NIPAGIN PREPARATION

1. The diazotization of the p-aminobenzoic acid

a) The diazotization of the p-aminobenzoic acid
Diazotization is a chemical process which results in the formation of the
diazonium salts.
The diazotization reaction involves the primary aromatic amines. They
transform into diazonium salts under the action of the nitrous acid (HNO2), at low
temperatures (050C), in the presence of strong mineral acids (HCl, H 2SO4) in
excess (2,53 moles relative to 1 mol of amine) and in diluted aqueous solution.
Diazotization is practically achieved by gradually adding, under continous
stirring, small portions of a concentrated solution of sodium nitrite, the equivalent
of a quantity of 1,02 -1,05 moles, to a cold mixture (05 0C) consisting of 1 mol of
aromatic amine and 2,53 moles of diluted mineral acid (between 1520%).
The diazotization agent is the nitrosonium ion (N +=O), which results from the
hetrolytic cleavage of the nitrous acid (obtained from the reaction between NaNO 2
and H2SO4), protonated by the strongly acidic medium.
HO

N=O

N=O

N =O

H2O

Diazonium salts are generally crystallized substances, easily soluble in

water, sparingly soluble in alcohol and ether, colourless, which become brown in
contact with air. The reaction underlying the diazotization of the paminobenzoic acid is the following:
COOH

NH2

COOH

HNO2 + H2SO4

+ 2 H2O

N ] HSO4

Necessary substances
The p-aminobenzoic acid (Mr=137)..................... 13,7 g (0.10 moles)
Sodium nitrite (Mr=69)............................................ 7 g (0.102 moles)
Concentrated sulfuric acid (Mr=98; d=1.84)....... 10,7 ml (0.20 moles)

Working technique
13,7 g of p-aminobenzoic acid are placed over a solution of sulfuric acid (10.7
ml of 96% H2SO4 in 60 ml of distilled water) in a Berzelius beaker, under
continous stirring, at high temperatures (on a water bath) in order to achieve its
partial solubilization. It is stirred at elevated temperatures for a period of 15-30
minutes.
The mixture is cooled down in an ice and salt bath, method which accelerates
the cooling process up to 050C, and by adding 25 g of ice (instead of water). The
following process extends over a period of 60 minutes and consists in the dropwise
addition of a solution of sodium nitrite under continous stirring. The sodium nitrite
solution is obtained by dissolving 7 g of NaNO2 in 15 ml of water.
In order to perfect the reaction the reaction mixture is stirred for an additional
period of 30 mnutes.
The diazonium salt solution preserved at low temperatures will be used in the
next phase (the final volume is 110 ml for 0.10 moles of p-aminobenzoic acid).
b) The hydrolysis of the p-aminobenzoic diazonium salt
The aromatic diazoderivatives (the diazonium salts) are relatively stable
combinations but only at low temperatures (050C) and for a limited period of
time. They are intermediate products used for the preparation of some organic
substances which can take part in two types of reactions:
1) reactions involving the elimination of the diazo group (-N=N-) under the
form of molecular nitrogen and its replacement with various substituents
(hydrogen, hydroxyl, halogens, cyano, mercapto etc.);
2) reactions involving the retention of the diazo group (the diazonium aryl
cation Ar-N=N+ being a weak electrophilic reactant), when the diazonium salts are
coupled with the phenols or the aromatic amines, resulting in diazo- or azoaminoderivatives.
The reaction of hydrolysis of the diazonium salt obtained in the diazotization
stage is the following:
COOH

COOH

H2O
-

N ] HSO4

50 0 C

H2SO4
OH

N2

H2SO4

Necessary substances
Diazonium salt solution (from the a phase).......................... 110 ml
Concentrated sulfuric acid (Mr=98; d=1.84)..........5.2 ml (0,1 moles).
Working technique
A solution consisting of 5.2 ml H2SO4 96 % (approximately 0.1 moles) and
7,5 ml of
water is introduced in a round-bottom flask equipped with a reflux condenser. The
diazonium salt solution resulted from the previous phase is added over this solution
and then the reaction mixture is heated on a water bath at a temperature of 4050 0C
until it finished releasing nitrogen.
The content of the round-bottom flask is decanted in a Berzelius beaker and
the reaction mixture is cooled down in an ice bath until the p-aminobenzoic acid
crystallizes.
The product is separated by means of filtration and the precipitate is washed
directly on the filter with cold water until the pH reaches a value of 5 and it is dried
at a temperature of 60700C .
The result is approximately 11.9 g p-hydroxybenzoic acid (=88%) under the
form of orange-brown crystals.
The pure p-hydroxybenzoic acid appears under the form of colourless crystals
with a value of the melting point of 210 0C. (In water, at a temperature of 150C, the
product has a solubility of 0.44 g at 100 ml of solution).