Year: 1886

page_text: This Specification was, upon the 8th day of December 1887, amended under
Sections 18 to 21 of the Patents, Designs, and Trade Marks Act, 1883.
[Communicated from abroad by Messieurs WIRTH & Co., of Frankfort on the Main,
in the Empire of Germany, Acting as Agents of A. Leonhardt & Co., of Mühlheim,
Grand Duchy of Hesse, in the Empire of Germany.]
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake, & Co., Patents Agents,
Southampton Buildings in the County of Middlesex do hereby declare the nature of
my invention to be as follows:-
This invention relates to the manufacture of colouring matters.
In the production of azo-colouring matters according to this invention, I take
paranitrotoluol in its commercial form and sulphurate it by means of sulphuric acid
with the aid of heat..
Suitable proportions for sulphurizing or sulphurating are for example as follows.
100 parts by weight of paranitrotoluol.
100 parts of anhydrous concentrated sulphuric acid of 66° Beaume.
200 parts of anhydrous fuming sulphuric acid containing 35% of free anhydrous
acid.
These substances, after being mixed, are heated to 130° C or more, for from 12 to
24 hours.
Instead of the fuming sulphuric acid, concentrated sulphuric acid with pyrosulphate
or monochlorhydrin or with any agent which effects sulphuration can be used; the
conditions of time and temperature also can be suitably modified according to the
concentration and quantity of the sulphurating agents.
The paranitrotoluolsulpho-compound thus obtained can be transformed according to
known methods, into the hydrazo-combination, which, by being treated with suitable
acids, is transformed into a new sulpho-acid which dissolves with difficulty and which
is considered to be paratolidinedisulpho-acid.

page_text: The formation of colouring matter is effected in the usual manner by causing
1 molecule of the new sulpho acid to act upon 2 molecules of nitrite, and by bringing
the tetrazo-body thus produced into further reaction with the following substances.
1. naphthionic acid
.
The formation of colouring matter is effected in the usual manner by causing
1 molecule of the new sulpho acid to act upon 2 molecules of nitrite, and by bringing
the tetrazo-body thus produced into further reaction with the following substances.
1. naphthionic acid
2. Brönner's ẞ naphthylaminesulpho-acid
yields purple-red and high red
colouring matters.
5.
naphthylamine
3. Liebmanns ẞ
do
4. Dahls 3
do
N° III
}
claret colouring matters.
yields violet colouring matters.
6. Laurent's amidonaphthalinesulpho-acid
7. a naphthylamine
8. ẞ naphtholdisulpho-acid
9.
naphtholmonosulpho-acid (Schäffer)
10. 3 naphthol and a naphthol
11. Resorcine-red coloring matter.
EXAMPLE FOR THE PRODUCTION OF THE COLOURING MATTERS.
40 kilogrammes of the sodium salt of the new sulphoacid are dissolved in water and
diazotized with 14 kilogrammes of nitrate and 50 kilogrammes of muriatic acid. The
tetrazobody thus produced is brought into reaction with 50 kilogrammes of the sodium
salt of the naphthylamine sulpho-acid (Brönner's naphthylaminesulpho-acid)
obtained from ẞ naphthol ẞ sulpho-acid to which a quantity of acetate of soda is
added as necessary for the neutralization of the free mineral acid. After being left
for some time to cool, the mixture is again heated and kept at a high temperature
until the reaction is completed. The free colouring acid is precipitated by means of
common salt and converted into its sodium salt.
Dated this 29th day of March 1886.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: Improvements in and relating to the Manufacture of Colouring
Matters.
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake & Co., Patent Agents,
45 Southampton Buildings, in the County of Middlesex do hereby declare the nature
of my invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
This invention relates to the manufacture of colouring matters.
In the production of azo-colouring matters according to this invention I take
paranitrotoluol. in its commercial form, and sulphurate it by means of sulphuric acid
with the aid of heat.
-
Suitable proportions for sulphurizing or sulphurating are, for example, as follows :-
100 parts by weight of paranitrotoluol..
100 parts of concentrated, sulphuric acid of 66° Baumé. and
200 parts of anhydrous fuming sulphuric acid containing 35% of free anhydrous
acid.
These substances after being mixed are heated to 120 C or more for from 12 to
24 hours.
Instead of the fuming sulphuric acid, concentrated sulphuric acid with pyrosulphate
or monochlorhydrin, or any agent which effects sulphuration, can be used; the
conditions of time and temperature also can be suitably modified according to
the concentration and quantity of the sulphurating agents.
If the paranitrotoluolsulpho compound thus obtained is treated with soda lye and
zinc-dust a new substance is obtained, which in the provisional specification of this
application was termed "paratolidinedisulpho acid."
From the continued experiments which have been made with the new substance
thus obtained, it has been found that this name does not indicate the chemical nature
of the said substance. This designation therefore is abandoned, the new substance
being hereinafter termed a "new amidosulphoacid." but that it has been found to he
disulpho acid of diamidostilben.
Instead of treating the paranitrotoluol sulpho acid with soda lye and zinc-dust
simultaneously, it can first be treated with soda lye and then reduced with zinc-dust in
an alkaline solution, or with proto-chloride of tin in an acid solution. This successive
treatment is preferable because the quantity of the product obtained is greater than
with the former method.
In manufacturing the new amidosulpho acid I accordingly proceed as follows:-
50 kilogrammes of the soda salt of paranitrotoluolsulpho acid are dissolved in
water and treated with about 30 kilogrammes of strong caustic soda lye. The result
s an intensely red fluid, from which a yellow colouring matter may be obtained by
alting out. But in the present instance I do not salt out, but add to the fluid as
nuch zinc-dust as necessary to render the fluid colourless. I then filtrate it and
precipitate the new amidosulpho-acid by means of hydrochloric or other suitable acid,

page_text: grammes of a-naphthol. The colouring matter, after standing for several hours, is
precipitated by means of common salt.
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 by my
foreign Correspondents I declare that what I claim is :-
First. The production of a new amidosulpho acid by simultaneously or successively
treating a paranitroluolsulpho acid by caustic lye and a reducing agent, such as zinc-
dust, the colourless solution thus obtained being then treated with hydrochloric or
other acid in order to precipitate the said new amidosulpho acid.
Second. The production of colouring matters by diazotizing, the new admidosulpho
acid and combining the diazo-product with one or other of the following substances
according to the colour desired.
DL

page_text: Date of Application, 29th Mar., 1886.
Complete Left, 20th Oct., 1886.
Complete Accepted, 25th Mar., 1887.
RESERVE
[Communicated from abroad by Messieurs WIRTH & Co., of Frankfort on the Main,
in the Empire of Germany, Acting as Agents of A. Leonhardt & Co., of Mühlheim,
Grand Duchy of Hesse, in the Empire of Germany.]
I, HENRY HARRIS LAKE, of the firm of Haseltine, Lake, & Co., Patent Agents,
Southampton Buildings in the County of Middlesex do hereby declare the nature of
my invention to be as follows:-
This invention relates to the manufacture of colouring matters.
In the production of azo-colouring matters according to this invention, I take
paranitrotoluol in its commercial form and sulphurate it by means of sulphuric acid
with the aid of heat.
Suitable proportions for sulphurizing or sulphurating are for example as follows.
100 parts by weight of paranitrotoluol.
100 parts of anhydrous concentrated sulphuric acid of 66° Beaume.
200 parts of anhydrous fuming sulphuric acid containing 35% of free anhydrous
acid.
These substances, after being mixed, are heated to 130° C or more, for from 12 to
24 hours.
Instead of the fuming sulphuric acid, concentrated sulphuric acid with pyrosulphate
or monochlorhydrin or with any agent which effects sulphuration can be used; the
conditions of time and temperature also can be suitably modified according to the
concentration and quantity of the sulphurating agents.
The paranitrotoluolsulpho-compound thus obtained can be transformed according to
known methods, into the hydrazo-combination, which, by being treated with suitable
acids, is transformed into a new sulpho-acid which dissolves with difficulty and which
is considered to be paratolidinedisulpho-acid,

page_text: The formation of colouring matter is effected in the usual manner by causing
1 molecule of the new sulpho acid to act upon 2 molecules of nitrite, and by bringing
the tetrazo-body thus produced into further reaction with the following substances.
1. naphthonic acid
2. Bronner's ẞ manhthylaminesulpho-acid
1
1
The formation of colouring matter is effected in the usual manner by causing
1 molecule of the new sulpho acid to act upon 2 molecules of nitrite, and by bringing
the tetrazo-body thus produced into further reaction with the following substances.
1. naphthonic acid
naphthylaminesulpho-acid
2. Brönner's
3. Liebmanns ẞ
4. Dahls ẞ
5.
naphthylamine
do
do
No III
Fields purple-red and high red.
colouring matters.
6. Laurent's amidonaphthalinesulpho-acid
7. a naphthylamine
8. ẞnaphtholdisulpho-acid
9.3 naphtholmonosulpho-acid (Schäffer)
10. ẞ naphthol and a naphthol
11. Resorcine-red coloring matter.
claret colouring matters.
yields violet colouring matters.
EXAMPLE FOR THE PRODUCTION OF THE COLOURING MATTERS.
40 kilogrammes of the sodium salt of the new sulphoacid are dissolved in water and
diazotized with 14 kilogrammes of nitrate and 50 kilogramines of muriatic acid. The
tetrazobody thus produced is brought into reaction with 50 kilogrammes of the sodium
salt of the naphthylamine sulpho-acid (Brönner's naphthylaminesulpho-acid)
obtained from ẞ naphthol B sulpho-acid to which a quantity of acetate of soda is
added as necessary for the neutralization of the free mineral acid. After being left
for some time to cool, the mixture is again heated and kept at a high temperature.
until the reaction is completed. The free colouring acid is precipitated by means of
common salt and converted into its sodium salt.
Dated this 29th day of March 1886.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.

page_text: The said new acid is purified by dissolving it in soda solution and precipitating with
hydrochloric acid.
Thus manufactured the new amido sulpho acid forms a yellowish powder, which is
insoluble in water or spirit, but dissolves easily in alkaline fluids.
If a concentrated watery solution of the new acid is treated with common salt, its
barium salt precipitates and crystallizes in mother-of-pearl-like leaves.
The diazocompound of the new amidosulpho acid is hardly soluble in water.
The formation of colouring matter is effected in the usual manner by causing
1 molecule of the new sulpho acid to act upon 2 molecules of nitrite, and by bringing
the tetrazo body thus produced into further reaction with 2 molecules of the following
substances.
Phenol and its hourologons
1. Red. 40 kilogrammes of the sodium salt of the new amido sulpho acid are
dissolved in water and diazotized with 14 kilogrammes of nitrite and 50 kilogrammes
of muriatic acid. The tetrazobody thus produced is brought into reaction with 50 kilo-
grammes of the sodium salt of the ẞ naphthylaminesulpho-acid (Brönner's naphthy-
lamine sulpho-acid) to which a quantity of acetate of soda is added as necessary for
the neutralization of the free mineral acid. After being left for some time to cool the
mixture is again heated and kept at a high temperature until the reaction is completed.
The free colouring acid is precipitated by means of common salt and converted into
its sodium salt.
2. Yellow. 8 Kilogrammes of the soda salt of the new amidosulpho acid are
dissolved in water and diazotized by means of 2.8 kilogrammes of nitrite of soda and
10 kilogrammes of hydrochloric acid. The diazo compound thus obtained is added to
an alkaline solution of 6 kilogrammes of salicylic acid. After standing for some time
the colour is precipitated by means of common salt.
3. Violet. 8 Kilogrammes of the new amidosulpho acid are diazotized in the above
described manner and the diazo-product is poured into an alkaline solution of 6 kilo-
grammes of a-naphthol. The colouring matter, after standing for several hours, is
precipitated by means of common salt.
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 by my
foreign Correspondents I declare that what I claim is :-
First. The production of a new amidosulpho acid by simultaneously or successively
treating a paranitroluolsulpho acid by caustic lye and a reducing agent, such as zinc-

page_text: dust, the colourless solution thus obtained being then treated with hydrochloric or
other acid in order to precipitate the said new amidosulpho acid.
Second. The production of colouring matters by diazotizing, the new amidosulpho
acid and combining the diazo-product with one or other of the following substances
according to the colour desired.
D1