DEPARTMENT OF BIOLOGICAL AND CHEMICAL SCIENCES

CHEM0625 – PRELIMINARY CHEMISTRY II

CARBOXYLIC ACIDS AND THEIR DERIVATIVES

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 CARBOXYLIC ACIDS AND THEIR DERIVATIVES

CARBOXYLIC ACIDS

 The combination of a carbonyl group and a hydroxyl group on the same carbon is called a
carboxyl group (-COOH).

 The carboxyl group can be either bonded to an alky group (aliphatic acid R-COOH) or an
aryl group (aromatic acid, Ar-COOH).

Nomenclature of Carboxylic Acids

1) Select the longest carbon chain containing the carboxyl group, and derive the parent
name by replacing the –e ending of the corresponding alkane with –oic acid.

2) The carboxyl carbon is always position-1. There is no need to designate its position.

3) Number the substituents according to their position on the chain, and write the name
listing the substituents in alphabetical order.

4) The dicarboxylic acids are named as alkanedioic acids.

Name the following compounds:

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Preparation of Carboxylic Acids

 Oxidation of alkenes.
 Oxidation of primary alcohols.
 Oxidation of aldehydes.
 Hydrolysis of nitriles by being boiled under reflux with aqueous alkali or mineral acid.
o E.g.

Reactions of Carboxylic Acids

1) Salt Formation
Carboxylic acids react with metals, carbonates, hydrogen carbonates and alkalis to form
salts.
 With metals:

 With carbonates:

 With alkalis:

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 2) Esterification
Carboxylic acids react with alcohols to form esters.
Equation:

3) Formation of Acid chlorides / acyl chlorides

Carboxylic acids react with phosphorus pentachloride (PCl5) or sulphur dichloride oxide
(SOCl2) to form acid chlorides.
Equations:

Acidity of Carboxylic Acids

 Carboxylic acids will partially ionise in water to from a carboxylate ion and hydroxonium
ion.
Equation:

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  The negative charge on the carboxylate ion is delocalised between the oxygen atoms
making it less ready to accept a proton than alkoxide ions (from alcohols).

 The carboxylate ion is a more stable conjugate base than the alkoxide ion. Carboxylic
acids are stronger acids than alcohols.

 If an electron withdrawing group is attached to the acid, its acidity is increased. Therefore
CH3COOH is weaker than CH2ClCOOH.

ACID CHLORIDES

Reactivity of Acid Chlorides

 Functional group:

 In acid chlorides, the carbonyl group is susceptible to attack by nucleophiles due to the
partial positive charge it has since it is attached to highly electronegative oxygen and
chlorine atoms.
 This is the reason why acid chlorides are more readily hydrolysed than chloroalkanes and
chloroarenes.
 In aromatic acid chlorides the partial positive charge is spread over the ring, therefore
they are less susceptible to nucleophilic attack than the aliphatic acid chlorides.

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Nomenclature of Acid chlorides

 These are named by dropping ‘–ic acid’ from the parent acid and then adding ‘-yl
chloride’.

Examples:

Reactions of Acid chlorides

1) Hydrolysis
Acid chlorides react with water to form carboxylic acids and HCl.
Equation:

2) Ester Formation
a) Acid chlorides react with alcohols in the presence of pyridine to form esters.
(Pyridine is a base which removes the HCl produced)
Equation:

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 b) Acid chlorides react with phenols in alkaline solution to form esters.
Equation:

3) Amide Formation
Acid chlorides react with ammonia, primary or secondary amines to form amides.
Equation:

4) Anhydride Formation
An acid chloride reacts with a carboxylate salt to produce an acid anhydride.

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ACID ANHYDRIDES
 Acid anhydrides react with water to form the parent acid.

Nomenclature of Acid anhydrides

 These are named by dropping the word ‘acid’ from the parent acid and then adding the
word anhydride.
Examples:

Reactions of acid anhydrides

 React in a similar way to acid chlorides.

ESTERS

Nomenclature of Esters
 The name of the alcohol (-yl replacing –anol) and the carboxylic acid (-ate replacing –ic
acid) makes up the ester. The portion of the name derived from the alcohol comes first.
Examples:

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Preparation of Esters
 The combination of acids or acid chlorides with alcohols or phenols gives rise to esters.

Hydrolysis
 Esters are hydrolysed by aqueous acid or base to form carboxylic acids and alcohols.
Hydrolysis in basic solution is called saponification (process is utilised in soap making).
Equation:

AMIDES (RCONH2)

Nomenclature of Amides
 Amides are named by dropping the word ‘oic acid’ from the parent acid and then adding
the word ‘amide’.
Examples:

References
 Ramsden, E. N. A-level Chemistry; Stanley Thornes, 1995.
 Wade, L. G. Organic Chemistry; Prentice-Hall, Inc. 1999.