Improvements in the Production of Colouring Matters.
Year: 1889

page_text: Date of Application, 9th July, 1889.
Complete Specification Left, 3rd Mar., 1890-Accepted, 5th Apr., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by Messrs. WIRTH & Co., of Frankfort-on-the-Main, in'
the Empire of Germany, acting as Agents for K. Oehler, of Offenbach-on-the-
Main, in the Empire of Germany.]
Improvements in the Production of Colouring Matters.
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
this invention to be as follows:-
My invention has for its object the production of new brown azo colouring
matters by first producing intermediate bodies having the general formula.
SO, HC. Hạn– [N = N, Hạn– (NH₂—)₂],
20
which are formed by the action of diazotized sulpho-acids of aromatic meta-diamines
upon two molecules of a diamine and combining these intermediate bodies with
diazotised aromatic sulpho-acids.
These colouring matters which have not heretofore been described. have the property
of dyeing unmordanted cotton in an alcaline bath brown.
The following examples are given to show the method of procedure.
1st Example. Preparation of the intermediate compound from the toluylene-
diamine-sulpho-acid 1: 2: 4:5= (CH, NH, NH, SO, H) (prepared by sulphur-
ising toluylene-diamine-Wiesinger, Berliner Berichte 7-464) and meta-phenylene-
diamine.
A solution cooled to 0° of 15 parts of the sodium salt of the toluylene-diamine-
sulpho-acid and 6, 9 parts of sodium-nitrite in 500 parts of water is slowly introduced
into diluted muriatic acid (containing 60 parts of muriatic acid of 22, 5° B.) and
cooled with ice. . As soon as it is found that there is no more nitrous acid in the liquid
it is mixed with a solution of 21 parts of meta-phenylene-diamine-sulphate and 100
parts of crystallized acetate of sodium in 1000 parts of water.
The intermediate compound obtained (toluylene diamine-sulpho-acid-diazometa-
phenylene-diamine-meta-phenylene-diamine) is formed at once and precipitates as a
dark-brown mass, which is filtered pressed, transformed in its sodium salt and dried.
The dye stuff is a brown powder, soluble in water with a yellow-brown colour; the
acid of the dye-stuff is only soluble in water with difficulty.
2nd Example. Intermediate compound from toluylene-diamine-sulpho-acid 1:2:
4:6= (CH, NH, SO, H: NH2) and meta-phenylene-diamine. The preparation
of this body is effected in the manner described in the first example, with this difference,
that there are used but 36 parts of muriatic acid of 22, 5° B. instead of 60 parts;
and 25 parts calcined soda instead of 100 parts of acetate of sodium.
In this case the body obtained is precipitated as a dark-brown mass, which is filtered,
pressed and dried. This intermediate body forms a reddish-brown powder, soluble in
water, with a light-yellow-brown colour; acids precipitate it from the watery solutions
as yellowish-orange flocks.
3rd Example. Intermediate compound from toluylene-diamine-sulpho-acid 1:2:
4:6 (CH, SO, H: NH, NH2) and meta-phenylene-diamine.
-
:
:
The diamido-acid used in this process is not yet known; it is obtained by reduction
of the dinitro-ortho-toluol-sulpho-acid described by Schwanert (Annalen der Chemie
u. Pharmacie 186, 349). Like its isomerics it is soluble with difficulty in cold water
and easily soluble in hot water; in diluted watery solutions the diamido-acid crystallizes
in the form of large light-brown coloured prisins.
The combination of the diazotized diamido-sulpho-acid with Meta-phenylene-diamine
حر

page_text: and the separation of the formed compound is operated in the same manner as described
in the 1st example. The body is a blackish-brown powder resembling the compounds
of the first and second example as regards its other properties.
A second series of very similar intermediate compounds is obtained in replacing
in the examples 1, 2 & 3 the meta-phenylene-diamine by meta-toluylene
diamine.
All these intermediate compounds are already able to dye cotton in an alkaline bath
brown and could be used as colouring matters, but I use them to produce other
brown colouring matters by allowing diazotized aromatic sulpho-acids to react upon
them especially upon the 1:2:4:6 (CH, NH, SO, H: NH2) (toluylene-diamine-
-
sulpho-acid-diazometa-phenylene-diamine-meta-phenylene-diamine).
The aromatic sulpho-acids most suitable for this reaction are :--
The method of procedure being the same in all cases it is only necessary to give
one example.
1 Example. Production of the brown azo dye-stuff from toluylene-diamine-sulpho-
acid (12:46 = CH, NH, SO, H: NH₂) meta-phenylene-diamine and sulfanil
acid.
:
100 parts of the intermediate compound obtained from toluylene-diamine-sulpho-
acid and 2 molecules meta-phenylene-diamine are taken still in humid state and mixed
with 184 parts diazo-sulfanil-acid in a solution of acetate of sodium. The formation
of the new dye-stuff goes on slowly and can be accellerated by moderately beating
the mass.
When the reaction is finished the liquid is neutralized with soda, boiled,
filtered and precipitated with salt.
The dye-stuff forms a blackish powder with a greenish hue; it dissolves in concen-
trated sulphuric acid with a brown violet red colour and in water with a brown
colour which is little altered by alkalies. The acid of the dye-stuff is soluble with
difficulty in cold water.
Dated this 8th day of July 1889.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Colouring Matters.
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
this invention and in what manner the same is to be performed, to be particularly
described and ascertained in and by the following statement :-
My invention has for its object the production of new brown azo colouring matters
by first producing intermediate bodies having the general formula.
which are formed by the action of diazotised sulpho-acids of aromatic meta-diamines
upon two molecules of a diamine and combining these intermediate bodies with
diazotised aromatic sulpho-acids.
These colouring matters which have not heretofore been described have the property
of dyeing unmordanted cotton in an alkaline bath brown.

page_text: The following examples are given to show the method of procedure.
:
1st Example. Preparation of the intermediate compound from the toluylene-
diamine sulpho-acid 1: 2: 4:5 = (CH, NH, NH, SO, H) (prepared by sulphur-
ising toluylene-diamine-Wiesinger, Berliner Berichte 7.464) and meta-phenylene
diamine.
A solution cooled to 0° of 15 parts of the sodium salt of the toluylene-diamine-
sulpho-acid and 6-9 parts of sodium-nitrite in 500 parts of water is slowly introduced
into diluted muriatic acid (containing 60 parts of muriatic acid of 22, 5° B.) and
cooled with ice. As soon as it is found there is no more nitrous acid in the liquid it
is mixed with a solution of 21 parts of meta-phenylene-diamine-sulphate and. 100 parts
of crystallized acetate of sodium in 1000 parts of water.
The intermediate compound obtained (toluylene-diamine-sulpho-acid-diazometa-
phenylenediamine-meta-phenylene-diamine) is formed at once and precipitates as a
dark-brown mass, which is filtered, pressed, transformed in its sodium salt and dried.
The dye-stuff is a brown-powder, soluble in water with a yellow-brown colour, the
acid of the dye-stuff is only soluble in water with difficulty.
2nd Example. Intermediate compound from toluylene-diamine sulpho-acid 1: 2:
4:6=(CH, NH, SO, H: NH,) and meta-phenylene-diamine. The preparation
of this body is effected in the manner described in the first example, with this
difference, that there are used but 36 parts of muriatic acid of 22, 5° B. instead of
60 parts, and 25 parts calcined soda instead of 100 parts of acetate of sodium.
In this case the body obtained is precipitated as a dark brown mass which is
filtered, pressed and dried. This intermediate body forms a reddish brown powder
soluable in water, with a light yellow-brown colour; acids precipitate it from the
watery solutions as yellowish orauge flocks.
3rd Example. Intermediate compound from toluylene-diamine-sulpho-acid 1:2:
4:6 (CH: SO, H: NH, NH,) and meta phenylene-diamine.
The diamido-acid used in this process is not yet known; it is obtained by reduction
of the dinitro-ortho-toluol-sulpho-acid described by Schwanert (Annalen der Chemie
u. Pharmacie 186, 349). Like its isomerics it is soluble with difficulty in cold water
and easily soluble in, hot water; in diluted water watery solutions the diamido-acid
crystallizes in the form of large light-brown coloured prisms.
The combination of the diazotized diamido-sulpho-acid with meta-phenylene-
diamine, and the separation of the formed compound is operated in the same manner
as described in the 1st example. The body is a blackish-brown powder resembling
the compounds of the first and second example as regards its other properties.
A second series of very similar intermediate compounds is obtained in replacing
in the examples 1, 2 and 3 the meta-phenylene-diamine by meta-toluylene-
diamine.
All these intermediate compounds are already able to dye cotton in an alkaline
bath brown and could be used as colouring matters, but I use them to produce other
brown colouring matters, by allowing diazotized aromatic sulpho-acids to re-act upon
them especially upon the 1:2:4:6 = (CH, NH, SO, H: NH2) (toluylene-
diamine-sulpho-acid-diazometa-phenylene-diamine-meta-phenelene-diamine).
:
The aromatic sulpho-acids most suitable for this reaction are
1) Sulfanil acid.
2) Ortho-toluidine sulpho-acid.
3) Amido-azo-benzol-sulpho-acid.
4) Naphtionic acid.
5) ẞ Naphtylamine sulpho-acid.

page_text: 100 parts of the intermediate compound obtained from toluylene-diamine-sulpho
acid and 2 molecules meta-phenylene-diamine are taken still in humid state and mixed
with 184 parts diazo-sulfanil-acid in a solution of acetate of sodium. The formation
of the new dye-stuff goes on slowly and can be accelerated by moderately heating the
When the reaction is finished the liquid is neutralized with soda, boiled,
filtered and precipitated with salt.
mass.
The dye-stuff forms a blackish powder with a greenish hue, it dissolves in concen-
trated sulphuric acid with a brown violet red colour and in water with a brown colour
which is little altered by alkalies. The acid of the dye-stuff is soluble with difficulty
in cold water.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed as communicated to me by
my foreign correspondent I declare that what I claim is :-
First The method of producing new brown azo-dye stuffs called intermediate
compounds by combining the 3 toluylene-diamine-sulpho-acids
1: 2 : : 5
1:
2 4:6
1:2:4: 6
=
=
CH : NH, :NH, : SO, H
CH, : NH, : SO, H :NH,
CH: SO_HINHANH
with meta-phenylene-diamine and meta-toluylene-diamine.
४
Second-The method of producing new brown azo-dye stuffs by combining the
intermediate compounds of the 3 toluylene diamine sulpho-acids and meta phenylene-
diamine above mentioned with diazotized aromatic sulpho acids.
Third As a new manufacture, the brown azo dye-stuffs produced according to
claims 1 and 2 and having the properties above described
with meta-phenylene-diamine and meta-toluylene-diamine.
Second The method of producing new brown azo-dye stuffs by combining the
intermediate compounds of the 3 toluylene diamine sulpho-acids and meta phenylene-
diamine above mentioned with diazotized aromatic sulpho acids.
Third As a new manufacture, the brown azo dye-stuffs produced according to
claims 1 and 2 and having the properties above described
Dated this 3rd day of March 1890.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, Agents for the Applicant.