Nanyang Junior College

H2 Chemistry (9647)

JC2 2015

Tutorial: Carboxylic Acids and Derivatives

Section A: Review Questions
1. Complete the following summary table of reactions of carboxylic acids.

OH

H3C C H

H3C C

Cl

10

4
O

H3C C N

H3C

H3C C
H

OH

O
H3C

C
-

O Na

Rxn

CH3
C

H3C

Reagents and Conditions

(Type of reaction)

Rxn

10

Reagents and Conditions

(Type of reaction)

2. Describe how bromobutane can be converted to the following compounds.

Give the reagents and conditions for each step, as well as indicate the type of
reaction.
(i)

butanoic acid

(ii)

pentanoic acid

(iii)

propanoic acid

(iv)

butanoyl chloride

3. Suggest reagents and conditions, and intermediate if necessary, to convert

O

(i)

OH into

OH

(ii)

ethanol into phenyl ethanoate

...

Problem Solving Skill Set (PS3) for Q2 & 3

1. Strategy for general synthesis questions: Check the difference between reactants
and products is there a change in carbon length? What functional groups are involved
in the reaction? Recall reagents and conditions for the reactions that occur.

4. Which one of the following is a product of the reaction between phenylmethanol, and
ethanoyl chloride, CH3COCl ?
A
OCOCH3

B
CH2OCOCH3

C
COOCH2CH3

D
CH2COOCH3

Problem Solving Skill Set (PS3)

1. Strategy for ester synthesis questions: students must be able to draw the structural
formula of the given reactants and hence give the esters required. Note that formula of
ester functional group is either written as COO- or OCO-. There is no ester written in
the form OOC-.
5. In its reaction with sodium, 1 mol of a compound X gives 1 mol of H2 (g). Which
compound might X be?
A

CH3CH2CH2CH2OH

(CH3)3OH

CH3CH2CH2CO2H

CH3CH( OH)CO2H

Problem Solving Skill Set (PS3)

1. Strategy for reaction questions involving arithmetic calculations: students must be
able to recall and balance reactions involving all the functional groups. Recall that each
mole of OH and CO2H will react with each mole of Na to give mole of H 2.

6. Ethyl propanoate, CH3CH2OCOCH2CH3 undergoes acidic hydrolysis in the presence

of H218O. Which of the following products are formed? (18O is an isotope of oxygen)
1

CH3CH218OH

CH3CH2CO18OH

CH3CH2OH

Problem Solving Skill Set (PS3)

1. Student must note that when an ester undergoes acidic hydrolysis, H atom is added to
the alcohol and the 18OH is added to the acid.

7. (a)

Explain why ethanoic acid is more acidic than ethanol.

(b)

Explain why chloroethanoic acid is more acidic than ethanoic acid.

Problem Solving Skill Set (PS3)

1. Student should be familiar with factors affecting stability of conjugate anion and relate
stability of anion to strength of acids. Must recall that comparisons can be between
different functional groups and also between different acids.

Section B: Discussion Questions

8. Hydroxyethanoic acid reacts as shown.

HOCH2CO2H

excess CH3NH2

excess PCl5

compound Q

compound R

heat

What are the formulae for compounds Q and R?

Compound Q
HOCH2COCl
ClCH2CO2H
ClCH2COCl
ClCH2COCl

A
B
C
D

Compound R
HOCH2CONHCH3
CH3NHCH2CO2H
CH3NHCH2COCl
CH3NHCH2CONHCH3

9. One industrial preparation of ethanoic acid is the direct carbonylation of methanol

using a rhodium catalyst
CH3OH

OH

rhodium
CH3

CO

catalyst

CO 2H
HC

CH 2CO 2H

Which compound could be expected to produce CH 2CO 2H

A

OH
HC

C
CO 2H

CH 2OH
HC

OH
HC

CH 2OH

CH 2CO 2H

CO 2H

CH 2CO 2H

OH
HC

CH 2CO 2H

CH 2CO 2H

CH 2OH

Problem Solving Skill Set (PS3)

Strategy for solving reactions not found in syllabus:
1. Observe the patterns in the reaction; what is the type of reaction?
2. What bonds are broken/formed. How is the CO group added to the alcohol?
3. What are the products formed from this reaction?

10. Which procedure gives the best yield of ethyl ethanoate, CH 3CO2CH2CH3, starting
from ethanoic acid, CH3CO2H, and ethanol, CH3CH2OH?

A
B
C
D

reacting CH3CO2H with SOCl2, then adding CH3CH2OH

reacting CH3CH2OH with SOCl2, then adding CH3CO2H
refluxing a mixture of CH3CO2H and CH3CH2OH with NaOH (aq)
refluxing CH3CH2OH with concentrated H2SO4, then adding CH3CO2H

Problem Solving Skill Set (PS3)

Strategy for solving questions that involve the largest yield of ester:
1. Recall the 2 different sets of reagents and conditions to yield esters
2. Which set gives a compete reaction (e.g. a larger yield)?
3. Recall reactions of functional groups in the above reactions and understand why 3
out of 4 options give a poor or no yield of ester.

11. Which compound is most readily hydrolysed by water?

A
B
C
D

CH3COCH2Cl
C6H5CH2COCl
CH3CHClCO2H
Cl

Cl

COCH 3
Cl

Problem Solving Skill Set (PS3)

Strategy for solving questions that involve the largest yield of ester:
1. Identify the functional group present.
2. Recall the order of ease of hydrolysis of different functional groups.

12. 2-hydroxybenzoic acid, A, is a useful intermediate for making aspirin (an analgesic)
and oil of wintergreen (used in ointments).

(a) Suggest suitable reagents and conditions for reaction II.

(b) Draw the structural formulae of the organic molecules produced when A reacts with
i.

iii.

Na

ii.

Na2CO3

SOCl2

iv.

Br2 (aq)

(c) A student proposes the following synthetic route to get aspirin.

CO2Na

CN

OCOCH3 HCl(aq)

OCOCH3 NaOH(aq)

CO2H
OCOCH3

reflux

Suggest what is wrong with the scheme and propose a correction to the scheme to
successfully get aspirin.

Error in the proposal: ..

..

Correction to the scheme: ..

..

(d) When an aspirin tablet was crushed up in water and titrated with 0.1 mol dm -3 sodium
hydroxide, 13.9 cm3 of alkali was required to neutralise its acidity.
Write a balanced equation for the reaction between aspirin and sodium hydroxide,
hence determine the mass of aspirin in the tablet?
Problem Solving Skill Set (PS3)
1. How can we determine mole ratio of aspirin to NaOH? Note that during
neutralisation reaction, all moles of COOH will be reacted away.
2. Consider how the reaction would change if heat was supplied?

(e) A soluble aspirin contains the calcium salt of aspirin.

(i)

What reagent could you use to convert aspirin into its calcium salt? Write an
equation to illustrate your answer.

(ii)

Suggest why aspirin is insoluble in water whereas its calcium salt is soluble.
Draw a suitable diagram to illustrate the solubility of the salt.

13. Compound L is used medicinally as an anti-spasmodic agent. Hydrolysis of L

produces equimolar amounts of phenylmethanol, M, and benzoic acid, N.

Compound P is an isomer of L, and is used in perfumes. Hydrolysis of P produces

4-methylphenol, Q, and benzoic acid, N.

(a) Suggest structures for L and P.

L

(b) Compound P can be synthesized from compounds Q and N through the

following synthesis process.

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(i)

Suggest reagents and conditions from steps (I) and (II).

Step (I):
Step (II):

(ii)

State the type of reaction that has taken place in step (II).

(iii)

Hence suggest a possible mechanism for step (II). In your answer,

show any relevant charges, lone pairs of electrons and movement of
electrons.

Problem Solving Skill Set (PS3)

1. You may find it helpful to make a comparison to nucleophilic substitution mechanism of
RX.
2. Note in the first step, NaOH is used to generate the phenoxide anion, a stronger
nucleophile than phenol (to subsequently attack the benzoyl chloride).

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N2009/II/5 modified
14. Values of the acid dissociations, K a, for some weak acids are given below.
acid
Benzoic acid

6.3 x 10-5

COOH

Carbonic acid

H2CO3

4.5 x 10-7

Ethanoic acid

CH3CO2H

1.8 x 10-5

Phenol

(a)

Ka / mold m-3

formula

1.3 x 10-10

OH

An aromatic ester E has the following percentage composition by mass,

C, 70.6; H, 5.9; O, 23.5
(i) Calculate the empirical formula of E.

(ii) Given that Mr of E is 136.0, suggest molecular formula of E.

When the aromatic ester E is hydrolysed with NaOH (aq) and the resulting mixture
acidified with a mineral acid such as sulfuric acid, methanoic acid, HCO 2H, is not
among the products.
(b)

(i) Use this information and your answer to (a)(ii) to suggest two possible
structural formulae for the ester E. Draw the displayed formulae of your
compounds in the boxes below.

Structure of E1

Structure of E2

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(ii) For each of your compounds E1 and E2, give the structural formulae of
the organic products that would be formed on heating it under reflux with
an excess of NaOH (aq).
E1 produces

(c)

E2 produces

Suggest what will be formed if CO2 is bubbled through each of the mixtures
formed in (b)(ii). If nothing is formed, write no reaction.

E1 produces

E2 produces

Explain your answer:

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15. Describe simple chemical tests which would enable you to distinguish the following
compounds. For each test, state the reagents and conditions, and state what would
be observed with each compound.
(a)

CH3COCl and CH3CH2Cl

(b)

O
O

Compound A
and
Compound B
(Hint: need to break linkage before distinguishing test can be done)

(c)

CH3COOH, CH3CH2OH and CH3COOCH3 (Hint: more than 1 test required)

14

16. Arrange the following organic compounds in order of increasing pH of solution

formed when the same amount of each compound is dissolved separately in water.
Explain your answer.
phenol

benzoic acid

ethyl ethanoate

ethanoic acid

Problem Solving Skill Set (PS3) for Qn 12

2. Student should be familiar with factors affecting stability of
conjugate anion and relate stability of anion to strength of
acids. Must recall that comparisons can be between
different functional groups and also between different acids.
3. Students may make reference to the diagram on the below
showing electron dispersion of benzoate anion to deduce
stability of the benzoate ion.

....

15

17. This question is about compound H, C5H10O2 which is soluble in water and neutral to
litmus.
Compound H readily forms compound I, C5H6O4 when refluxed with acidified
potassium dichromate (VI), Compound I forms a diester when warmed with 2 moles
of ethanol and concentrated sulphuric acid.
On reaction with aqueous bromine, compound H produced compound J, C5H11O3Br
and decolourized bromine water.
Strong oxidation of H by hot acidified potassium manganate (VII) causes it to form
only one organic product M, C3H4O4.
M can be synthesized as indicated in the following reaction scheme.

CHOCH2Cl

LiAlH 4, ether
reflux

KCN
ethanol

i) H (aq), heat
2-

ii) Cr2O7 /H , reflux

Deduce the structures of compounds H to M. Explain the chemistry of the reactions

described, with the aid of equations where appropriate.
*Please write your explanation in a piece of foolscape paper.
H

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Nanyang Junior College

H2 Chemistry (9647)

JC2 2015

Carboxylic Acids and Derivatives Assignment

Name: ..
CT

Marks:

15

: 14 ..

18. Trichloroethanal (choral), CCl3CHO, was much used up to the middle of this century
as a drug and a stimulant. Choral is easily oxidised to trichloroethanoic acid.
(a)

Draw a displayed formula of trichloroethanoic acid.

(b)

Explain why this acid is a much stronger acid than ethanoic acid.

[2]

[2]
19. In 1991, 3-methylhex-2-enoic acid, MHA, was identified as one factor responsible for
the offensive odour of human sweat.
CH3CH2CH2C(CH3)=CHCO2H
MHA
(a)

Draw the structures of possible organic products when MHA reacts with the
reagents in the table below, and state the type of reaction in each case.
(i) SOCl2

(ii) HBr

Type of reaction:
(iii) LiAlH4, in dry ether

Type of reaction:
(iv) Hot acidified KMnO4

Type of reaction:

Type of reaction:
[8]

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(b)

The odour of MHA is removed by reacting it with aqueous sodium carbonate.

Draw the structure of the organic product of this reaction, and hence suggest
why it has no odour.

[3]

(a) describe the formation of

carboxylic acids from alcohols,
aldehydes and nitriles
(b) describe the reactions of
carboxylic acids in the formation of
(i) salts
(ii) esters on reaction with alcohols,
using ethyl ethanoate as an example
(iii) acyl chlorides, using ethanoyl
chloride as an example
(c) explain the acidity of carboxylic
acids and of chlorine-substituted
ethanoic acids in terms of their
structures
(d) describe the hydrolysis of acyl
chlorides
(e) describe the reactions of acyl
chlorides with alcohols, phenols and
primary amines
(f) describe the relative ease of
hydrolysis of acyl chlorides, alkyl
chlorides and aryl chlorides
(g) describe the formation of esters
from acyl chlorides, using phenyl
benzoate as an example
(h) describe the acid and base
hydrolysis of esters

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