IV,81.

DIAZOAMINOBENZENE
In a 250 ml. flask place 75 ml. of water, 24 g. (20 ml.) of concentrated
hydrochloric acid and 14 g. (13 7 ml.) of aniline. Shake vigorously (1) and
then add 50 g. of crushed ice. Run in a solution of 5-2 g. of sodium nitrite in 12
ml. of water, with constant shaking, during a period of 5-10 minutes. Allow to
stand with frequent shaking (1) for 15 minutes, and add a solution of 21 -0 g. of
crystallised sodium acetate in 40 ml of water during 5 minutes. A yellow
precipitate of diazoaminobenzene begins to form immediately; allow to stand
with frequent shaking for 45 minutes and do not allow the temperature to rise
above 20 (add ice, if necessary). Filter the yellow diazoaminobenzene on a
Buchner funnel, wash with it 250 ml. of cold water, drain as completely as
possible, and spread it on a sheet of filter paper to dry. The yield of crude
diazoaminobenzene, m.p. 91, is 15 g. (2). Recrystallise a small portion from
light petroleum, b.p. 60-80 : the pure compound, m.p. 97, is obtained.
Notes.
(1) For preparations on a larger scale, mechanical stirring is
recommended: a beaker or bolt-head flask should be used.
(2) About 200 ml. of light petroleum is required for recrystallisation. It is
therefore advisable, for the sake of economy when the preparation is
conducted by a large class of students, that only about 1 g. of the crude
material be recrystallised from this solvent. The crude compound may be
employed in the preparation of p-amino-azobenzene.
IV,82. p-AMINO-AZOBENZENE
Dissolve 5 g. of finely-powdered diazoaminobenzene (Section IV,81) in
12-15 g. of aniline in a small flask and add 2-5 g. of finely-powdered aniline
hydrochloride (1). Warm the mixture, with frequent shaking, on a water bath at
40-45 for 1 hour. Allow the reaction mixture to stand for 30 minutes. Then add
15 ml. of glacial acetic acid diluted with an equal volume of water : stir or shake
the mixture in order to remove the excess of aniline in the form of its soluble
acetate. Allow the mixture to stand, with frequent shaking, for 15 minutes : filter
the amino-azobenzene at the pump, wash with a little water, and dry upon filter
paper Recrystallise the crude p-amino-azobenzene (3-5 g. ; m.p. 120) from 1520 ml. of carbon tetrachloride to obtain the pure compound, m.p. 125.
Alternatively, the compound may be recrystallised from dilute alcohol, to which
a few drops of concentrated ammonia solution have been added. To prepare the

hydrochloride, dissolve about 1 g. of the compound (which need not be perfectly

dry) in about 8 ml. of alcohol. Add this solution to boiling dilute hydrochloric
acid (10 ml. of the concentrated acid and 80 ml. of water). Boil for 5 minutes,
filter the hot solution if necessary, and allow to cool. p-Amino-azobenzene
hydrochloride separates in steel-blue crystals. Filter, wash with a little dilute
hydrochloric acid, and dry. To recover the free base, dissolve the hydrochloride
in the minimum volume of boiling alcohol, add concentrated ammonia solution
dropwise until a clear solution results and the blue colour has become light
brown. Add water carefully until a cloudiness appears, warm on a water bath
until the cloudiness just disappears, and allow to cool. Yellow crystals of pamino-azobenzene separate on cooling.
Note.
(1) The aniline hydrochloride may be prepared by treating 2 g. of aniline
with an excess (about 3 ml.) of concentrated hydrochloric acid in a small
beaker, cooling, filtering at the pump, washing with a small volume of
ether, and drying between filter paper.