Introduction

Benzoic acid with the Latin name Acidum

benzoicum. Benzoic acid, C7H6O2 (or
C6H5COOH), is a colorless crystalline solid and
the simplest aromatic carboxylic acid .
Benzoic acid is produced for medicinal purposes
as an API for use as an antifungal and as an
antibacterial agent. It is also used as a
preservative in food and in cosmetics.

INTRODUCTION CONTD
It was first discovered in benzoic gum. It is
encountered in the free state in some
resins, balsams (Peru and tolu balsam)
and cranberries.

PRINCIPLES
The main starting material is benzyl
chloride.
Through the process of oxidization, benzyl
chloride is converted to benzoic acid in the
presence of potassium permanganate.
Sodium carbonate provides the alkaline
medium for the reaction.

PRINCIPLES CONT
Potassium permanganate oxidizes benzyl
alcohol to potassium benzoate
HCl hydrolyse potassium benzoate to the
acid which is seen as a ppt & manganese
dioxide
Sodium sulphite dissolves manganese
dioxide which remains in filtrate.

PRINCIPLES CONTD
For all syntheses, benzoic acid can be
purified by recrystallization from water
because of its high solubility in hot water
and poor solubility in cold water

LABORATORY SYNTHESIS
Benzoic acid is cheap & readily available
BA purified by recrystallization from water
due to high solubility in hot water & poor
solubility in cold water.
Other recrystallization solvents used:
acetic acid (anhydrous / aq), benzene, pet
ether, ethanol + water

 REAGENTS:

Benzyl chloride
Potassium permanganate
Anhydrous sodium carbonate
Hydrochloric acid
20% sodium sulphite

PROCEDURE FOR SYNTHESIS

To 200ml of water in a conical flask, add 5g of
anhydrous sodium carbonate, 10g of potassium
permanganate crystals and 5ml of the benzyl
chloride solution.
Connect the conical flask to a reflux condenser
and do the refluxing for about one and a half
hour to ensure that is completely oxidized and
there is no oily droplets of benzoic acid in the
condensate.

 Cool the solution, and acidify with enough

hydrochloric acid to ensure precipitation of
all the benzoic acid.
Add 20% sodium sulphite solution until all
manganese dioxide dissolves
Filter the benzoic acid crystals and wash
repeatedly with water.
Recrystallize from boiling water, wash and
dry to obtain the pure crystals.

PROCEDURE FOR
SYNTHESIS
The purity is tested by
determining its melting point and
comparing it with literature values.

 OTHER METHODS
By hydrolysis
Like any other nitrile or amide, benzonitrile
and benzamide can be hydrolyzed to
benzoic acid or its conjugate base in acid
or basic conditions.

 From benzaldehyde
The base-induced disproportionation of benzaldehyde,
the Cannizzaro reaction, affords equal amounts of
benzoate and benzyl alcohol; the latter can be removed
by distillation.

OTHER METHODS
From bromobenzene
Bromobenzene can be converted to
benzoic acid by "carbonation" of the
intermediate phenylmagnesium bromide:
[5]
C6H5MgBr + CO2 C6H5CO2MgBr
C6H5CO2MgBr + HCl C6H5CO2H +
MgBrCl

 Oxidation of toluene to benzoic acid

Toluene can be converted to benzoic acid by
oxidizing its side chain, i.e. the CH3 group,
by means of permanganates or dichromates.
The process is catalyzed by cobalt or
manganese naphthenates. The process uses
cheap raw materials, proceeds in high yield,
and is considered environmentally green.

PRECAUTIONS
1. Refluxing is done for a longer period of
time at least one hour thirty minutes.
This is to ensure that the reaction is
complete and that all the benzyl chloride
has been oxidised to benzoic acid. This
is seen with the absence of oil droplets in
the condenser.

PRECAUTIONS
2. Potassium permanganate is a strong
oxidising agent and very corrosive
so,gloves and protective clothing should
be worn whilst handling it to prevent the
staining of fingers and clothing,
3.When toluene is used as a starting
material,open flames should be avoided.
This is to prevent the starting of fire due to
the flammmability of toluene.

PRECAUTIONS CONTD
4.Gloves should be worn when handling
sodium sulphite this is to prevent its
irritating reaction.

MODERN ADVANCEMENT
Historical preparation involved the reaction of
benzotrichloride with calcium hydroxide in water using
iron as catalyst but pdt contained significant amounts of
chlorinated benzoic acid derivatives
Also formerly prepared by the chlorination of toluene with
the subsequent hydrolysis of the benzotrichloride
Modern commercial preparation is by catalytic oxidation
of toluene with oxygen at elevated temp. with a cobalt
catalyst and purification by sublimation

Modern lab methods include

Hydrolysis of a benzonitrile or benzamide in
acidic or basic medium
Refluxing benzyl alcohol with permanganate or
other oxidizing agents in water. The mixture hot
filtered to remove manganese oxide and then
allowed to cool to afford benzoic acid
Grignard reaction
Prolonged oxidation of alkyl benzene with
permanganate regardless of the length of the
alkyl group

In this experiment you will make the Grignard reagent phenyl

magnesium bromide; this reagent will then be treated with carbon
dioxide to form benzoic acid.

Uses of benzoic acids

Na salt is used as antifungal agent in
pceutical prep e.g. Whitfield's ointment
Used as food preservative cos it inhibits
growth of mould, yeast and some
bacteria. conc. used is normally 0.05-1.0%
Na benzoate is used as preservative for
beverages e.g. fruit juices, soft drinks
Benzoic esters are used as solvents

Uses contd
Benzyl benzoate is used in artificial
flavours and insect repellents
Used as a tabletting lubricant
Used to produce Glycol benzoate for
application of plasticizer for adhesive
formulations
Used as corrosion inhibitor in industries
Used as a stabilizer in photographic
processing