The Manufacture and Production of New Basic Colouring Matters.
Year: 1895

page_text: PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
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) to be as follows:
This invention consists in the manufacture and production of new basic colouring-
matters which appear to be related to the acridine series and to resemble phosphine
in their properties. The said new colouring-matters are obtained from certain
substituted auramines by treatment as hereinafter described. The substituted
auramines which appear to be most suited for conversion into the new colouring-
matters are the met-amido-phenyl-auramines and met-amide-tolyl-auramines, which
can be regarded as derivatives of meta-phenylene and toluylene-diamine on the one
hand, and on the other hand of tetra-methyl or tetra-ethyl-diamido-diphenyl-
methane. The hydro-chlorates of the said substituted auramines on heating either
by themselves or admixed with meta-phenylene-diamine and meta-toluylene-
diamine, as such or as hydrochlorates-with or without the addition of a
condensing agent, yield the new colouring-matters. As an instance of a suitable
condensing agent, I mention chloride of zinc.
The substituted auramines can be prepared in the manner described in the
Specification of Letters Patent No. 5741 of 1884 (granted to John Henry
Johnson), or any other known or suitable method for the preparation of auramine
dyes may be used. It is usually not necessary to use pure isolated substituted
auramines, as my foreign correspondents have discovered that the crude melt or
reaction product containing the said substituted auramines can be, and preferably
are, directly used in the process, according to this invention.
The following example will serve to further illustrate the nature of the invention
but it can be varied in many respects and I do not confine myself to the said
example. The parts are by weight.
PRODUCTION OF A META AMIDO-PHENYL-AURAMINE
INTO NEW COLOURING MATTER.
AND ITS CONVERSION
Mix together about forty parts of tetra-methyl diamido-benzo-phenone, twenty
seven parts of meta-phenylene-diamine-dihydrochlorate and about nine parts of
meta-phenylene-diamine-base and heat the mixture ou the oil-bath in a closed
enamelled vessel provided with an outlet for the vapours evolved and furnished
with a stirrer. Stir continuously and maintain the temperature of the oil bath at
about from one hundred and ninety five to two hundred and fifteen degrees Centi-
grade. The substituted auramine dye is first formed but it is gradually converted
into new colouring matter. Withdraw test portions from time to time dissolve
them in dilute hydrochloric acid and boil the solution. The substituted auramine
yields under these conditions an orange-yellow solution which becomes nearly
colourless on boiling, whilst the new colouring matter yields a brownish-yellow.
solution which remains unchanged on boiling. Interrupt the heating of the whole.
melt when the tests shew that no further change into the new colouring matter is
[Price 8d 1

page_text: taking place. Allow the melt to cool. It solidifies to a dark coloured mass
possessing a greenish metallic, lustre. Dissolve the whole in about four hundred
parts of boiling water to which about twenty parts of hydrochloric acid (containing
about thirty per cent. real acid HCI) have been added. Allow the liquid to cool
and then filter and precipitate the colouring matter from the filtered solution by
the addition of common salt and chloride of zinc. Collect the precipitate and mix
it with twenty parts of hydrochloric acid (containing about thirty per cent. real
acid HCl) and heat the mixture on the water bath in order to obtain a readily
soluble salt, next evaporated to dryness and reduce to powder.
Under certain conditions (for instance when the temperature of the melt has
risen too high) besides the desired colouring matter a brownish colouring matter is
also formed. This can readily be removed from the product by taking advantage
of its lesser solubility in hydrochloric acid.
The desired colouring matter thus obtained dissolves readily in water giving a
brownish-yellow solution possessing a green fluorescence. It dyes cotton mordanted
with tannin and it also dyes leather giving brownish-yellow shades.
Instead of meta-phenylene-diamine in the above example meta-toluylene-diamine
can be used and a similar colouring matter be obtained. Similarly also the tetra-
ethyl-diamido-benzophenone can be used instead of the methyl derivative in which
case it is advisable to add zinc chloride to the melt.
The same series of new colouring-matters can also be obtained by heating the
bydrols derived from the methane compounds herein before mentioned with the
meta-diamines together with the hydrochlorates thereof.
Dated this 19th day of January 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Basic Colouring Matters.
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 & 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 and production of new basic colouring
matters which appear to be related to the acridine series and to resemble phosphine
in their properties. The said new colouring matters are obtained from certain
substituted auramines by treatment as hereinafter described. The substituted
auramines which appear to be most suited for conversion into the new colouring
matters are the metamido-phenyl-auramines and metamido-tolyl-auramines which
can be regarded as derivatives of meta-phenylene and toluylene-diamine, on the one
hand, and, on the other hand, of tetra-methyl, or tetra-ethyl, diamido-diphenyl-
methane. The hydrochlorates of the said substituted auramines on heating, either
by themselves, or admixed with meta-phenylene-diamine and meta-toluylene-
diamine (as such, or as hydrochlorates ;) with, or without, the addition of a
condensing agent, yield the new colouring-matters. As an instance of a suitable
condensing agent, I mention chloride of zinc.
The substituted auramines can be prepared in the manner described in the
Specification of Letters Patent No. 5741 of 1884 (granted to John Henry
Johnson) or any other known, or suitable, method for the preparation of auramine
dyes may be used. It is usually not necessary to use pure isolated substituted
auramines as my foreign correspondents have discovered that the crude melt, or

page_text: reaction product, containing the said substituted auramines, can be, and preferably
is, directly used in the process according to this invention.
The following example will serve to further illustrate the nature of the invention,
and the manner in which it can be carried into practical effect but it can be varied
in many respects, and I do not confine myself to the said example. The parts are
by weight.
PRODUCTION OF A
META-AMIDO-PHENYL-AURAMINE,
INTO NEW COLOURING MATTER.
AND ITS CONVERSION
Mix together about forty parts of tetra-methyl-diamido-benzo-phenone, twenty
seven parts of meta-phenylene-diamido-dihydrochlorate, and about nine parts of
meta-phenyleue-diamine-base and heat the mixture, on the oil bath, in a closed
enamelled vessel, provided with an outlet for the vapours evolved, and furnished
with a stirrer. Stir continuously, and maintain the temperature of the oil bath at
about from one hundred and ninety five, to two hundred and fifteen, degrees
Centigrade. The substituted auramine dye is first formed, but it is gradually
converted into new colouring matter. Withdraw test portions from time to time,
dissolve them in dilute hydrochloric acid, and boil the solution. The substituted
auramine yields, under these conditions, an orange-yellow solution which becomes
nearly colourless on boiling, whilst the new colouring-matter yields a brownish-
yellow solution which remains unchanged on boiling. Interrupt the heating of the
whole melt when the tests shew that no further change into the new colouring-
matter is taking place. Allow the melt to cool. It solidifies to a dark coloured
mass, possessing a greenish metallic lustre. Dissolve the whole in about four
hundred parts of boiling water to which about twenty parts of hydrochloric acid,
(containing about thirty per cent. real acid HCl), have been added. Allow the
liquid to cool and then filter and precipitate the colouring matter from the filtered
solution by the addition of common salt and chloride of zinc. Collect the
precipitate, and mix it with twenty parts of hydrochloric acid, (containing about
thirty per cent. real acid HCI), and heat the mixture on the water bath, in
order to obtain a readily soluble salt; next evaporate to dryness and reduce
to powder.
Under certain conditions, (for instance when the temperature of the melt has
risen too high), besides the desired colouring-matter, a brownish colouring-matter
is also formed. This can be removed from the product by taking advantage of its
lesser solubility in hydrochloric acid.
The desired colouring matter thus obtained dissolves readily in water giving a.
brownish-yellow solution possessing a green fluorescence. It dyes cotton mordanted
with tannin, and it also dyes leather giving brownish-yellow shades. Instead of
meta-phenylene-diamine, in the above example, meta-toluylene-diamine can be used
and a similar colouring matter be obtained. Similarly also the tetra-ethyl-diamido-
benzo-phenone can be used instead of the methyl-derivative, in which case it is
advisable to add zinc chloride to the melt.
The same series of new colouring matters can also be obtained, but less advanta-
geously by heating the hydrols derived from the methane compounds hereinbefore
mentioned with the meta-diamines together with the hydrochlorates thereof, with,
or without, a condensing agent. This can, for instance, be effected by proceeding
as described in the example, but using the corresponding quantity of the hydrol,
instead of the benzo-phenone derivative.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed I declare that what I
claim is :-
1. The manufacture of new basic colouring matters, by heating substituted
uramines, such as the hydrochlorate of metamido-phenyl-auramine, or metamido-

page_text: tolyl-auramine, or a crude melt or reaction product, containing such substituted
auramine, either by themselves, or admixed with meta-phenylene diamine, or
meta toluylenediamine, (as such or as hydrochlorates) with, or without, the
addition of chloride of zinc or other condensing agent substantially as hereinbefore
described.
2. The manufacture of the new basic dyes by heating the hydrols hereinbefore
defined with the meta diamines, and their hydrochlorates, with, or without, a
condensing agent, substantially as herein before described.
3. The manufacture and isolation of the new basic colouring matters in the
manner herein before described in the example.
4. As new products the new basic dyes such as can be obtained substantially in
the manner herein before described and claimed.
Dated this 16th day of October 1895.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.