Year: 1888

page_text: Date of Application, 31st May, 1888
Complete Specification Lefr, 23rd Feb.. 1889
Complete Specification Accepted, 6th Apr., 1889
56
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 :-
This invention relates to the production of yellow and orange coloured azo dye
stuffs or colouring matters from cresolcarbon acid.
The oxytoluyl acids known under the name of cresotin acids or cresolcarbon acids
could not hitherto be used for the production of azo dye stuffs of any practical value..
According to the present invention however, the said cresotin acids may now be used
for this purpose.
It has been found that one molecule of a cresolcarbon acid made by the well known
methods of Kolbe (German Patent No. 426) or of Schmitt (German Patent No. 29939)
from one of the isomeric cresols can be combined with the Tetrazo compounds of the
benzidin or tolidin to form so called intermediate compounds, which give technically
valuable azo dye stuffs, when further treated with cresolcarbon acid, salicylic acid or
(NH):
toluylendiaminsulpho acid C. H, CH...
SO, H
These azo dye stuffs dye cotton in an alkaline soap bath yellow and orange without
other mordants.
For manufacturing the above I proceed as follows:-
-
(1) Dye stuff from 1 molecule tetrazodiphenil-chloride and 2 molecules ortho-
cresolcarbon acid.
I dissolve 18.4 lbs. of Benzidin in 500 lbs. of water and 48 lbs. of muriatic acid
of 20° Bé. To this solution I add whilst cooling another solution of 28 lbs, of nitrite

page_text: of soda in 150 lbs. of water. This mixture is then allowed to run into a solution of
30.4 lbs. of ortho cresol-carbon acid (ẞ cresolin acid Beilsteins Handbuch page 1458)
and 27 lbs. of hydrate of soda in 600 lbs. of water. The whole is well stirred and
after some hours the dye stuff is precipitated as a yellow-brown powder. It is filtered,
pressed and dried; it dyes cotton in the soap bath light lemon yellow.
2) Dye stuff from I molecule tetrazo ditolylchloride and 2 molecules ortho-cresol-
carbon acid.
If in the above proceeding 21,2 lbs. of tolidin are taken instead of benzidin, a colour-
ing matter will result, which dyes cotton a shade redder than that above described.
3) Dye stuff from 1 molecule-tetrazodiphenyl-chloride 1 molecule ortho-cresol-
carbon acid and 1 molecule salicylic acid.
A solution of tetrazodiphenyl, chloride prepared as described above (No. 1) runs
into a solution of 15,2 lbs. of ortho-cresolcarbon acid and 20 lbs. of soda in 300 lbs. of
water whilst continually stirring. The intermediate compound is slowly formed as a
flaky precipitate. As soon as the reaction is finished a solution of 13,6 lbs. of salicylic
acid and 25 lbs. of hydrate of soda in 300 lbs. of water is added and well stirred. At
first the precipitate is partly dissolved with a red yellow colour and then begins the
separation of the dye stuff which is filtered off, pressed and dried. It dyes cotton
yellow.
Jf 21,2 lbs. of tolidin are taken instead of benzidin in the foregoing process the
intermediate compound is obtained as a gelatinous brown mass, which is used for the
production of the
4) Dye stuff from 1 molecule tetrazo-ditolylchlorido, 1 molecule ortho-cresolcarbon
acid and 1 molecule salicylic acid.
This dye-stuff has a somewhat redder shade than the foregoing No. 3.
5) Dye stuff from 1 molecule tetrazoditolylchloride, Imolecule, Ortho-cresolcarbon
acid and 1 molecule toluylendiaminsulpho acid.
To produce this dye stuff I first prepare a solution of tetrazoditolylchloride from
21,2 lbs. of tolidin in the above described manner adding to it a solution of 15,2 lbs.
_ of ortho-cresolcarbon acid and 20 lbs. of calcined soda in 300 lbs. of water. The
intermediate compound is slowly formed as a gelatinous--brown-mass. As soon
as the reaction is finished I add a solution of 20,2 lbs. of toluylendiaminsulpho acid
and 6 lbs. of soila in 300 lbs. of water stir it for 24 hours, heat it to the boiling-point,
precipitate the dye stuff with common salt filter it off, press and dry it.
It dyes cotton orange in an alkaline soap bath.
If in the above processes No. 1-5 equal quantities of meta-cresolcarbon acid
(pcresolin acid, Beilstein handbook page 1459) are taken instead of ortho-cresolcarbon
acid, the following dye stuffs will be obtained in all the same manner.
6) Dye stuff from one molecule tetrazodiphenylchloride and 2 molecules meta-
.cresolcarbon acid.
7) Dye stuff from 1 molecule tetrazoditolylchloride and 2 molecules meta-cresol-
carbon acid.
8) Dye stuff from 1 molecule tetrazodiphenylchloride, 1 molecule meta-cresolcarbon
acid and 1 molecule salicylic acid.
9) Dyo stuff from 1 molecule tetrazoditolylchloride 1 molecule meta-cresolcarbon
acid and 1 molecule salicylic acid.
10) Dye stuff from 1 molecule tetrazoditolylchloride 1 molecule meta-cresolcarbon
acid and 1 molecule toluylendiaminsulpho acid.
These colouring matters dye cotton in nearly all the same shades as the corre-
sponding dye stuffs of ortho-cresolcarbon acid.
The intermediate compound of tetrazodiphenylchloride and meta-cresolcarbon acid
is a gelatinous brown precipitate whereas that of tetrazoditolylchloride and meta
cresolcarbon acid forms fine red brown flakes.
To characterize the dye-stuffs N 1-—4 and N 6–9 I may remark, that they are not
easily soluble in cold water. The acids of the dye stuffs are precipitated as yellow
rown flakes from their watery solutions by diluted sulphuric acid. They dissolve
with violet,colour in concentrated sulphuric acid,

page_text: The orange dye stuffs N 5 and 10 are somewhat more soluble in cold water than
the forenamed colouring matters N 1-4 and 6-9. The precipitate from their
watery solutions by adding diluted acids, is brown. The solution of these dye stuffs
in concentrated sulphuric acid is violet red.
Dated th: 011
1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture 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 he performed, to be particularly
described and ascertained in and by the following statement :-
This invention relates to the production of yellow and orange coloured azo dye
stuffs or colouring matters from cresolcarbon acid.
The Crytoluy acids known under the name of cresotin acids could not hitherto
be used for the production of azo dye stuffs of any practical value. According to
the present invention however, the said cresotin acids may now be used for this
purpose.
It has been found that one molecule of a cresolcarbon acid made by the well
known methods of Kolbe (German Patent No. 426) or of Schmitt (German Patent
No. 29939) from one of the isomeric cresols can be combined with the tetrazo
compounds of the benzidin or tolidin to form so called intermediate components
which give technically valuable azo dye stuffs when further treated with cresol-carbon
acid, salicylic acid or toluyl-endiaminsulpho acid.
These azo dye stuffs dye cotton in an alkaline soap bath yellow and orange without
other mordants.
For manufacturing the above I proceed as follows
(1) Dye stuff from 1 molecule tetrazo-diphenyl-chloride and 2 molecules ortho
cresol carbon acid.
I dissolve 18,4 lbs. of benzidin in 500 lbs. of water and 48 Hs. of muriactic acid
of 20° Bé. To this solution I add, whilst cooling another solution of 28 lbs. of
nitrite of soda in 150 lbs. of water. This mixture is then allowed to run into a

page_text: solution of 30.4 lbs. of ortho cresol-carbon acid and 27 lbs. of hydrate of soda in
600 lbs. of water. The whole is well stirrer and after some hours the dye stuff is
precipitated as a yellow-brown powder. It is filtered, pressed and dried; it dyes
cotton in the soap bath light lemon yellow.
2) Dye stuff from 1 molecule tetrazo-ditolylchloride and 2 molecules ortho-cresol
carbon-acid.
If in the above proceeding 21,2 lbs. of tolidin are taken instead of benzidin, a
colouring matter will result which dyes cotton a shade redder than that above
described.
3) Dye stuff from 1 molecule tetrazo-diphenyl chloride, 1 molecule ortho-cresol
carbon-acid and 1 molecule salicylic acid.
A solution of tetrazo-diphenylchloride prepared as described above (No. 1) runs
into a solution of 15-2 lbs. of ortho cresolcarbon acid and 20 lbs. of soda in 300 lbs.
of water whilst continually stirring. The intermediate compound is slowly formed as
a flaky precipitate. As soon as the reaction is finished a solution of 13,6 lbs. of
salicylic acid and 25 lbs. of hydrate of soda in 300 lbs. of water is added and well
stirred. At first the precipitate is partly dissolved with a red yellow colour and then
begins the separation of the dye stuff which is filtered off, pressed and dried. It dyes
cotton yellow.
If 21,2 lbs. of tolidin are taken instead of benzidin in the foregoing process, the
intermediate compound is obtained as a gelatinous brown mass, which is used for the
production of the
4) Dye stuff from 1 molecule tetrazoditolylchloride, 1 molecule ortho-cresolcarbon
acid and 1 molecule salicylic acid.
This dye stuff has a somewhat redder shade than the foregoing No 3.
5) Dye stuff from 1 molecule tetrazo-ditolylchloride,-1-molecule ortho-cresolcarbon
acid and 1 molecule toluylendiaminsulpho acid.
To produce this dye stuff I first prepare a solution of tetrazo-litolylchloride from
21,2 lbs. of tolidin in the above described manner adding to ita solution of 15,2 lbs. of
ortho-cresolcarbon acid and 20 lbs. of calcined soda in 30 lbs. of water. The
intermediate compound-is-slowly-formed-asa. gelatinous brown_mass. As soon as
the reaction is finished I add a solution of 20,2 lbs. of toluylendiamin sulpho acid
and 6 lbs. of soda in 300 lbs. of water, stir it for 24 hours, heat it to the boiling
point, precipitate the dye stuff with common salt, filter it off, press and dry it.
It dyes cotton orange in an alkaline soap bath.
If in the above processes No. 1-5 equal quantities of meta-cresolcarbon acid
are taken instead of ortho-cresolcarbon acid the following dye stuffs will be obtained
in all the same manner.
6) Dye stuff from 1 molecule tetrazodiphenylchloride and 2 molecule meta-
cresolcarbon-acid.
7) Dye stuff from 1 molecule tetrazoditolylchloride and 2 molecules meta-cresol-
carbon acid.
8) Dye stuff from 1 molecule tetrazodiphenylchloride, 1 molecule meta-cresol-
carbon acid and 1 molecule salicylic acid.
9) Dye stuff from 1 molecule tetrazoditolylchloride 1 molecule meta-cresolcarbon
acid and i molecule salicylic acid.
10) Dye stuff from 1 molecule tetrazoditolyl chloride, 1 molecule meta-cresol-
carbon acid and 1 molecule toluylendiaminsulpho acid.
These colouring matters dye cotton in nearly all the same shades as the corre-
sponding dye stuffs of ortho-cresolcarbon acid.
The intermediate compound of tetrazodiphenyl-chloride and meta-cresolcarbon acid
is a gelatinous brown precipitate, whereas that of tetrazoditolylchloride and meta-
cresolcarbon acid forins fine red brown flakes.
To characterise the dye stuffs N 1-4 and N 6-9 I may remark, that they are
not easily soluble in cold water. The acids of the dye stuffs are precipitated as
yellow brown flakes from their watery solutions by diluted sulphuric acid. They
dissolve with violet color in concentrated sulphuric acid.

page_text: The orango dye stuffs N 5 and 10 are somewhat more soluble in cold water than
the forenamed coloring matters N.1-4 and 6-9. The precipitate from their watery
solutions by adding dilated acids, is brown. The solution of these dye stuffs in
concentrated sulphuric acid is violet red.
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 correspondents I declare that what I claim is :-
First. The method of producing so called intermediate compounds containing a
diazo-group capable of reacting by combining molecule of a salt of tetrazo-
diphenyl or tetrazoditoly with one molecule ortho-cresolcarbon acid (CH³: OH:
CO OH 1:2:3) or with one molecule meta-cresolcarbon acid (CH³: OH: CO OH=
1:3:4).
Second. The method of producing new yellow and orange azo dye stuffs by
combining one molecule of the intermediate compounds named sub 1 with one
molecule salicylic acid and one molecule ortho or meta-cresolcarbon acid or one
molecule toluylindiaminsulpho acid.
Dated this 92.11 of Wabo 1000
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London,
Agents for the Applicant.