic acids to form esters.

(e) ethanoyl
chloride, rtp

OH

with

O
O CCH3

H
ClCH2

CH CHCH2OH

OH

H
ClCH2

1. Nucleophilic substitution /
acylation
(f) aqueous
iodine, rtp

CH CHCH2O CCH3

O CCH3
O

OH

OH
I

I
H
ClCH2

CH CHCH2OH

ClCH2

OH

1. Electrophilic addition
2. Easy electrophilic
substitution

C
OH

CH CHCH2OH
I

OH I

Can have alternative product (EA)

3. Outline, with equations, reagents and essential conditions, how the following conversions
could be efficiently carried out:
(a)
Butan-1-ol to butan-2-ol

H H H H

H H H H

H C C C C H

H C C C C H

H H H OH
1 alcohol

H H OH H
2 alcohol

H H H H

II

H C C C C H
H H

H H H H
I:

H C C C C H
H H H OH

H H H H
H C C C C H

+ H2O

H H

Reagents & Conditions:

excess concentrated H2SO4, heat, 170C
Type of reaction:
Elimination

II :

H H H H

H C C C C H

H2O

H H H H
H C C C C H

H H

H H OH H

Reagents & Conditions:

steam, H3PO4, heat at 300C, 70 atm
Type of reaction:
Electrophilic addition
(b) cyclopentanol to cyclopentylmethanol (hint: 4 steps)
5 carbon
alcohol

OH

CH2OH

IV

6 carbon
1 alcohol

II

Cl

I:

+ PCl5

OH

III

CN

Cl

COOH

+ POCl3 + HCl

Reagents & Conditions:

PCl5 , room temperature
Type of reaction:
Nucleophilic substitution

II :

+ KCN

Cl

CN

+ KCl

Reagents & Conditions:

alcoholic KCN, heat
Type of reaction:
Nucleophilic substitution

III :

CN

+ HCl + 2 H2O

Reagents & Conditions:

dilute HCl, heat
Type of reaction:
Acidic hydrolysis

COOH

+ NH4Cl

IV :

COOH

CH2OH

+ 4[H]

+ H2O

Reagents & Conditions:

LiAlH4 in dry ether, rtp
Type of reaction:
Reduction
O
OH

C
CH2

CH2CH2OH
to

(hint: 3 steps)

(c)

O
OH
O

CH2CH2OH

C
CH2

III

OH

OH
CH2COOH

CH2COCl

II
OH

OH
CH2CH2OH

+ 2[O]

CH2COOH

+ H2O

I:

Reagents & Conditions:

Type of reaction:

K2Cr2O7 in H2SO4 (aq), heat

Oxidation

*** cannot use KMnO4,

otherwise side chain
oxidation will result in
benzoic acid formed

OH

OH
CH2COOH
+

CH2COCl
+

PCl5

POCl3

HCl

II :
Reagents & Conditions:
Type of reaction:
III :

PCl5 (s), rtp

Nucleophilic substitution

Reagents & Conditions: rtp

Type of reaction: Nucleophilic substitution

2. Acyl chloride + phenol ester

Concepts: 1. cyclic ester

4. Cyclohexanol can be synthesised from cyclohexene as follows:

Br

OH

CH2NH2

Step I

Step III

Step II

(a) State the type of reaction and essential reagents and conditions for step I and II.
I:
II:

Reagent/Conditions: HBr (g), r.t.p

Type of rxn: Electrophilic Addition
Reagent/conditions: Aqueous KOH, reflux
Type of rxn: Nucleophilic Substitution

(b) Suggest a suitable synthesis pathway for step III using the minimum number of steps.

OH

PCl5,
rtp

Cl

Alc.
KCN,
heat

CN

LiAlH4
in dry
ether,
rtp

CH2NH2

(c) Explain why phenol could not be synthesised from bromobenzene.

Br

OH

Electrophilic
substitution

The p orbital of the bromine atom can overlap with the -electron cloud of the
benzene ring. As a result, the lone pair of electrons on the Br atom can
delocalise into the benzene ring.

This results in partial double bond character in C-Br bond and the
strengthening of the C-Br bond.

(d)

Br

does not undergo nucleophilic substitution/

substitution by a nucleophile / OH- is difficult

Draw the structural formula of all the organic products formed when compound Z
reacts with the following reagents.
OH
Cl
OH

CH2

CH
CH3

(d)(i) Hot, aqueous sodium hydroxide

O-Na+ OH
OH
CH2

CH
CH3

(d)(ii) Br2 in CCl4, absence of ultraviolet light

(d)(iii) Hot acidified KMnO4

5. Describe simple chemical tests to distinguish butanol, butan-2-ol and 2-methylbutan-2-ol.

You must include chemical reagents and conditions and write down appropriate
balanced chemical equations in your answer.

Step 1

Add potassium
dichromate(VI),
H2SO4(aq) to each
of the compound
separately and heat.

Step 2

Add 2,4-DNPH into

the resulting
mixtures from step 1
at rtp.

butanol
Orange turns green

No orange ppt

Observations
butan-2-ol
2-methylbutan-2-ol
Orange turns
Remains orange
green

Orange ppt
formed

No orange ppt

Equations:
CH3CH2CH2CH2OH + 2[O] CH3CH2CH2COOH + H2O
CH3CH2CH(OH)CH3 + [O] CH3CH2COCH3 + H2O

CH3CH2
C N N H

H N N H
NO2

NO2

CH3CH2COCH3 +

(will be covered in carbonyl compound)

CH3

NO2

NO2

+ H2O

6. Compound C is a diol commonly used in perfumes. It is also a useful intermediate for

the synthesis of other organic compounds as illustrated by the following scheme.

Given that compound C contains a tertiary alcohol, suggest structures for compounds
C, D, E and F.

H3C

OH

OH

CH3

CH3

H3C

OH

CH3

H3C

OH

CH3

7.

O-Na+

O-Na+ O

CH3

H3C

CH3

CH3

Alcohol B forms 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.
E, a structural isomer of B, decolourises purple potassium manganate (VII) to produce
a compound F, C5H10O. E forms a yellow precipitate G, when warmed with alkaline
aqueous iodine. When E is heated with concentrated sulfuric acid, it produces
CH3CH2CH=CHCH3 as one of the products.
Suggest the structures for B, C, D, E, F and G and explain the reactions involved.
Analysis (flowchart)

Analysis (flowchart)

Alcohol B (C5H12O) undergoes oxidation with hot acidified K2Cr2O7 to form C

(C5H10O2)
B is a primary (1) alcohol
C is a carboxylic acid (C5H10O2)

B undergoes elimination of H2O with hot Al2O3 to form D

D is an alkene (C5H10)

D undergoes oxidation to form 2-methylpropanoic acid as one of the products.

H H OH
2

H C C C O
H CH3
D has total 5 carbon: 4 Carbon

1 Carbon

D is an alkene with a terminal double bond

D:

H H H H
H C C C C H
H CH3
H H
H C C

H H
C C H

H CH3 H OH

CH3 H

O
C
OH

 B:

C:

(1 alcohol)

(carboxylic acid)

*** Chemical Equations are not required in this question.

Oxidation of B:
CH3CH(CH3)CH2CH2OH + 2[O] CH3CH(CH3)CH2COOH + H2O
Elimination of B:
CH3CH(CH3)CH2CH2OH CH3CH(CH3)CH=CH2 + H2O
Oxidation of D:
CH3CH(CH3)CH=CH2 + 5[O] CH3CH(CH3)COOH + CO2 + H2O
4

E (C5H12O), a structural isomer of B, undergoes oxidation with hot acidified KMnO4

to form F (C5H10O)
F has only one O atom it is a ketone (C5H10O)
E is a secondary (2) alcohol

E undergoes oxidation with alkaline aqueous iodine to form G

E is an must contain structure
H

C CH3
OH
G is yellow ppt, CHI3

H H H H
H C C C C CH3
6

E undergoes elimination to form

E:
(C5H12O)

H H H H

H H

as one of the products.

F:
(C5H10O)

H C C C C CH3

H H H
H C C C C CH3
H H H O

H H H OH
*** Chemical Equations are not required in this question.

Oxidaton of E to F:

H H H H
H C C C C CH3
H H H OH

H H H
H C C C C CH3
H H H O

[O]

+ H2O

Positive iodoform test of E to give G:

H H H H
H C C C C CH3

+ 4I2 + 6 OH

COO-

CH3CH2CH2

+ 5 I + 5H2O + CHI3

H H H OH
Elimination reaction of E:
CH3CH2CH2CH(OH)CH3

CH3CH2CH=CHCH3 + H2O

N2008/III/Q1(e)
The molecules of compound P, C7H15Br, are chiral. On treatment with NaOH (aq), P
produces alcohol Q, C7H15OH, which does not react with hot, acidified Na2Cr2O7 (aq).
The elimination of HBr from compound P produces a mixture of 4 different isomeric
alkenes with the formula C7H14, only two of which are geometrical isomers of each
other.
Suggest the structural formulae of compound P and the four alkenes.

Analysis: Q must be a 3 alcohol since it cannot be oxidised by hot acidified Na2Cr2O7

Compound P

CH3
H 3C C
H

Compound Q

Br

C CH3

CH3

CH3
H 3C C 3
H

OH

C2

C1 CH3

C 4H 3 H

CH3

Br

H 3C C

Remove H from C4
and Br from C2

Remove H from C3
and Br from C2

Remove H from C1
and Br from C2

CH3
H

C1 CH3

C 4H 3 H

H3C C

CH3

H
C

C CH3

CH2

H3 C C

CH3
H 3C

CH3
C C

CH3

cis isomer

H 3C C
H

C C

CH3

C CH3

CH3 H

CH3

H 3C C
H

CH3 H

CH3

CH3

H
CH3

trans isomer

2012/CJC/P2/Q5
9 (a) A reaction scheme involving compound B is shown below.

(i) Based on the above information, draw three possible structural isomers of B, which
are labelled as B1, B2 and B3.

B1
B2

B3

(ii) Based on the structural isomer B1, draw the structural formulae of C, D and E.

(b) A structural isomer of D, C8H8O, which is labelled as F, contains a C-O-C bond.

F does not react with HBr(g).
(i) Suggest a structural formula of F.

or

(ii) Although F does not react with HBr(g), it can react with concentrated HBr(aq). The
reaction of F with concentrated HBr(aq) is similar to the reaction of primary alcohols
with concentrated HBr(aq). The process involves the following two stages:

Suggest a mechanism for the Stage II process in the reaction of F with concentrated
HBr(aq), including curly arrows to denote movement of electrons, and all charges. You
do not need to draw the 3-dimensional representation of the molecules involved.

OR

[arrows, lone pair on Br- indicated, SN2 mechanism]

10. A student was given 5 unlabelled bottles and each bottle contains one of the following
organic substances.

CH3CH2CH2Br

CH3CH2CH(OH)CH3

C6H5CHCH2

C6H5OH

C6H5CH2OH

Outline a sequence of simple chemical tests which the student could use to identify
each of the above organic substances. For each test, state the reagents and
conditions used, type of reaction and describe the expected observations.
Test
1

Procedure
Add NaOH(aq) to each compound separately
and heat.
Acidify with excess dilute HNO3and then add
2-3 drops of AgNO3(aq).

Observation

Cream ppt. is observed in the

test tube that contains
CH3CH2CH2Br.
No cream ppt is observed in the
other test tubes
Decolourisation of brown
solution is seen. Yellow ppt of
CHI3 is formed for propan-2-ol
No yellow ppt. observed in other
test tubes.

Add I2(aq) to each of the remaining compound

separately, followed by NaOH(aq) and warm.

Add neutral FeCl3 (aq) to each of the

remaining compound separately at rtp.

Purple/violet complex observed

Add Br2(aq) in the dark to each of the

remaining compound separately at rtp.

Decolourisation of reddish-

To the last organic compound (C6H5CH2OH),

add KMnO4(aq) in H2SO4 (aq) and heat.
Or
To the last organic compound (C6H5CH2OH),
add K2Cr2O7(aq) in H2SO4 (aq) and heat.

Purple KmnO4 decolourised

Alternative Test for C6H5CH2OH.

To the last organic compound (C6H5CH2OH
add PCl5 at rtp and test gas evolved with
damp blue litmus paper.
END

for C6H5OH.
No purple/violet complex
observed in other test tubes.
brown solution observed for
C6H5CHCH2
No decolourisation of reddishbrown solution observed in
other test tubes.

Orange K2Cr2O7 turns green

White fumes of HCl that turns

damp blue litmus paper red

Name:

Date:

Class:

Score:

/20

Assignment Hydroxyl Compounds

[These questions are for submission.]
Deadline for submission __________________
1

(a)

Draw the structure of the organic product when compound Z reacts with the
following reagents.
CH3CH2
C
CH3

CHCH2OH

Cl

Z
(i)

Acidified KMnO4, heat

COOH

COOH
(ii)

[1]

Br2 (aq), room temperature and pressure

OH Br
CH3CH2

CHCH2OH

Cl

CH3 H
(iii)

[1]

CH3COOH, concentrated H2SO4, heat

CH3CH2
C

CHCH2

Cl

CH3

(b)

CH3

[1]

Outline, with reagents and essential conditions, how the following conversion could
be efficiently carried out.
CH3

CHO

to

CH3

COOH
KMnO4,
H2SO4
(aq),
heat

CH2OH
1. LiAlH4
in dry
ether
2. H2O,
heat

K2Cr2O7,
H2SO4 (aq),
heat with
distillation

CHO

[2] for all reagents and conditions correct

[5]

N11/A levels/P2/Q6 (modified)

2 Compound W has a molecular formula of C7H7OCl. It is an aromatic compound which
contains two functional groups.
Data about the reactions of W are given in the table.
Reaction
Reagent
1
AgNO3 (aq), warm
2
3

4
5

(i)

Result
White solid formed which is soluble in an
excess of NH3 (aq)
Br2 (aq) in excess
White solid formed which has an Mr = 379.2
MnO4 /OH
MnO4- is decolourised;
heat under reflux One organic product formed with Mr =138
then acidify
Na
Colourless gas evolved;
White solid formed which is soluble in H2O
NaOH(aq) at room Colourless solution formed
temperature

Identify the white solid formed in reaction 1, and hence name the functional group
that shows to be present in W.
White solid: AgCl (s)
Functional group: halogenoalkane [1] for both correct ans

(ii)

Based on reaction 4, two different functional groups could be present in W. Which

of these functional group is confirmed by reaction 5? Explain your answer.
Two functional groups that could be present: alcohol and phenol
Functional group confirmed by reaction 5: phenol [1]
Phenols are slightly acidic and can undergo neutralisation with NaOH (aq) at

r.t.p. [1] Alcohol is considered to be neutral thus it will not undergo acid-base
reaction with NaOH (aq).

(iii)

Using your answers in (i) and (ii), as well as information from the table above,
draw the fully displayed structure of W. Explain clearly why you have placed each
of the two functional groups in their particular positions.
H
H
C
Cl

H O
[1]

Chlorine atom must not be attached to the benzene ring to form

chlorobenzene.
white ppt of silver chloride will not be formed as the p orbital of the Cl
atom can overlap with the -electron cloud of the benzene ring. As a
result, the lone pair of electrons on the Cl atom can delocalise into
the benzene ring.
-

This results in partial double bond character in C-Cl bond and the
strengthening of the C-Cl bond.

Hence, the Cl atom is difficult to substitute. [1]

3 bromine atoms must be substituted into compound W when it reacted

with Br2 (aq) thus the substituents must be in the 1 and 3 positions
respectively. [1]
[6]

SRJC 2008 Prelim/II/Section B Q7(a) modified

3
When treated with cold dilute alkaline potassium manganate (VII), P, C10H12 forms
compound Q. However, on heating P with acidified potassium manganate (VII), 2
products, compound R, C8H8O and compound S, C2H4O2 are formed.
When R was warmed with 2,4-dinitrophenylhydrazine, an orange precipitate was
obtained.
On refluxing Q with ethanoic acid in the presence of concentrated sulphuric acid,
compound U, C14H18O4 is obtained.
Deduce, with reasoning, the structures of P, Q, R, S, T and U.
P undergoes (mild) oxidation to form Q.
P contains C=C
Q contains diol / alcohol [1]
P undergoes oxidationto form compounds R and S.
P contains C=C
R is a ketone
S is a carboxylic acid [1]

[9]

R undergoes condensation[1] to form orange precipitate.

R is a ketone
Q undergoes esterification/ nucleophilic substitution [1] to form
compound T.
Q contains diol
T is a diester[1]
Max 3 marks for reasoning
Structure: [1] each (total 6 marks)
H3C

H3C

CH3

HO

O
H3C

C
CH3

OH

H3C

CH3
O

CH3

CH3

T
END

OH

CH3