The Manufacture or Production of New Nitro Derivatives of the Anthracene Series.
Year: 1898

page_text: PROVISIONAL SI EUITIATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of New Nitro Derivatives of the
Anthracene Series.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
In the Specifications of Letters Patent No. 23927% and 4961%, my foreign
correspondents have described the production of valuable condensation products
aromatic
from one molecule of purpurine and one or two molecules of an
amine, and of sulphonic acids of the said condensation products.
My foreign correspondents have now found, that by treating the products
above mentioned with one or two molecules of nitric acid, nitro derivatives of
a high technical value are obtained. Each of the nitro derivatives which can
thus be obtained corresponds with one of the following formulae (R and R₁
meaning radicles of sulphonated or non-sulphonated aromatic hydrocarbons):
--

page_text: If boric is present, the reaction proceeds more smoothly. The products thus
obtained are more uniform, and therefore of a higher value.
In order to illustrate the new process, the following typical examples are
given. The parts are kilos. by weight.
EXAMPLE I.
NITRODERIVATIVE OF THE SULPHONIC ACID OF PURPURINE MONO-ANILIDE.
In order to produce this compound, the sulphonation of the purpurin-mono-
anilide, and the nitration of the sulphonic acid thus obtained, is profitably
combined in one operation. 10 parts of purpurine moncanilide are dissolved in
100 parts of concentrated sulphuric acid (66 degrees Baumé). The resulting-solu-
tions is heated to from 50 to 60 degrees Centigrade, until the formation of the
sulphonic acid is finished. Subsequently, the solution is cooled to 15 degrees
Centigrade, and then slowly mixed, under continuous stirring, with 9 litres
of a mixture of concentrated sulphuric acid and concentrated nitric acid which
contains 1.8 parts of pure HNO3. During this operation, care must
taken that the temperature does not exceed 20 degrees Centigrade.
further stirring for one hour, the reaction mixture is poured into 1000 litres
of water, and the finished nitro compound is precipitated in the shape of brown
flakes. It is soluble with difficulty in acidulated water, and soluble in hot
wafer. By caustic soda lye, it is dissolved with a red colour.
After
It is capable of dyeing chrome mordanted-wool yielding from violet to violet-
black fast shades.
EXAMPLE II.
10 parts of purpurine mono-anilide are dissolved in 100 parts of concentrated
sulphuric acid, and sulphonated as described in the foregoing example. Sub-
sequently, 10 parts of crystallized boric acid are added to the mixture, the
boric acid ether of the purpurine derivative being thus produced. When the
formation of the boric acid ether is finished, which is the case if the color of the
mixture has changed into blue, the mixture is cooled down to from 10 to 15
degrees Centigrade. It is then mixed (while well stirring) with 9 litres of
a mixture of concentrated sulphuric acid and concentrated nitric acid which
contains 1.8 parts of pure HNO3. After further stirring for about one hour, the
mixture is poured into 1000 litres of water, the finished dye-stuff being thus
obtained in the shape of a brown flaky precipitate.
This dye-stuff is very similar to that described in the foregoing example, but
yields much deeper shades. According to the researches of my foreign corre-
spondents, it has probably the formula:-

page_text: EXAMPLE III.
10 parts of purpurine mono-anilide are dissolved, at about 10 degrees Centi-
grade, in a solution prepared from 100 parts of concentrated sulphuric acid
(66 degrees Baumé) and 10 parts of boric acid. To the resulting solution,
9 litres of a mixture of concentrated sulphuric acid and concentrated nitric acid
which contains 1.8 parts of pure HNO,, are added, with stirring, at from 10 to
15 degrees Centigrade. After further stirring for about one hour, the mixture
is poured into water. The brown flaky precipitate thus obtained is purified by
a recrystallisation from pyridine, from which it crystallises in the shape of
reddish-brown glittering crystals, that dissolve in aniline with a red colour,
and in concentrated sulphuric acid with a violet colour.
By treating this nitro compound with sulphuric mono-hydrate, or with a weakly
fuming sulphuric acid, it is transformed into a sulphonic acid which dyes chrome-
mordanted wool from grey to black shades.
EXAMPLE IV.
10 parts of purpurine dianilide are sulphonated, at about 60 degrees. Centi-
grade, by means of 100 parts of concentrated sulphuric acid (66 degrees Baumé).
After adding 10 parts of crystallized boric acid to this solution, it is stirred
for about half an hour. It is then cooled to 10 degrees Centigrade, and slowly
mixed (while continuously stirring) with 19.5 litres of a mixture of sulphuric
acid and nitric acid which contains 3.9 parts of HNO, the temperature being
kept below 20 degrees Centigrade. On pouring the mixture into water, the new
dinitrated dye-stuff is precipitated in the shape of brown flakes. It dyes chrome-
mordanted wool deep and fast black shades.
My foreign correspondents wish it to be understood that they do not intend to
confine themselves to the particulars given in the examples, as these are merely
typical, and can be varied within wide limits. Thus, for instance, the anilido
derivatives from purpurine used in the examples, can be replaced by the con-
densation products from one molecule of purpurine with one or two molecules
of other aromatic amines. The process then proceeds in an analogous manner.
Dated this 22nd day of July 1898.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Nitro Derivatives of the
Anthracene Series.
I, HENRY EDWARD NEWTON, of the Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, 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 the Specifications of Letters Patent Nos. 23927% and No. 4961%, my foreign
correspondents have described the production of valuable condensation products
from one molecule of purpurine and one or two molecules of an aromatic
amine, and of sulphonic acids of the said condensation products.
My foreign correspondents have now found that by treating the products
above mentioned with one or two molecules of nitric acid, nitro derivatives of
a high technical value are obtained. Each of the nitro derivatives which can

page_text: thus be obtained corresponds with one of the following formulae (R and R
meaning radicles of sulphonated or non-sulphonated aromatic hydrocarbons):-
OH
2
All thes new nitro compounds are decomposed under regeneration of. pur-
purine, when they are heated with a sulphuric acid of 60 degrees Baumé.
The new process is profitably performed in concentrated sulphuric acid
solution. It can be carried out either with or without the presence of boric
acid.
If boric acid is present during the reaction, the resulting nitro products are
more uniform, and therefore of a higher value.
In order to illustrate the new process, the following typical examples are
given. The parts are kilos. by weight.
EXAMPLE I.
NITRODERIVATIVE OF THE SULPHONIC ACID OF PURPURINE MONO-ANILIDE.
In order to produce this compound, the sulphonation of the purpurinmono-
anilide, and the nitration of the sulphonic acid thus obtained, is profitably
combined in one operation. 10 parts of purpurine monoanilide are dissolved in
100 parts of concentrated sulphuric acid (66° Baumé). The resulting-solu-
tion is heated to form 50 to 60 degrees Centigrade, until the formation of the
sulphonic acid is finished. Subsequently, the solution is cooled to 15 degrees
Centigrade, and then slowly mixed, under continuous stirring, with 9.5 litres
of a mixture of concentrated sulphuric acid and concentrated nitric acid, the said
9.5 litres containing 1.9 parts of pure HNO,. During this operation, care must
be taken that the temperature does not exceed 20 degrees Centigrade. After
further stirring for one hour, the reaction mixture is poured into 1000 litres
of water, by means of which operation the finished nitro compound is precipitated
in the shape of brown flakes. It is soluble with difficulty in acidulated water, and
soluble in hot water. By caustic soda lye it is dissolved with a red color.
It is capable of dyeing chrome-mordanted wool, yielding from violet to violet-
black fast shades.
EXAMPLE IL
10 parts of purpurine mono-anilide are dissolved in 100 parts of concentrated
sulphuric acid, and sulphonated as described in the foregoing example. Sub-
sequently, 10 parts of crystallized boric acid are added to the mixture, the
boric acid ether of the purpurine derivative being thus produced. When the
forination of the horic acid ether is finished (which is the case if the color of the
mixture has changed into blue), the mixture is cooled down to from 10 to 15
degrees Centigrade. It is then mixed (while being well stirred) with 9.5 litres of

page_text: a mixture of concentrated sulphuric acid and concentrated nitric acid, the said
9.5 litres containing 1.9 parts of pure HNO3. After further stirring for about
one hour, the mixture is poured into 1000 litres of water, the finished dye-stuff
being thus obtained in the shape of a brown flaky precipitate.
This dye-stuff is very similar to that described in Example I, but
yields much deeper shades. According to the researches of my foreign corre-
spondents it has probably the formula:
to light, to milling, and to acids.
EXAMPLE III.
10 parts of purpurine mono anilide are dissolved, at about 10 degrees Centi-
grade, in a solution prepared from 100 parts of concentrated sulphuric acid
(66 degrees Baumé) and 10 parts of boric acid. To the resulting solution,
9.5 litres of a mixture of concentrated sulphuric acid and concentrated nitric acid
(the said 9.5 litres containing 1.9 parts of pure HNO3) are added, with stirring,
at from 10 to 15 degrees Centigrade. After further stirring for about one
hour, the mixture is poured into water. The brown flaky precipitate thus
obtained is purified by a recrystallisation from pyridine, from which it crystallizes
in the shape of reddish-brown glittering crystals, that dissolve in aniline with a
red color, and in concentrated sulphuric acid with a violet color.
By treating this nitro compound with sulphuric monohydrate, or with weak
fuming sulphuric acid, it is transformed into a dye-stuff, which dyes chrome-
mordanted wool from grey to black shades.
EXAMPLE IV.
10 parts of purpurine dianilide are sulphonated, at about 60 degrees Centi-
grade, by means of 100 parts of concentrated sulphuric acid (66 degrees Baumé).
After adding 10 parts of crystallized boric acid to this solution, it is stirred
for about half an hour. It is then cooled to 10 degrees Centigrade, and slowly
mixed (while being continually stirred) with 15.5 litres of a mixture of sul-
phuric acid and nitric acid (the said 15.5 litres containing 3.1 parts of HNO3),
the temperature being kept below 20 degrees Centigrade. On pouring the
mixture into water, the new dinitrated dye-stuff is precipitated in the shape of
brown flakes. It dyes chrome-mordanted wool deep and fast black shades.
My foreign correspondents wish it to be understood that they do not intend to
confine themselves to the particulars given in the examples, as these are merely
typical, and can be varied within wide limits. Thus, for instance, the anilido
derivatives from purpurine used in the examples, can be replaced by the con-
densation products from one molecule of purpurine, with one or two molecules
of other aromatic amines. The process then proceeds in an analogous manner.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed (as communicated
to me from abroad), I declare that what I claim is:-
1. The process for producing new dye-stuffs of the anthraquinone series, by

page_text: treating with one or two molecules of nitric acid, in or without the presence of
boric acid, the condensation products of one molecule of purpurine, with one or
two molecules of aromatic amines, or the sulphonic acids of these condensation
products (which condensation products and sulphonic acids are described and
claimed in the Letters Patent No. 23927% and No. 496195), substantially as herein-
before described.
2. As new articles of manufacture, the new products obtainable by the processes
herein before described and claimed.