A Process for the Production of a New a ẞ Naphthylene-diamine- mono-sulpho Acid.
Year: 1890

page_text: Date of Application, 24th June, 1890
Complete Specification Left, 21st Mar., 1891-Accepted, 2nd May, 1891
A Process for the Production of a New a ẞ Naphthylene-diamine-
mono-sulpho Acid.
JOHN DAWSON of Kirkheaton Color Works near Huddersfield and ROBERT
HIRSCH Ph. D. of Huddersfield do hereby declare the nature of this invention to
be as follows:-
In Patent 4065/1884, a process is described, according to which, by the addition
of the nitrates of primary aromatic amines to thoroughly cooled sulphuric acid,
the metanitro-derivations are almost exclusively obtained. The description of this
process mentions only m. nitroaniline, m. nitro-ortho and m. nitropara-toluidine.
But as Friedländer (in Die Fortschritte der Theerfarbenfabrikation. Page 531.)
justly remarks, this process is very far from furnishing exclusively the meta-
combinations. If an attempt is made to nitrify a napthylamin in the same
manner, the product of the reaction is a black pitch, from which, only with great
difficulty about 10% nitronapthylamin can be isolated.
The reaction with ẞnapthylanin is quite different. Two distinct nitronapthyl-
amines are formed, which differ from those hitherto known, in that the nitro
group is formed on the one side of the molecule and the amido group on the other.
The nitro group occupies the alpha position as by boiling the diazo combinations of
the new nitronapthylamine, alphanitronapthalene is formed. It occupies a place in
the other half of the nucleus, as the napthylendiamine obtained by reduction differs
from the napthylendiamines

page_text: The mother-liquor, from which this nitronapthylamine has been extracted, gives
another nitronapthylamine by neutralization, which is distinguished from the first
by its F.P. 105° and its greater solubility. It matters very little if alcohol, acetic-
acid or benzol be used for crystallisation. The salts also are more easily soluble &
more stable than those of the first described. The separation may also be effected
by the partial precipitation of the hot acid solutions with soda ash. The more
insoluble nitronapthylamine F.P. 143°, separates first, forming small needles. If a
filtered sample instead of forming needles with a further addition of soda ash, gives
an oily precipitate, it is necessary to filter off. The acetyl-compound of the nitro-
napthylamine F.P. 105°, as also that of the isomeric melts at 1970.
If both are
boiled with diluted sulphuric acid, the recovered nitronapthylamines have the same
F.P. of 143° resp. 105°.
:―
The way to carry out our invention may be seen from the following example
10 kilo. of nitrate of ẞ napthylamine are added slowly and in small quantities to
40 kilo. of sulphuric acid monohydrate, which has been cooled down to 0°. From
time to time the water formed by the reaction is carried off by adding adequate
quantities of fuming sulphuric acid; for this purpose about 20 kilo. sulphuric acid
20% SO, are consumed.
When the operation is finished, the sulphuration is mixed with 500 litres of water
and filtered off hot from some pitchy impurities. The sulphate of the nitro-
napthylamines F.P. 143° crystallises while cooling and must be separated from the
acid mother liquor. The latter is neutralized to about with milk of lime, filtered
off hot from the precipitated gypsum & the nitronapthylamine F.P. 105° is
precipitated by neutralising with soda ash.
The free base is produced by treatment of the sulphate of nitronapthyl-
amine F.P. 143° with a warm solution of soda ash. 10 kilo. thereof are reduced in a
still with 15 kilo. of iron borings & 2 kilo. acetic acid. at a temperature of about 100°
& when the reaction is finished, boiled up with 500 litres of water & 5 kilo.
hydrochloric acid. By adding 10 kilo. hydrochloric acid or 50 kilo. sodium chloride
to the filtered extraction, the muriatic salt is precipitated & filtered off. This,
after being dried, is heated with 40 kilo. sulphuric acid 66 Bé for 4 hours at a
temperature of 125°-130° & the sulphuration poured into 500 litres of water.
The precipitated sulpho acid is dissolved in soda ash. The filtered solution may be
used direct for the manufacture of coloring matters.
Dated this 23rd day of June 1890.
JOHN DAWSON.
ROBERT HIRSCH, Ph. D.
COMPLETE SPECIFICATION.
A Process for the Production of a New a ẞ Naphthylene-diamine-
mono-sulpho Acid.
We, JOHN DAWSON of Kirkheaton Color Works near Huddersfield, and
ROBERT HIRSCH Ph. D. of Huddersfield, do hereby declare the nature of this
invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
In Patent 4065/1884 a process is described, according to which by the addition of
the nitrates of primary aromatic amines to thoroughly cooled sulphuric acid, the
metanitro-derivations are almost exclusively obtained. The description of this
process mentions only m. nitro aniline, m. nitro ortho- and m. nitro para-toluidine.
But as Friedländer (in Die Fortschritte der Theerfarbenfabrication. Page 531.)
justly remarks, this process is very far from furnishing exclusively the meta-
combinations. If an attempt is made to nitrify napthylamine in the same manner,
the product of the reaction is a black pitch, from which, only with great difficulty
about 10% nitronapthylamine can be isolated.
(L

page_text: The reaction with B napthylamine is quite different. Two distinct nitro-
napthylamines are formed, which differ from those hitherto known in that the nitro
group is found on the one side of the molecule and the amido group on the other.
The nitro group occupies the alpha position, as by boiling the diazo combinations
of the new nitronapthylamine, alphanitronapthalene is formed. It occupies a place
in the other half of the nucleus, as the napthylendiamine obtained by reduction
differs from the nanthylendiamines
hitherto known.
.
The nitronapthylamine which forms the chief product of the reaction, gives a
yellow sulphate scarcely soluble in cold water, and which is precipitated when the
liquid of the reaction is poured into cold water. After crystallizing once or twice
with benzol or alcohol the base produced from this salt is obtained in beautiful,
long, red needles F.P. 143°; their acetyl compound melts at 1970. The salts
dissociate by the addition of water and can only be diazotized in a strong acid
solution. The nitronapthol obtained by boiling the diazo compound with water,
formis long, yellow needles F.P. 148°. The napthylendiamine obtained by reducing
this nitronapthylamine with tin and hydrochloric acid gives a salt which is very
slightly soluble in strong hydrochloric acid and may best be separated in this form.
Its solution turns a pale violet by ferric chloride and if boiled with it yields a black
violet precipitate. The free base is oily and gives an acetyl compound F.P. 260°,
which is scarcely soluble in alcohol, but easily in acetic acid. By sulphonating the
napthylendiamine with fuming sulphuric acid, or the sulphate with strong sulphuric
acid at a temperature of above 100°, the chief product formed is a mono sulpho
acid almost insoluble in cold water and crystallizing in small needles containing
water of crystallization, which if boiled with an insufficient quantity of water
change in a characteristic manner into short, heavy prisms. The salts show a blue
violet fluorescence.
The mother liquor, from which this nitronapthylamine has been extracted, gives
another nitronapthylamine by neutralization, which is distinguished from the first
by its F.P. 105° and its greater solubility. It matters very little if alcohol, acetic
acid or benzol be used for crystallization. The salts also are more easily soluble
and more stable than those of the first described. The separation may also be
effected by the partial precipitation of the hot acid solutions with soda ash. The
more insoluble nitronapthylamine F.P. 143°, separates first, forming small needles.
If a filtered sample, instead of forming needles with a further addition of soda ash,
gives an oily precipitate, it is necessary to filter off. The acetyl-compound of the
nitronapthylamine F.P. 105°, as also that of the isomeric melts at 197°. If both
are boiled with diluted sulphuric acid, the recovered nitronapthylamines have
respectively the same F.P. of 143° and 105°.
The way to carry out our invention may be seen from the following example:
10 kilos. of nitrate of ẞ napthylamine are added slowly and in small quantities
to 40 kilos. of sulphuric acid monohydrat, which has been cooled down to 0°: From
time to time the water formed by the reaction is carried off by adding adequate
quantities of fuming sulphuric acid; for this purpose about 20 kilos. of sulphuric
acid 20% SO, are consumed.
When the operation is finished, the sulphuration is mixed with 500 litres of water
and filtered off hot from some pitchy impurities. The sulphate of the nitro-
napthylamines F.P. 143° crystallizes while cooling and must be separated from the

page_text: acid mother liquor. The latter is neutralized to about with milk of lime, filtered
off hot from the precipitated gypsum and the nitronaphtylamine F.P. 105° is
precipitated by neutralizing with soda ash.
The free base is produced by treatment of the sulphate of nitronapthyl-
amine F.P. 143° with a warm solution of soda ash. 10 kilos. thereof are reduced in a
still with 15 kilos. of iron borings and 2 kilos. of acetic acid, at a temperature of
about 100° and when the reaction is finished, boiled up with 500 litres of water and
5 kilos. of hydrochloric acid. By adding 10 kilos. of hydrochloric acid or 50 kilos.
of sodium chloride to the filtered extraction, the muriatic salt is precipitated and
filtered off. This after being dried, is heated with 40 kilos. of sulphuric acid 66 Bé
for 4 hours at a temperature of 125-130° and the sulphuration poured into 500 litres
of water. The precipitated sulpho-acid is dissolved in soda ash. The filtered
solution may be used direct for the manufacture of coloring matters.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :
1. The manufacture of a mixture of nitronapthylamines of F.P. 143° and
F.P. 105° substantially as herein before described.
II. The separation of the abovenamed nitronaphtylamines substantially as herein
before described.
III. The production of the new a napthyldiamine-mono sulpho acid by
reduction of the nitronapthylamine of F.P. 143° and sulphonation of the base
obtained substantially as herein before described.
Dated this 21st day of March 1891.
JOHN DAWSON.
ROBERT HIRSCH.