The Manufacture and Production of New Mordant-dyeing Colouring Matters related to the Rosaniline Series.
Year: 1891

page_text: Date of Application, 16th Mar., 1891
Complete Specification Left, 9th Dec., 1891-Accepted, 9th Jan., 1892
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Mordant-dyeing Colouring
Matters related to the Rosaniline Series.
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 com-
municated to me from abroad by The Badische Anilin and Soda Fabrik of Lud-
wigshafen-ou-Rhine in the Empire of Germany) to be as follows :—
In the Specification of Letters Patent No. 4850 of the 13th March 1884 granted
to John Henry Johnson the production of certain halogen derivatives of tetra-
methyldiamido-benzophenone and analogous ketone-bases is described. The said
halogen derivatives are obtained by treating the ketone-bases with phosphorus
oxychloride (or certain equivalents) and are used in the manufacture of dyestuff's.
It is explained in the hereinbefore inentioned Specification that it is unnecessary
to prepare the halogen derivatives and then act with these on the appropriate
materials for preparing dyestuffs as the materials for the formation of the halogen
derivatives and the other compounds necessary for the formation of the dyestuff's
may be mixed together and the whole process carried on in one operation. The
production of basic dyestuff's related to the rosaniline series is more particularly
described in the Specification of Letters Patent No. 5038 of the 18th March 1884
granted to John Henry Johnson.
The present invention is based on the discovery that by the condensation of
suitable hydroxylated compounds with tetra-alkyl-diamido-benzophenone com-
pounds (or their halogen derivatives as above explained) new hydroxylated
colouring matters can be obtained which in consequence of their hydroxylated
nature possess the valuable quality of combining with metallic mordants to give
beautiful shades of colour. By the aid of these new dyestuffs the dyer and printer
is enabled to achieve colour effects which were hitherto impossible.
As instances of the tetra-alkyl-diamido-benzophenone compounds my foreign
correspondents mention tetra-methyl-diamido-benzophenone and tetra-ethyl-
diamido-benzophenone, but other analogous compounds including benzhydrols thio-
ketones and thio-hydrols may be employed.
The following hydroxylated compounds give good results but the invention is
not confined to their use as other analogous compounds can be employed instead.
(1) Dihydroxynaphthalene (2×3).
(2) Dihydroxynaphthalene (12).
(3) Dihydroxynaphthalene (27 or 2.2¹).
(4) Pyrogallol (pyrogallic acid).
The following directions for the preparation of one of the new dyestuffs will
serve as an example to illustrate the nature of this invention but I do not bind
myself to details. The parts are by weight.
Heat together about one hundred parts of tetra-methyl-diamido-benzophenone
with about two hundred parts of phosphorus oxychloride for about ten minutes on
the water bath and then add about sixty parts of 23 dihydroxynaphthalene (see
Gerinan Application for Patent B 10958). Continue beating on the water bath
for about two hours stirring all the time. Then allow the melt to cool and dissolve
it carefully in about two hundred and sixty parts of acetic acid (containing about
thirty per cent. real acetic acid) and pour the solution into water filter off the
dyestuff which separates out and wash with water. The dyestuff can either be
dried or preserved for use in the form of paste. It dyes chrome mordanted animal
and vegetable fibre giving beautiful bluish shades.

page_text: For the tetra-methyl-liamido-benzophenone in the above example tetra-ethyl-
diamido-benzophenone and other analogous compounds can as aforesaid be sub
stituted. It is also possible to use other condensing agents instead of phosphorus
oxychloride (such as phosphorus trichloride and other compounds) but the best
results have as yet been attained with phosphorus oxychloride. Further all the
hydroxylated compounds hereinbefore mentioned as suitable give good results when
applied in the place of the 23 dioxy-naphthalene and other hydroxylated com-
pounds can also be used.
Dated his ca.
1001
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Mordant-dyeing Colouring
Matters related to the Rosaniline Series.
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-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 :-
In the Specification of Letters Patent No. 4850 of the 13th March 1884
granted to John Henry Johnson the production of certain halogen derivatives of
tetramethyl-diamdo-benzophenone and analogous ketone bases is described. The
said halogen derivatives are obtained by treating the ketone-bases with phosphorus
oxychloride (or certain equivalents), and are used in the manufacture of dyestuffs.
It is explained in the aforesaid Specification that it is unnecessary to prepare the
halogen derivatives and then act with these on the appropriate materials for pre-
paring dyestuff's; as the materials for the formation of the halogen derivatives
and the other compounds necessary for the formation of the dyestuffs may be
mixed together and the whole process be carried on in one operation.
production of basic dyestuff's related to the rosaniline series is more particularly
described in the Specification of Letters Patent No. 5038 of the 18th March 1884
granted to John Henry Johnson.
The
The present invention is based on the discovery that by the condensation of
suitable hydroxylated compounds with tetra-alkyl-diamido-benzophenone com-
pounds (or their halogen-derivatives as above explained) new hydroxylated
colouring matters can be obtained which, in consequence of their hydroxylated
nature, possess the valuable quality of combining with metallic mordants to give
beautiful shades of colour. By the aid of these new dyestuff's the dyer and printer
are enabled to achieve colour effects which were hitherto impossible.
Of the
tetra-alkyl-diamido-benzophenones my foreign correspondents employ
either tetra-methyl-diamido-benzophenone or tetra-ethyl-diamido-benzophenone.
No claim is made to the dyes obtained by the condensation of the corresponding
benzhydrols with the hydroxylated compounds and subsequently oxidising the
resulting leuco bodies as they differ from and are inferior to those produced as
herein described according to this invention.
The following hydroxylated compounds give good results:-
(1) Dihydroxynaphthalene (2.3).
(2) Dihydroxynaphthalene (1-2).
(3) Dihydroxynaphthalene (2.7 or 2.2').
(4) Pyrogallol (pyrogallic acid).
The following directions under Example 1 will serve to illustrate the nature of

page_text: EXAMPLE 1.
Heat together about one hundred parts of tetra-methyl-diamido-benzo-
phenone with about two hundred parts of phosphorus oxychloride for about
ten minutes on the water-bath; and then add about sixty parts of 2-3 dihydroxy-
naphthalene (English Patent No. 158032). Continue heating on the water-bath
for about two hours stirring all the time. Then allow the melt to cool and dissolve
it carefully in about two hundred and sixty parts of acetic acid (containing about
thirty per cent, real acetic acid) and pour the solution into water, filter off the dye-
stuff which separates out and wash with water. The dyestuff can either be dried
or be preserved for use in the form of paste. It dyes chrome mordanted animal
and vegetable fibre giving beautiful bluish shades.
For the tetra-methyl-diamido-benzophenone in the above example, tetra-ethyl-
diamido-benzophenone can as aforesaid be substituted. It is also possible to use
other condensing agents instead of phosphorus oxychloride (such as phosphorus
tri-chloride, hydrochloric acid and similar compounds). In the case of the
dihydroxynaphthalenes the best results have been obtained with phosphorus
oxychloride but when condensing pyrogallol with tetra-alkyl-diamido-benzo-
phenones, hydrochloric acid can advantageously be used as the condensing agent,
and the product obtained is, when purified, identically the same in each case as
when using the phosphorus oxychloride.
The following example will illustrate the manner of carrying the invention into
effect using hydrochloric acid as the condensing agent.
EXAMPLE 2.
Mix about ten parts by weight of pyrogallol and fifteen parts of tetra-methyl-
diamido-benzophenone with about twenty parts of hydrochloric acid (containing
about thirty per cent. real hydrochloric acid HCI) and heat the mixture in a closed
enamelled iron vessel, for about twelve hours on the water-bath. A red melt of
syrupy consistency is formed which assumes a metallic sheen. This is dissolved
in water and the dye is precipitated with common salt and sodium-acetate solution.
To purify, extract the precipitate with acetic acid, and reprecipitate with common
salt. Instead of heating a mixture of the tetra-alkyl-diamido-benzophenone and
pyrogallic acid with aqueous hydrochloric acid, gaseous acid may be passed into a
heated mixture of these bodies.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new hydroxylated mordant dyeing colouring matters by
the condensation of the hereinbefore mentioned tetra-alkyl-diamido-benzo-phenones
and the hereinbefore mentioned hydroxylated compounds, substantially as described.
2. As new products, the mordant-dyeing colouring matters resulting from the
condensation of the tetra-alkyl-diamido-benzophenones herein before mentioned
with 2:3, 1×2 or 2·7 or 2-2¹ dihydroxynaphthalene or with pyrogallol.
Dated this 9th day of December 1891.
J. H. JOHNSON & Co.,
Agents.