Alehydes, Ketones and Carboxylic Acid

Aldehydes and Ketones: Introduction

Aldedydes and ketones are organic compounds that contain carbon-oxygen doule bonds.

The general formula for aldehydes is

O

C

R H

The general formula for ketones is

O

C

R R’

Aldedydes and ketones are well-known for their fragrance and flavour.

They are used as solvents and as starting material for the synthesis of various other
products.
Aldehydes and Ketones: Nomenclature

The common names of aldehydes are derived from the names of the corresponding
carboxylic acids by replacing ‘-ic acid’ by ‘-aldehyde’.

In the IUPAC system, aldehydes are named by replacing the ‘-e’ of the corresponding
alkane with ‘al’.

In case of branched chain aldehydes, the longest chain carrying the aldehyde group is
considered the parent structure and is numbered starting from the carbon of the aldehyde
gropu.

When the aldehyde is attached to a ring system, the suffix carbaldehyde is added after the
full name of the ring.

In the common system, ketones are named simply by adding the suffix ‘ketone’ to the
name of two alkyl groups.

A ketone on which the acyl group is attached to a benzene ring is named a phenone.

In the IUPAC system, ketones are named by replacing –e of the corresponding alkane with
– one.
In certain poly-functional compounds, the presence of a carbonyl group can be indicated
by the prefix “oxo” with a number to show its position in a molecule.

Aldehydes and Ketones: Structure of the Carbonyl Group and Physical

Properties

In carbonyl group, the carbon-oxygen double bond is polar in nature due to the
electronegativity difference between carbon and oxygen.

At room temperature, formaldehyde is a gas and acetaldehyde is a volatile liquid. Other

aldehydes and ketones are liquids or solids at room temperature.
Aldehydes and ketones have higher boiling points, than hydrocarbons and ethers of
comparable molecular weights.

Lower aldehydes and ketones such as formaldehyde, acetaldehyde an acetone, are miscible
in water in all proportions because of their ability to form hydrogen bonding with water.

The lower aldehydes and ketones have a characteristic pungent odour. With an increase in
the size of the molecule, the odour becomes less pungent and more fragrant.

Aldehydes and Ketones: Chemical Reactions – I

The c = o groups govern the chemistry of aldehydes and ketones by providing a site for
nucleophilic addition and by increasing the acidity of the hydrogen atoms to the α-carbon.

The typical reactions of aldehydes and ketones are nucleophilic addition reactions.

The reactivity of the carbonyl group towards nucleophilic addition depends mainly upon
the electronic factor and the steric factor.

Aldehyde reacts with alcohol in the presence of anhydrous hydrogen chloride to form an
unstable intermediate known as hemiacetal.

Aldehydes and ketones react with primary amines to form substituted imines.

Aldehydes and ketones react with hydroxylamine to form the corresponding oximes.

Aldehydes and ketones react with hydrazine and its derivatives to form the corresponding
hydrazones.

Oximes and hydrazones are used to detect and purify aldehydes and ketones.

Carboxylic Acids: Nomenclature

Organic compounds that contain the carboxyl functional group, - COOH, are called
carboxylic acids.
Higher members of aliphatic carboxylic acids are known as fatty acids.

In the common system, aromatic acids are named as the derivatives of benzoic acid,
C6H5COOH.

In the IUPAC system, carboxylic acids are named by replacing the ending ‘e’ of the
corresponding alkane by ‘-oic acid’ to form alkanoic acid.

Compounds with more than one carboxyl group are named by retaining the ending ‘e’ of
the alkane, and adding the multiplicative prefix di, tri, etc. to the term ‘oic acid’.

Carboxylic Acids: Preparation

On oxidation, primary alcohols or aldehydes, gives carboxylic acids with same unmer of
carbon atoms.

Aldehydes can also be oxidised to the corresponding carboxylic acids even with mild
oxidising agents such as Tollen’s reagent or Fehling’s reagent.

The oxidation of alkyl benzene is one of the most useful methods for preparing an
aromatic carboxylic acid.

The carbonation of Grignard reagents and hydrolysis of nitriles can be used for converting
alkyl halides into the corresponding carboxylic acids having more than one carbon atom
than the parent alkyl halide.

The hydrolysis of acid derivatives such as amides, acid chlorides, anhydrides and esters
yields carboxylic acids.

Carboxylic Acids: Properties – I

The first four members of carboxylic acids are fairly soluble in water due to the ability of
the carboxyl group to form hydrogen bonds with water molecules.

Higher carboxylic acids are virtually insoluble in water due to the greater influence of the
hydrocarbon part.
The boiling points of carboxylic acids are higher than that of aldehydes, ketones and
alcohols of comparable molecular weights.

Unlike phenols, carboxylic acids react even with weaker bases such as carbonates and
bicarbonates to form the corresponding salts with the evolution of carbon dioxide.

The reaction of carboxylic acids with carbonates and bicarbonates is used to detect the
presence of the carboxyl group in an organic compound.

Every carboxylic acid has its characteristic Ka, which indicates how strong an acid is.

Electron-withdrawing groups increase the acidity of carboxylic acids by stabilising the

anion through the dispersal of the negative charge on the carboxylate ion by the inductive
or resonance effects.

Electron-donating groups, decrease the acidity by destabilising the anion by intensifying

the negative charge.

Carboxylic Acids: Properties – II

The reaction of carboxylic acids with weak bases is used to detect the presence of the
carboxyl group in an organic compound.

Carboxylic acids react with alcohols in the presence of a mineral acid catalyst to form
esters. The reaction is reversible and is known as esterification.

The esterification of carboxylic acids with alcohols is a nucleophilic acyl substitution

reaction.

When carboxylic acids are treated with phosphorous halides or thionyl chloride, the OH
group is replaced y a chlorine atom to form acid chlorides.

Carboxylic acids, on reduction with lithium aluminium hydride or diborane, give primary
alcohols.

When heated with soda lime, the sodium salts of carboxylic acids lose carbon dioxide to
form hydrocarbons. This reaction is known as decarboxylation.

Carboxylic acids with an alpha hydrogen react with chlorine or bromine in the presence of
a small amount of red phosphorus to give α-Halocarboxylic acids. This reaction is known
as the Hell-Volhard-Zelinsky reaction.
Carboxylic acids do not undergo the Friedel Crafts reaction because the carboxyl group is
deactivating and the catalyst, aluminium chloride, which is a Lewis acid, gets bonded to
the carboxyl group strongly.