Production of a New Colouring Matter Suitable for Dyeing and Printing Cotton Without the Aid of a Mordant.
Year: 1889

page_text: Date of Application, 27th Aug., 1889
Complete Specification Left, 25th Apr., 1890-Accepted, 21st June, 1890
PROVISIONAL SPECIFICATION.
The Production of a New Colouring Matter Suitable for Dyeing and
Printing Cotton Without the Aid of a Mordant.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention which has been communi-
cated to me from abroad by the Badische Anilin and Soda Fabrik of Ludwigshafen
on the Rhine in the Kingdom of Bavaria and Empire of Germany to be as
follows:-
-
-
This Invention relates to the manufacture of new colouring matters suitable for
dyeing and printing cotton without the aid of a mordant. The said colouring
matters belong to the class of the so-called tetrazo-compounds (that is bodies
which contain two N
= N groups). As is well known the tetrazo-compounds
derived from benzidine and from ortho-tolidine by the action of nitrous acid on these
bases yield when combined with naphthylamine-sulpho acids; naphthol-sulpho acids;
salicylic acid; phenols and the like a series of dye stuffs. Up to the present time
however no colouring matters capable of dyeing or printing cotton a good colour
without a mordant have been obtained from the meta-substitution derivatives of
benzidine. The present invention is based upon the discovery that the known base
ortho-meta-dimethyl-benzidine (also called ortho-meta-tolidine) and a new base mono-
meta-methyl-benzidine (the production of which also forms part of this invention)
and mixtures of these two bases in any proportions can be made to yield colouring
matters which will dye or print cotton readily without the aid of a mordant. By the
use of these new dye stuffs yellow red and purple tints may be obtained different
from those resulting from the use of the corresponding benzidine and ortho tolidine
derivatives.
The new colouring matters from the known base ortho-meta-tolidine (the prepara-
tion of which base is described by Schultz in the Berichte der Deutschen Chem.
Gesellschaft Vol. XVII page 46) are obtained by acting on one molecule of this
body preferably in the form of its sulphuric acid salt with two molecules of sodium
nitrite in an acid solution the temperature being kept at about the freezing point.
In this way the corresponding tetrazo-compound is obtained which is used for obtaining
the dye stuffs by combining one molecule of it with two molecules of either of the
ollowing bodies.
Resorcinal or any other suitable body. Or one molecule of the tetrazo-compound
may be combined with one molecule of one of these bodies and one molecule of another
just as the tetrazo-compound from beuzidine when combined with one molecule of
naphthionic acid and one molecule of alpha-naphthol-alpha-sulpho-acid yields the
dye stuff known in commerce as Congo Corinth.
The combination of this base which up to the present appears likely to have the
greatest technical value is that with two molecules of naphthionic acid which dyes or
prints cotton a bright scarlet colour without the aid of a mordant the colour having a
yellower shade than the corresponding so called "Congo" colour obtained from
benzidine itself and naphthionic acid.
The new basic mono-meta-methyl benzidine hereinbefore referred to may be
prepared by the following process.
An amido-azo-compound is prepared by acting on diazo-benzene chloride with
ortho toluidine and this amidoazo compound is converted into the azo compound by

page_text: splitting off the amido-group. From this azo compound the mono-meta methyl-
benzidine is prepared by the action of a reducing agent such as stannous chloride in a
hot acid alcoholic solution.
This body when freed from tin salts and other impurities is pure enough to be used
for the preparation of dye stuffs in a manner similar to ortho-meta-tolidine by com-
bining it as described with the hereinbefore named or similar bodies. The technical
product contains varying proportions of ortho-meta-tolidine which does not interfere
with its application. Benzidine is quite absent.
In this case as in the case of ortho-meta-tolidine the combination with naphthionic
acid appears at present to be likely to have the greatest technical value. It fixes
itself on cotton without the aid of mordants giving a rather bluer shade of colour than
the corresponding dye from ortho-meta-tolidine.
Dated this 27th day of August 1889.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Production of a New Colouring Matter Suitable for Dyeing and
Printing Cotton Without the Aid of a Mordant.
I, JAMES YATE JOHNSON of 47 Lincoln's Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this Invention (which has been
communicated to me from abroad by the Badische Anilin and Soda Fabrik of
Ludwigshafen on the Rhine Germany) and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
1
This Invention relates to the manufacture of new colouring matters suitable for
dyeing and printing cotton without the aid of a mordant. The said colouring matters
being to the class of the so called dis-azo-compounds (that is bodies which contain
the N N group twice). As is well known the tetrazo-compounds derived
from benzidine and from orthotolidine by the action of nitrous acid on these bases
yield when combined with certain naphthylamine sulphoacids, naphthol sulphoacids,
salicylic acid, phenols and the like a series of dyestuffs, several of which have great
value in commerce owing to their property of dyeing cotton from the alkaline bath
without the aid of a mordant. Up to the date of the present Invention, however,
no colouring matter capable of dyeing or printing cotton a good colour without
the aid of a mordant, had been obtained from any meta-substitution derivatives of
benzidine and it was indeed generally believed by tinctorial chemists that this class
of bodies was incapable of yielding them (Schultz, Chemie des Steinkohlentheers
2nd Edition Vol. 2, page 258; Weingärtner, Chemiker, Zeitung, March 25th 1888,
No. 25).
This Invention is based upon the discovery that ortho-meta-dimethylbenzidine
(usually called ortho meta tolidine) can be made to yield colouring matters, which
dye and print cotton readily without the aid of a mordant. By combining the tetrazo-
compound from the said ortho-meta-tolidine with phenolic and amido bodies a large
number of colouring matters can be obtained and of these the combination with
naphthionic acid appears to be of technical importance. The alkaline salts of this
compound dye cotton a bright red colour from the boiling alkaline or soap bath, the
colour being of a yellower tint than that obtained by the use of the corresponding so
called Congo and Benzopurpurine dyestuffs resulting from the combination of
naphthionic acid with benzidine and orthotolidine respectively.
The following is an example of the manner in which this Invention can be carried
into practical effect (the parts are by weight). Take about ten parts of orthometa-
tolidine sulphate (Schultz, Berichte der deutschen chemischen Gesellschaft 17,47)
and stir well with about eighteen and a half parts of hydrochloric acid containing
about twenty five per cent. of real hydrochloric acid (H CI) and about three hundred

page_text: parts of water and about one hundred parts of ice, and run slowly into this a solution
of about four and a half parts of sodium nitrite (containing about ninety six per cent.
real Na NO2) in about nine parts of water and continue stirring for about two hours.
During the whole operation and reaction the temperature should be kept at about
0° Centigrade. Next pour the solution of the tetrazo compound thus obtained into a
solution of about twenty two and a half parts of crystallized naphthionate of soda and
about twenty parts of crystallized sodium acetate in about four hundred and fifty parts
of water and keep the temperature of this solution at about 0° Centigrade while
mixing Stir for about an hour and then add about nine parts of calcined soda and
continue stirring for three or four days. To practically completely precipitate the
colouring matter, which may already have partially separated out, add common salt,
collect and press, and purify, when necessary, by repeatedly dissolving in hot water
and re-precipitating with common salt.
Having now particularly described and ascertained the nature of the said Inven-
tion and in what manner the same is to be performed 1 declare that what I
claim is :-
:-
As a new article of manufacture the dis azo-dyestuff obtained substantially as herein-
before described from ortho-metatolidine and naphthionic acid.
Datad this with dayst Annil 1900
J. H. JOHNSON & Co.,
Agents.