S6 CHEMISTRY 12/APR/2022

Carboxylic acids
Introduction

 These are organic compounds that possess the carboxyl group as a functional group.
 Structure of the carboxyl group is as follows:

 The carboxyl group contains both a carbonyl group and a hydroxyl group; hence the name.

Classification and nomenclature

 Carboxylic acids can be saturated or unsaturated; aliphatic or aromatic and monocarboxylic or

polycarboxylic acids.
 Monocarboxylic acids are named by replacing the final – 𝑒 in the name of the parent alkane by
the suffix – 𝑜𝑖𝑐.
 Where necessary, the position(s) and name(s) of the substituents are indicated as before with
the carbonyl carbon always counted as the first in the carbon chain.
 Examples of some common carboxylic acids are:
HCOOH 𝐶𝐻3COOH 𝐶𝐻3 𝐶𝐻2 COOH
Methanoic acid Ethanoic acid propanoic acid
𝐶𝐻2 = 𝐶𝐻𝐶𝑂𝑂𝐻
Propenoic acid

Benzoic acid 2 −phenylethanoic acid

4−nitrobenzoic acid Benzene−1,2 −dicarboxylic acid

HOOC−COOH HOOC𝐶𝐻2COOH HOOC𝐶𝐻2 𝐶𝐻2COOH
Ethanedioic acid Propane−1,3 −dioic acid Butane−1,4 −dioic acid
(oxalic acid) (malonic acid) (succinic acid)

 Saturated aliphatic monocarboxylic acids have the general formula; 𝐶𝑛 𝐻2𝑛+1 𝐶𝑂𝑂𝐻 or
simply; 𝑅𝐶𝑂𝑂𝐻.

Question:
Write the structural formula of the each of the following compounds.
(i) Pentanoic acid (vi) 3 −methylbutanoic acid
(ii) 2 −chloro−3 −methylpropanoic acid (vii) Chloroethanoic acid
(iii) tribomoethanoic acid (viii) 4 −methylbenzoic acid
(iv) Benzene−1,4 −dicarboxylic acid (ix) 2,2 −dimethylpropanoic acid
(v) Pent-3-enoic acid (x) cyclohexane carboxylic acid
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Preparation of carboxylic acids

 Some of the common methods employed are:

(a) Oxidation of primary alcohols or aldehydes (see previous notes)
(b) Hydrolysis of nitriles or amides

Note:
Both acid hydrolysis and base hydrolysis of nitriles give an amide as an intermediate.

Question:
Write equations to show how the following conversion can be effected.
(a) Methanol to propanoic acid (b) Benzyl chloride to 2-phenylethanoic acid

(c) Grignard synthesis

Note:
This reaction is used in organic synthesis to increase carbon chain. In the preparation of
benzoic acid, solid carbon dioxide is used to help cool the reaction mixture.

Question:
Write equations to show how the following conversions can be effected.
(a) Benzene to benzoic acid (c) Ethyene to benzoic acid
(b) Ethanol to propanoic acid

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 (d) Hydrolysis of esters

Base hydrolysis of esters is referred to as saponification; reaction used in soap

manufacture.
(e) From methylbenzene

Note:
Regardless of the length of R, the main product is always benzoic acid.

R can be −𝐶𝐻2 𝐶𝐻3; −𝐶𝐻2 𝐶𝐻2 𝑂𝐻 and so on.

Isomerism in carboxylic acids

 Monocarboxylic acids are isomeric with esters.

 For example;
The isomers of 𝐶2 𝐻4 𝑂2 are:

The isomers of 𝐶3 𝐻6 𝑂2 are:

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Physical properties of carboxylic acids

 Simple acids with less than 10 carbon atoms are liquids at room temperature; with a sharp,
pungent odour/smell. For example, the sharp characteristic smell of vinegar is due to ethanoic
acid in it.
 Aromatic acids are crystalline solids.
 The acids are polar and just like alcohols, form hydrogen bonds amongst themselves and with
water molecules.
This explains why:
(a)Aliphatic monocarboxylic acids are less volatile than aliphatic compounds of comparable
relative molecular mass.
Monocarboxylic acids are less volatile than monohydric alcohols of similar RMM. For
example, butan-1-ol boils at 117℃ wheares propanoic acid boils at 141℃. This due the fact
that:
(i) There are many hydrogen bonds between a pair of molecules of acids than between
a pair of molecules of alcohols.
(ii) The hydrogen bonds in acids are stronger than those in alcohols. This is due to the
highly polar nature of the carboxyl group caused by the withdrawal of electrons
away from the hydrogen atom towards the carbonyl oxygen atom.
(b) Lower members are miscible with water/soluble in water. Solubility decreases with
increase in molecular mass. This because as the RMM increases, the length of the
water−insoluble hydrocarbon portion increases and hence, its properties outweigh that of
the carboxyl group in the molecule.
(c) Lower members exist as dimers in organic solvents and vapour phase. This explains why
RMM determination of lower acids by freezing point depression method (cryoscopy) or
boiling point elevation method (ebullioscopy) gives twice the expected value. Aromatic
acids are only sparingly soluble in cold water but readily dissolve in hot water and reform
on cooling.
 All carboxylic acids readily dissolve in organic solvents.

Acidity of carboxylic acids

 The carbonyl oxygen atom being more electronegative than the carbonyl carbon atom, it
strongly withdraws bonding electrons more towards itself. The magnitude of the partial
positive charge on the carbonyl carbon atom increases. The electron deficiency on the carbonyl
carbon atom makes it strongly pull the bonding electrons in the oxygen−hydrogen bond. As a
result, the magnitude of the partial positive charge on the hydrogen atom increases,
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 oxygen−hydrogen bond weakens and the bond readily breaks to release a proton. Thus,
monocarboxylic acids are weak, monobasic acids.
 In a dilute aqueous solution, the following equilibrium is established:
𝑅𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐻2 𝑂(𝑙) ⇌ 𝑅𝐶𝑂𝑂− (𝑎𝑞) + 𝐻3 𝑂+ (𝑎𝑞)
Or simply as 𝑅𝐶𝑂𝑂𝐻(𝑎𝑞) ⇌ 𝑅𝐶𝑂𝑂− (𝑎𝑞) + 𝐻 + (𝑎𝑞)
 The negative charge on the carboxylate ion (𝑅𝐶𝑂𝑂 − ) formed is delocalised over the two oxygen
atoms. This makes the carboxylate ion very stable and does not easily accept a proton back once
lost.

 The above factors make carboxylic acids stronger acids than alcohols.
 The introduction of electron-withdrawing groups into the carboxylic acid molecule promotes
proton loss and makes the compound more acidic. For example, ethanoic acid is a weaker acid
than chloroethanoic acid or nitroethanoic acid.
 Similarly, the presence of electron donating groups in a molecule of a carboxylic acid make
proton loss more difficult and thus, the acid strength reduces.
 In methanoic acid, the hydrogen atom bonded to the carboxyl group of the acid has no inductive
effect. Thus, the 𝑂 − 𝐻 bond is weak and readily breaks to release hydrogen ions in aqueous
solution.
 The, strengths of weak acids under similar conditions can be approximately compared
by means of the 𝐾𝑎 or 𝑝𝐾𝑎 values.

Note:
 By definition 𝑝𝐾𝑎 = − log10 𝐾𝑎
 The advantage in using 𝑝𝐾𝑎 values is that cumbersome numbers are converted to
relatively simpler ones.
 The higher the 𝐾𝑎 value, the lower is the 𝑝𝐾𝑎 value.

 The table below shows values of 𝐾𝑎 alongside the 𝑝𝐾𝑎 values for some selected weak
acids.
Acid Formula 𝑲𝒂 (𝒎𝒐𝒍 𝒅𝒎−𝟑 ) 𝒑𝑲𝒂
Methanoic acid HCOOH 1.78 × 10 −4
3.75
Ethanoic acid CH3COOH 1.74 × 10 −5
4.76
Chloroethanoic acid ClCH2COOH 1.38 × 10 −3
2.86
Dihloroethanoic acid Cl2CHCOOH 5.12 × 10 −2
1.29
Trihloroethanoic acid Cl3CCOOH 2.24 × 10 −1
0.65
Bromoethanoic acid BrCH2COOH 1.26 × 10 −3
2.90
Benzoic acid C6H5COOH 6.31 × 10 −5
4.20
Phenol C6H5OH 1.00 × 10 −10
10.00

 The higher/larger the 𝐾𝑎 value (the lower the 𝑝𝐾𝑎 value), the stronger is the acid.

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 Thus, in the above table, the strongest acid is trichloroethanoic acid and the weakest
acid is phenol.

Activity
1. Explain each of the following observations.
(a) Methanoic acid is a stronger than ethanoic acid.
Solution
In ethanoic acid, the ethyl group bonded to the carboxyl group has positive
inductive effect. It releases electrons towards the oxygen−hydrogen bond.
The magnitude of the partial positive charge on the hydrogen atom reduces
and the oxygen−hydrogen bond becomes stronger. Thus, a hydrogen ion is not
easily lost into solution.
Whereas in methanoic acid, the hydrogen atom bonded to the carboxyl group
has no inductive effect. The oxygen−hydrogen bond is weaker and thus, the
hydrogen ion is easily lost into solution.

Note:
The magnitude of the inductive effect of the alkyl groups increases with
increase in the number of carbon atoms.
For example, propanoic acid is a weaker acid than ethanoic acid.

(b) Ethanoic acid is a weaker acid than haloethanoic acid.

Solution
In ethanoic acid, the ethyl group bonded to the carboxyl group has positive
inductive effect. It releases electrons towards the oxygen−hydrogen bond.
The magnitude of the partial positive charge on the hydrogen atom reduces
and the oxygen−hydrogen bond becomes stronger. Thus, the hydrogen ion is
not easily lost into solution.
Whereas in haloethanoic acid, the halogen atom is more electronegative than
the carbon atom. The halogen atom attracts/pulls the bonding electrons more
towards itself. The magnitude of the partial positive charge on the hydrogen
atom increases. The oxygen−hydrogen bond becomes weaker and the hydrogen
ion is easily lost into solution.

Note:
 When the halogen atom has a smaller atomic radius and is more
electronegative, the oxygen−halogen bond is greatly weakened and a
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 proton is easily released into aqueous solution. For example,
chloroethanoic acid is a stronger acid than bromoethanoic acid. Thus, the
acid strength decreases in the order:
𝐹𝐶𝐻2 𝐶𝑂𝑂𝐻 > 𝐶𝑙𝐶𝐻2 𝐶𝑂𝑂𝐻 > 𝐵𝑟𝐶𝐻2 𝐶𝑂𝑂𝐻 > 𝐼𝐶𝐻2 𝐶𝑂𝑂𝐻 > 𝐶𝐻3 𝐶𝑂𝑂𝐻
 The more the number of halogen atoms attached to the carboxyl group,
the weaker the oxygen−halogen bond becomes and the more easily a
proton is released into aqueous solution. For example, trichloroethanoic
acid is a stronger acid than dichloroethanoic acid which is in turn a
stronger acid than chloroethanoic acid. Thus, the acid strength increases
in the order: 𝐶𝐻3 𝐶𝑂𝑂𝐻 < 𝐶𝑙𝐶𝐻2 𝐶𝑂𝑂𝐻 < 𝐶𝑙2 𝐶𝐻𝐶𝑂𝑂𝐻 < 𝐶𝑙3 𝐶𝐶𝑂𝑂𝐻

(c) Chloroethanoic acid is a stronger acid than ethanoic acid.

(d) The acid dissociation constant, 𝐾𝑎 , of bromoethanoic acid is greater than that
of ethanoic acid, at the same temperature.
(e) The dissociation constant, 𝐾𝑎 , of methanoic acid is higher than that of
ethanoic acid.
(f) Ethanoic acid is a weaker acid than dichloroethanoic acid.
(g) The acid dissociation constant, 𝐾𝑎 , of chloroethanoic acid is greater than that
of bromoethanoic acid, at the same temperature.
2. The table below shows acid dissociation constants, 𝐾𝑎 , for some acids at 25℃.
Acid 𝑲𝒂 (𝒎𝒐𝒍 𝒅𝒎−𝟑 )
𝐻 − 𝐶𝑂𝑂𝐻 1.75 × 10−4
𝐶𝐻3 𝐶𝑂𝑂𝐻 1.70 × 10−5
𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐻 1.35 × 10−5
State and explain the trend in acid strength of the acids in the table above.
3. The acid strength of some selected organic acids increases in the order:
𝐶𝐻3 𝐶𝑂𝑂𝐻 < 𝐶𝑙𝐶𝐻2 𝐶𝑂𝑂𝐻 < 𝐶𝑙2 𝐶𝐻𝐶𝑂𝑂𝐻 < 𝐶𝑙3 𝐶𝐶𝑂𝑂𝐻. Explain.

Salts of carboxylic acids

 The salts are ionic and named by replacing the ending ‘ic’ in the parent acid by ‘ate’.
 For example;
𝐻𝐶𝑂𝑂− 𝑁𝑎+ 𝐶𝐻3 𝐶𝑂𝑂− 𝑁𝐻4+ (𝐶𝐻3 𝐶𝑂𝑂)2 𝐶𝑎
Sodium methanoate Ammonium ethanoate Calcium ethanoate
(𝐶𝐻3 𝐶𝑂𝑂)2 𝐶𝑢 (𝐻𝐶𝑂𝑂)3 𝐹𝑒
Copper(II) ethanoate Iron(III) methanoate
Lead(II) benzoate

 The salts of the acids are formed when the acids react with highly electropositive metals,
bases/alkalis, carbonates and hydrogencarbonates.

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 The reaction of carboxylic acids with:
(a) highly electropositive metals (like sodium) is used to confirm the presence of a hydroxyl
group in the acid molecules.
Observations:
Bubbles of a colourless gas
Equation:
2𝑅𝐶𝑂𝑂𝐻 + 2𝑁𝑎 → 2𝑅𝐶𝑂𝑂− 𝑁𝑎+ + 𝐻2
In this case, the carboxylic acids resemble alcohols which also possess the hydroxyl group.
(b) a (saturated) solution of sodium carbonate or sodium hydrogencarbonate serves to
distinguish carboxylic acids from simple phenols which are weak acids and do not liberate
carbon dioxide. The reaction also serves to confirm the presence of carboxyl group in a
molecule of the compound.
Observations:
Carboxylic acids: Bubbles of a colourless gas
Phenols: No bubbles of a colourless gas
Equations:
2𝑅𝐶𝑂𝑂𝐻 + 𝑁𝑎2 𝐶𝑂3 → 2𝑅𝐶𝑂𝑂− 𝑁𝑎+ + 𝐶𝑂2 + 𝐻2 𝑂
𝑅𝐶𝑂𝑂𝐻 + 𝑁𝑎𝐻𝐶𝑂3 → 𝑅𝐶𝑂𝑂 − 𝑁𝑎+ + 𝐶𝑂2 + 𝐻2 𝑂
(c) alkalis (e.g. sodium hydroxide solution or potassium hydroxide solution) is used to
determine the amount of acid in a given sample during titration using a suitable indicator.

Reactions of carboxylic acids

 Some important reactions of carboxylic acids are:

(a) Formation of acid chlorides; RCOCl

 Observations: Misty fumes evolved

 The use of sulphur dichloride oxide is more convenient since, all the other bi-products
are gaseous.
 The above reactions serve to identify presence of a hydroxyl group in the acid molecule.
(b) Halogenation
The reaction readily occurs at carbon atom number 2.
For example, ethanoic reacts with chlorine or bromine as follows:

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 Higher carboxylic acids require slight warming and the use of a small amount of phosphorus
trihalide as a catalyst.

Benzoic acid and other aromatic carboxylic acids undergo electrophilic substitution when
treated with chlorine or bromine in the presence of a halogen carrier. Substitution occurs at
position 3 in the ring.

Question:
Describe how the conversion of ethanol to hydroxyethanoic acid can be effected. No
equations required.

(c) Reduction
 Only powerful reducing agents (such as 𝐿𝑖𝐴𝑙𝐻4 /dry ether or diborane, 𝐵2 𝐻6 ) can be
used to effected reduction. Primary alcohol is formed.

 Diborane is a selective reducing agent and may be used to reduce the carboxyl group in
presence of other unsaturated groups.
For example;
𝐵2 𝐻6
𝐶𝐻2 = 𝐶𝐻𝐶𝑂𝑂𝐻 → 𝐶𝐻2 = 𝐶𝐻𝐶𝐻2 𝑂𝐻
(d) Formation of amide; 𝑅𝐶𝑂𝑁𝐻2

 Hofmann degradation is used in organic synthesis to reduce the carbon chain.

Question:
Write equations to show how the following conversions can be effected.
(a) Ethanol to ethylamine
(b) Ethanol to methylamine

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 (e) Decarboxylation

Question:
Write equations to show how the following conversions can be effected.
(a) Phenylmethanol to nitrobenzene
(b) Propanoic acid to ethane

(f) Esterification
Refer to the reactions of alcohols for details.

Question:
Write equations to show how the following conversions can be effected.
(a) Bromoethane to methyethanoate
(b) Propanoic acid to ethane

(g) Oxidation reaction of carboxylic acids

Carboxylic acids except methanoic acid and oxalic acid, are extremely resistant to oxidation.
Methanoic acid gives a positive test with common oxidising agents because it contains an
aldehyde group which makes it act as a reducing agent. And thus, it is oxidized by the
common oxidising agents.

Observations.
(i) With acidified potassium manganate(VII) solution
Purple solution turns colourless on heating.
(ii) With acidified potassium dichromate(VI) solution
Orange solution turns green on heating.
The half equation for reaction involving methanoic acid with the reagents in (i) and (ii) is:
𝐻𝐶𝑂𝑂𝐻(𝑎𝑞) ⟶ 𝐶𝑂2 (𝑔) + 2𝐻 + (𝑎𝑞) + 2𝑒 −
(iii) With ammoniacal silver nitrate solution (commonly called Tollens’ reagent)
Silver mirror is formed on warming.
𝐻𝐶𝑂𝑂𝐻(𝑎𝑞) + 2𝐴𝑔+ (𝑎𝑞) + 2𝑂𝐻 − (𝑎𝑞) ⟶ 𝐶𝑂2 (𝑔) + 2𝐻2 𝑂(𝑙) + 2𝐴𝑔(𝑠)
(iv) Fehling’s solution and Benedict’s solution
A reddish brown precipitate is formed on heating/warming. This reaction is however
very slow if it occurs.
𝐻𝐶𝑂𝑂𝐻(𝑎𝑞) + ⏟ 2𝐶𝑢2+ (𝑎𝑞) + 4𝑂𝐻 − (𝑎𝑞) ⟶ 𝐶𝑂2 (𝑔) + 3𝐻2 𝑂(𝑙) + ⏟ 𝐶𝑢2 𝑂(𝑠)
𝑖𝑛 𝐹𝑒ℎ𝑙𝑖𝑛𝑔′𝑠/𝐵𝑒𝑛𝑒𝑑𝑖𝑐𝑡′𝑠 𝑠𝑜𝑙𝑢𝑡𝑖𝑜 𝑟𝑒𝑑𝑑𝑖𝑠ℎ−𝑏𝑟𝑜𝑤𝑛
𝑝𝑟𝑒𝑐𝑖𝑝𝑖𝑡𝑎𝑡𝑒

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 Note:
 The salts of the methanoic acid (e.g. sodium methanoate, HCOONa) also give
positive tests with the common oxidizing agents due to the presence of the
aldehyde group.

 Ethanedioic acid (commonly called oxalic acid) and its salts (e.g. sodium
oxalate/sodium ethanedioate) give positive tests with some common oxidising
agents.
 For example:
The acid and its salts turns acidified potassium manganate(VII) solution from
purple to colourless on heating.
The half equation for the oxidation of the acid or salt being:
𝐶2 𝑂42− (𝑎𝑞) ⟶ 2𝐶𝑂2 (𝑔) + 2𝑒 −
⏟
𝑖𝑛 𝑎𝑐𝑖𝑑 𝑜𝑟 𝑠𝑎𝑙𝑡
𝐴𝑙𝑡𝑒𝑟𝑛𝑎𝑡𝑖𝑣𝑒𝑙𝑦 𝑓𝑜𝑟 𝑡ℎ𝑒 𝑎𝑐𝑖𝑑 𝑤𝑒 𝑚𝑎𝑦 𝑤𝑟𝑖𝑡𝑒:
𝐻2 𝐶2 𝑂4 (𝑎𝑞) ⟶ 𝐶𝑂2 (𝑔) + 2𝐻 + (𝑎𝑞) + 2𝑒 −
 Thus, it is possible to differentiate the following pairs of compounds/ions.
O O O

(a) HO C C OH and CH3C OH

(b) COO- or C2O42- and CH3C OO-

COO-

(c) COONa or Na2C2O4 and CH3C OONa

COONa
(d) HCOOH and CH3C OOH

(e) HCOONa and CH3C OONa

(f) H2C2O4 and HCOOH

(g) Na2C2O4 and CH3COONa

(h) Reaction of carboxylic acids with neutral iron(III)

chloride solution
 Aliphatic carboxylic acids produce red colouration when treated with neutral iron(III)
chloride solution.
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  For example:
𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑎𝑞) + 𝐹𝑒𝐶𝑙3 (𝑎𝑞) ⟶ (𝐶𝐻3 𝐶𝑂𝑂)3 𝐹𝑒(𝑎𝑞) + 3𝐻𝐶𝑙(𝑎𝑞)
(𝑠𝑜𝑙𝑢𝑏𝑙𝑒 𝑠𝑎𝑙𝑡)
 Aromatic carboxylic acids (e.g. benzoic acid) give a reddish-brown precipitate (or
simply brown precipitate/buff coloured precipitate) when treated with neutral iron(III)
chloride solution.
COOH
COO
3 (aq) + FeCl3(aq) (aq)
3Fe(s) + 3HCl(aq)

(insoluble salt)

Uses of carboxylic acids

 Methanoic and ethanoic acids are used to coagulate rubber latex.
 Aqueous solution of ethanoic acid is used as vinegar.
 Ethanoic acid is used as a solvent.
 Ethanoic acid is used as a starting material in the preparation a poly(ethenyl ethanoate),
cellulose ethanoate (for artificial fibres such as varnish, films and lacquer) and the drug aspirin.
 Chloroethanoic acid is used in the manufacture of the weedkiller 2,4-D
 Benzoic acid is used as a food and drug preservative.
 Long chain carboxylic acids are used in manufacture of soaps.
 Hexanedioic acid and benzene-1,4-dioic acid are used in the manufacture of nylon-6,6 and
terylene respectively.

Derivatives of carboxylic acids

Name General formula
Acid halides O

R C
X
Acid anhydride O
O O
R C
O C
or R O C R

R C
O
Esters O

R C O RI or RCO2RI

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 Amides O

R C NH2 or RCONH2

 Note:
 R may be aliphatic or aromatic.
 R and RI may be identical or not.
O
All the derivatives have R C called the acyl group


Physical properties of the acid derivatives

 Acid halides, anhydrides and esters have boiling points which are similar to those of carbonyl
compounds of comparable relative molecular mass.
 Acid halides, anhydrides and esters have much lower boiling and melting points than carboxylic
acids of comparable relative molecular mass. This is due to their inability to associate via
hydrogen bonding since their molecules lack a highly polar oxygen−hdrogen bond.
 Molecules of amides associate via hydrogen bonding/hydrogen bonds due to the presence of a
highly polar nitrogen−hydrogen bond.
 The presence of hydrogen bonds between the molecules of amides, make amides:
 exist as solids except methanamide, HCONH2.
 boil and melt at very high temperatures (i.e. much less volatile).
 readily soluble in water.

Acid halides
(a) Introduction, structure and nomenclature
 The most important are the acid chlorides, RCOCl.
 HCOCl (methanoyl chloride) has not been isolated.
 The other examples are:
CH3COCl; ethanoyl chloride

CH3CH2COCl; propanoyl chloride

COCl; benzoylchloride

(b) Preparation of acid chlorides

 Refer to the previous sections for details.
(c) Properties of acid chlorides:
 Lower members are colourless liquids with sharp, irritating smell.
 They give misty fumes in moist air due to ready hydrolysis which liberates hydrogen chloride.
𝐶𝐻3 𝐶𝑂𝐶𝑙(𝑙) + 𝐻2 𝑂(𝑙) ⟶ 𝐶𝐻3 𝐶𝑂𝑂𝐻(𝑙) + 𝐻𝐶𝑙(𝑔)
Mechanism for the hydrolysis reaction:

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 Question:
Complete and outline the acceptable mechanism for the following reaction:
COCl
H2O

 Under suitable conditions, they react with phenols and alcohols to form esters.
The reaction with alcohols requires pyridine, an organic base to absorb hydrogen chloride
formed.
The reaction with phenols require an alkaline medium.
The mechanism is the same as that of hydrolysis except that the nucleophiles are the phenoxide
ion and alcohol molecule, instead of the water molecule.

Question:
Complete and outline the acceptable mechanism of the following reactions:
(a) CH COCl + CH OH pyridine
3 3

OH
CH3COCl
(b)
NaOH(aq), room temperature

 They react with primary amines, secondary amines and concentrated amine at room
temperature to form amides.
O
I o
R NH2 (1 amine)
R C NHRI + HCl
N-substituted amide
O
O
excess conc NH3
R C R C NH2 + HCl

Cl amide

O
I o
R 2NH (2 amine)
R C NRI2 + HCl
N,N-disubstituted amide
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 The mechanisms for the above reactions are similar to of hydrolysis already discussed.
Note: Tertiary amines (𝑅3 𝑁) do not react due to lack of the 𝑁 − 𝐻 bond.
Question:
Complete and outline the acceptable mechanism for the following reactions:
𝑒𝑥𝑐𝑒𝑠𝑠 𝑐𝑜𝑛𝑐 𝑁𝐻3
(a) 𝐶𝐻3 𝐶𝑂𝐶𝑙 →
𝐶𝐻3 𝐶𝐻2 𝑁𝐻2
(b) 𝐶𝐻3 𝐶𝑂𝐵𝑟 →
𝐶𝐻3 𝐶𝑂𝐶𝑙
(c) (𝐶𝐻3 )2 𝑁𝐻 →

 Acid chlorides are readily reduced and the product depends on the reducing agent employed.
H2, 'posioned' Pd/BaSO4
heat RCHO + HCl (Rosenmund Reaction)
H2/Pt or Pd
1,2-dimethylbenzene solvent RCH2OH + HCl
RCOCl
LiAlH4/dry ether
RCH2OH
or NaBH4/water or methanol

 The acid chlorides also react with benzene in the presence of a halogen carrier to form aromatic
carbonyl compounds. Refer to Friedel-Crafts acylation for details.

Questions:
1. Complete and outline the mechanism for the following reaction.
O

RC Cl/AlCl3

𝑁𝑎𝑂𝐻(𝑎𝑞),ℎ𝑒𝑎𝑡
𝐶𝐻3 𝐶𝑂𝐶𝑙 + 𝐶𝐻3 𝐶𝑂𝑂𝐻 →
2. Show how the following conversions can be effected.
O

(a) CaC2 C O

(b) Ethyne diphenylmethanone

(c) Methylbromide ethanal

(d) Methanol ethanol

Esters
(a) Introduction and nomenclature
 These occur naturally in fats, oils, many fruits, flowers and waxes.
 Examples of some esters are:
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 𝐻𝐶𝑂𝑂𝐶𝐻3 𝐶𝐻3 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 O
methyl methanoate ethyl ethanoate
CH3C O
𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑂𝐶𝐻2 𝐶𝐻3 𝐶6 𝐻5 𝐶𝑂𝑂𝐶𝐻3
ethyl propanoate methyl benzoate phenyl ethanoate

(b) Physical properties of esters:

 Simple esters are colourless liquids with sweet/pleasant fruity smell and are commonly used in
scenting perfumes and flavouring food.
 Their boiling points are much lower than their parent acids despite having higher relative
molecular masses. For example, methanoic acid (RMM=46) boils at 101oC whereas methyl
methanoate (RMM=60) boils at 32oC.
 The lower members are moderately soluble in water but the solubility decreases rapidly with
increasing molecular mass; esters are soluble in most organic solvents.

(c) Preparation of esters:

 Refer to the previous sections/topics for details.

(d) Reactions of esters:

(i) Hydrolysis
 The process can be effected by use of either acid or base catalysis.
 The products are both the parent acid and parent alcohol.

 Base catalysed hydrolysis proceeds to completion as compared to the acid catalysed

hydrolysis.
This is because the acid formed is converted by the base into a salt. Equilibrium
concentration of the acid formed reduces and this disturbs the equilibrium. In order, to
restore the equilibrium position, further hydrolysis occurs.
 Base catalysed hydrolysis is referred to as saponification because it is the type of
reaction used in preparing soaps.
 General mechanisms for both acid and base hydrolysis are:
(i) Acid catalyzed hydrolysis

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 (ii) Base catalyzed hydrolysis

Question:
Complete and outline the mechanism for the following reaction.
ℎ𝑒𝑎𝑡
(a) 𝐻𝐶𝑂2 𝐶𝐻2 𝐶𝐻3 + 𝑁𝑎𝑂𝐻(𝑎𝑞) →
𝐻2 𝑂/𝐻 + ,𝑟𝑒𝑓𝑙𝑢𝑥
(b) 𝐶6 𝐻5 𝐶𝑂𝑂𝐶𝐻3 →

(ii) Amide formation

 Mechanism is similar to the base catalysed hydrolysis of esters.

 Primary and secondary amines react with esters in a similar way like ammonia.
(iii) Reduction
 Only effected by powerful reducing agents like LiAlH4/dry ether or H2, CuO/CuCrO4
catalyst at 250oC and 150 atmospheres.
 Depending on the structure of the ester used, the process yields two primary alcohols
which many be identical or not.
𝐿𝑖𝐴𝑙𝐻4 /𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
 For example: 𝑅𝐶𝑂𝑂𝑅 𝐼 → 𝑅𝐶𝐻2 𝑂𝐻 + 𝑅 𝐼 𝑂𝐻
⏟
𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝑎𝑙𝑐𝑜ℎ𝑜𝑙𝑠
(e) Uses of esters
 Esters are used:
(i) as solvents
(ii) for preparation of synthetic perfumes and fruit essences.

Amides
(a) Introduction and nomenclature
 Amides may be classified as follows:

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 Primary O

R C NH2 or RCONH2
Secondary

Tertiary

 Examples of some amides are:

𝐻𝐶𝑂𝑁𝐻2 ; methananide 𝐶𝐻3 𝐶𝑂𝑁𝐻𝐶𝐻3; N-methylethanamide
𝐶𝐻3 𝐶𝑂𝑁𝐻2 ; ethanamide 𝐶6 𝐻5 𝐶𝑂𝑁𝐻2 ; benzenecarboxamide (or benzamide)
𝐶𝐻3 𝐶𝐻2 𝐶𝑂𝑁(𝐶𝐻3 )2; N,N-dimethylpropanamide

(b) Physical properties of amides:

 All are solids except methanamide.
 They possess hydrogen bonds between their molecules except tertiary amides which possess
no highly polar hydrogen−nitrogen bond. The molecules of tertiary amides associate via weak
van der Waals forces of attraction.
 Thus, tertiary amides have normal boiling points.
 All amides are virtually insoluble in hydrocarbon solvents like methylbenzene, benzene etc.

(c) Preparation of amides:

 Refer to the previous sections for details.

(d) Reactions of amides:

(i) Basicity
 The lone pair of electrons on the nitrogen atom gives amides a slightly basic character.
 However, amides are less basic than amides. Refer to amines for details.

(ii) Hydrolysis
 Can be base or acid catalysed.
𝐻2 𝑂/𝐻 + ,ℎ𝑒𝑎𝑡
𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝐶𝑂𝑂𝐻 + 𝑁𝐻4+
𝐻2 𝑂/ 𝑂𝐻 − ,ℎ𝑒𝑎𝑡
𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝐶𝑂𝑂− + 𝑁𝐻3
 The mechanism for the hydrolysis of amides is similar to that of esters.
(iii) Reduction
𝐿𝑖𝐴𝑙𝐻4 /𝑑𝑟𝑦 𝑒𝑡ℎ𝑒𝑟
 For example: 𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝐶𝐻
⏟ 2 𝑁𝐻2
𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝑎𝑚𝑖𝑛𝑒
 The reduction can also be effected by use of sodium in ethanol.
(iv) Dehydration
𝑃2 05 , ℎ𝑒𝑎𝑡
 For example: 𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝐶 ≡ 𝑁 + 𝐻2 𝑂
⏟
𝑛𝑖𝑡𝑟𝑖𝑙𝑒

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 Question
Write equations to show how methanol can be converted into ethylamine.

(v) Reaction with nitrous acid

𝑁𝑎𝑁𝑂2 /𝑐𝑜𝑛𝑐 𝐻𝐶𝑙, <10𝑜 𝐶
 For example: 𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝐶𝑂𝑂𝐻 + 𝑁2 + 𝐻2 𝑂
 A mixture of 𝑁𝑎𝑁𝑂2 /𝑐𝑜𝑛𝑐 𝐻𝐶𝑙 𝑎𝑡 < 10 𝐶 gives a very unstable nitrous acid.
𝑜

(vi) Hofmann degradation

𝐵𝑟2 /𝑐𝑜𝑛𝑐 𝑂𝐻 − (𝑎𝑞), 𝑤𝑎𝑟𝑚
 For example: 𝑅𝐶𝑂𝑁𝐻2 → 𝑅𝑁𝐻 𝐵𝑟 − + 𝐶𝑂32− + 𝐻2 𝑂
⏟ 2 +⏟
𝑝𝑟𝑖𝑚𝑎𝑟𝑦 𝑜𝑡ℎ𝑒𝑟 𝑚𝑖𝑛𝑜𝑟 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠
𝑎𝑚𝑖𝑛𝑒
 This reaction leads to formation of a primary amine and is used in organic synthesis for
carbon chain reduction.
Question
Write equations to show how ethanol can be converted into methylamine.

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