The Manufacture and Production of Mordant Dyeing Colouring Matters, and of Intermediate Products relating thereto.
Year: 1896

page_text: Date of Application, 1st July, 1896
Complete Specification Left, 26th Mar.. 1897-Accepted, 1st May. 1997
PROVISIONAL SPECIFICATION.
The Manufacture and Production of Mordant Dyeing Colouring
Matters, and of Intermediate Products relating thereto.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Eields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
communicated to me by The Badische Anilin and Soda Fabrik of Ludwigshafen-
on-Rhine in the Empire of Germany) to be as follows:-
This invention consists in the manufacture of colouring matters, of which some
are new, whilst others are apparently identical with products hitherto known. (See
for instance English Patent 19962°³.)
It is well known that aromatic nitroso compounds readily react with bodies
containing amido- or hydroxy-groups, and yield indamine, or ind ophenol, colouring
matters, which may, or may not, under the conditions prevailing, or by subsequent
treatment, be converted into colouring matters of other series such as oxazines, or
thiazines. In all cases in which a practical manufacture of dyestuff has been based
upon these reactions the condensation has been effected in aqueous, alcoholic, or
acetic acid, solution, or the like, in the absence of mineral acid. In the presence
of mineral acid little, or no, useful product is obtained because the indamines and
indophenols are easily destroyed thereby.
My foreign correspondents have discovered that useful thiazine colouring-matters
can be obtained by the condensation of certain nitroso-naphthol-sulphoacids with a
para-diamine-thio-sulphonic acid, provided that the condensation be effected in
concentrated sulphuric acid solution.
The nitrosc-naphthol-sulphoacids which can be used are for instance:-1. nitroso-
2-naphthol-3.3-disulphoacid (obtained from the so-called R-acid) and 1. nitroso-
2-naphthol-3'-sulphoacid. (See English Patent No. 22648 and German Patent
No. 28065.)
If molecular proportions of one of the said nitroso-naphthol-sulpboacids and of
a para-diamine-thiosulphonic acid be dissolved in concentrated sulphuric acid and
the mixture be heated on the water-bath, the mass soon turns green and a colouring-
matter is formed which is precipitated on pouring into water. It dyes blackish-
blue shades on chrome-mordanted wool. In sulphuric acid the colouring matter
so obtained yields a green solution, in concentrated hydrochloric acid the solution
is dirty violet. The dyes of this series are new and I call them thiazines A.
If these colouring-matters be heated for a short time with dilute acid, or with
dilute soda, they are converted into a different series of thiazines which I term
thiazines B. These yield green solutions in both sulphuric acid and hydrochloric
acid and give blue shades on chrome mordanted wool.
The following examples will serve to further illustrate the nature of the invention
but the invention is not confined to these examples. The parts are by weight.

page_text: dimethyl-aniline-thio-sulphonic acid (molecular proportions) to about one thousand
five hundred parts of sulphuric acid (containing about ninety-five per cent. H,SO).
Heat the mixture on the boiling water-bath and keep it well stirred until no further
formation of colouring-matter is observed. This usually requires in this case about
six hours. Allow the mass to cool and pour it into ice-water, and collect the colouring-
matter on the filter and wash with cold water.
dimethyl-aniline-thio-sulphonic acid (molecular proportions) to about one thousand
five hundred parts of sulphuric acid (containing about ninety-five per cent. H,SO).
Heat the mixture on the boiling water-bath and keep it well stirred until no further
formation of colouring-matter is observed. This usually requires in this case about
six hours. Allow the mass to cool and pour it into ice-water, and collect the colouring-
matter on the filter and wash with cold water.
EXAMPLE 2.
CONVERSION OF THIAZINE A INTO A THIAZINE B.
Dissolve the thiazine A in the requisite quantity of a dilute so la solation
(containing say about eight parts of Na,CO, in a thousand parts of water). Boil
the solution until a test portion of the dye after precipitation, dissolves with a
green colour in concentrated hydrochloric acid. When this point is reached
precipitate the dye by means of an acid filter and wash.
Instead of soda, other alkalies, or dilute acids, can be used; for instance dilute
sulphuric acid containing about 70% H₂SO, can be employed.
Dated this 1st day of July 1896
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of Mordant Dyeing Colouring
Matters, and of Intermediate Products relating thereto.
I, JAMES YATE JOHNSON, of 47 Lincoln's Inn Fields, in the County of London,
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-Rhine, in the Empire of Germany) and in what manner the
same is to be performed to be particularly described and ascertained in and by
the following statement :-
This invention consists in the manufacture of colouring matters, of which some
are new, whilst others are apparently identical with products hitherto known.
(See for instance the Specification of Letters Patent 19962 of 1893.)
It is well known that aromatic nitroso-compounds readily react with bodies
- containing amido- or hydroxy-groups, and yield indamine, or indophenol, colouring-
matters which may, or may not, under the conditions prevailing, or by subsequent
treatment, be converted into colouring-matters of other series such as oxazines, or
thiazines. In all cases in which a practical manufacture of dyestuff has been
based upon these reactions the condensation has been effected in aqueous alcoholic,
or acetic acid, solution, or the like, in the absence of mineral acid. In the
presence of mineral acid little, or no, useful product is obtained because the
indamines and indophenols are easily destroyed thereby.
My foreign correspondents have discovered that useful thiazine colouring-
matters can be obtained by the condensation of certain nitroso-naphthol-sulpho-
acids with a para-diamine-thio-sulphonic acid, provided that the condensation be
effected in concentrated sulphuric acid solution.
The ritroso-naphthol-sulphoacids which can be used are for instance :-
1 nitroso-2-naphthol-3.3'-disulphoacid (obtained from the so-called R-acid), and
1 nitroso-2-naphthol-3'-sulphoacid. (See the Specification of Letters Patent
No. 2264 of 1884, and the Specification of the German Patent No. 28065.)
If molecular proportions of one of the said nitroso-naphthol-sulphoacids aud of

page_text: 5. As new articles of manufacture the new intermediate products "thiazines A "
such as can be obtained as herein before described.
Dated this 26th day of March 1897.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.