Improvements in the Manufacture of Blue Mordant Dyeing Colouring Matters.
Year: 1891

page_text: Date of Application, 12th Nov., 1891
Complete Specification Left, 10th Sept.; 1892-Accepted, 12th Jan., 1893
PROVIDIUNAL DECIFICATION.
Improvements in the Manufacture of Blue Mordant Dyeing
Colouring Matters.
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) to be as follows:-
In the Specifications annexed to my applications for Letters Patent dated
A.D. 1888 Nos. 14,353 and 15121 it is stated that certain colouring matters of the
alizarine group by suitable treatment with sulphuric acid in its various forms,
become capable of transformation into other dyes. Thus for instance_alizarine
blue-green is converted into alizarine green by heating it with monohydrated or
concentrated sulphuric acid; and similarly alizarine green on heating with strong
sulphuric acid changes into alizarine indigo-blue.
The present invention is based upon the discovery that by subjecting nitro-
anthra-quinones to suitable treatment with sulphuric acid in operations analogous
to those described in the aforesaid Specifications new mordant dyeing colouring
matters are obtained which dye in greenish-blue to blue shades and possess most
valuable properties.
The treatment of the nitro-anthraquinones to obtain new dyes is performed in
two steps or stages:
1st. The nitro-anthraquinone is treated with fuming sulphuric acid under suitable
conditions until a colouring matter soluble in water is formed.
is
2nd. The product obtained as the result of the first stage of the
process
suitably treated with concentrated or monohydrated sulphuric acid until the said
soluble product is converted into the new dyestuff which is practically insoluble in
water.
The nature of the product obtained, varies according to the strength of the
fuming sulphuric acid used in the first stage, the duration of the operation and the
temperature at which it is carried on." Different products likewise result if
the soluble colouring matters produced in the first stage of the process be isolated
and purified and then this purified product be subjected to the treatment with
concentrated sulphuric acid as described in the second stage, thus dividing the
treatment into two separate processes, instead of diluting the whole melt obtained
in the 1st stage to the requisite strength, and proceeding at once with the second
part of the treatment.
According to the present invention blue dyes are obtained by treating nitro-
anthraquinones, first with fuming sulphuric acid and isolating the soluble colouring
matter obtained, and subsequently treating this purified product with concentrated
sulphuric acid, thus dividing the manufacture into two separate operations.
The production of soluble colouring matters by treatment of nitro-anthraquinones
with fuming sulphuric acid (that is to say the first stage of the process of manu-
facture herein before described) is known and has been published in print (Specifica-
tion of German Patent No. 6526).
The following description of a method of obtaining a blue dye according to this
invention is given merely as an example the method of manufacture being susceptible
of variation in many details without changing the essential characteristics of the
products.

page_text: EXAMPLE. a. FIRST STAGE.
Mix about ten parts of alpha-dinitro-anthraquinone with from about fifty to a
hundred parts of fuming sulphuric acid containing about forty per cent. of free
anhydride (SO), heat the mixture to a temperature of from about one hundred
to one hundred and thirty degrees centigrade and maintain this heat for about
three hours or until the conversion of the nitro-anthraquinone into the soluble
colouring matter hereinafter described is effected. Cool the melt and when cold
pour it into water and precipitate the colouring matter formed by means of common
salt. Filter, press and dry.
The product thus obtained by proceeding in a manner similar to that described
in the aforesaid German Patent No. 6526 forms when dry, a black powder with a
metallic lustre and dissolves in water forming a red solution. It is also soluble in
alkalies, its solution in caustic soda being of a greenish-blue colour and its solution
in carbonate of soda being of a blueish-violet colour.
b. SECOND STAGE.
Mix one part of the dry soluble colouring matter hereinbefore described (obtained
either as hereinbefore described or otherwise) with about ten parts of ordinary
concentrated sulphuric acid containing about ninety five per cent. of real acid
(H₂SO). Heat the mixture to about one hundred and thirty degrees centigrade
for about five hours or until the resulting dye is practically insoluble in water.
Then pour the whole into water, filter, wash with warm water, press and dry. The
parts referred to in this example are parts by weight.
The dyestuff thus obtained can be used in dyeing and printing either directly
in the form of a paste or in the form of an alkaline salt. When dry it constitutes
a dark powder having a metallic lustre. It is soluble in alcohol and glacial acetic
acid giving a reddish solution with yellow fluorescence, in caustic soda it gives a
blue solution and in concentrated sulphuric acid, a violet blue solution with a strong
brown-red fluorescence. In warm aniline it dissolves giving a red solution. It
can be recrystallized from glacial acetic acid and on submitting the recrystallized
product so obtained to analysis it is found to contain neither sulphur nor nitrogen.
Instead of the alpha-dinitro-anthraquinone mentioned in the example hereinbefore
described certain other nitro and amido anthraquinones can be used the results
obtained being of an analogous character.
Dated this 12th day of November 1891.
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
-
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Blue Mordant Dyeing
Colouring Matters.
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 :—
New inventions were set forth in the Specifications of Letters Patent Nos. 14353
dated the 5th of October 1888 and 15121 dated the 20th October 1888 granted to
me on communications from my foreign correspondents to which I refer.
Descriptions were therein given of means for converting alizarine dyes into valuable
dyestuffs by alternate treatment first with fuming sulphuric acid and then with

page_text: concentrated sulphuric acid either in one continuous process or in two operations
separated by the isolation of a product resulting from the first stage of the process.
The same, or similar processes, have been applied to other alizarine dyes and some
other allied bodies (see the following Patents Nos. 8725, 12715, 17712 and 18729
of 1890 and Nos. 1883 and 4871 of 1891).
My foreign correspondents have discovered that by subjecting certain di-nitro-
anthra-quinones to suitable treatment with sulphuric acid in operations analogous
to those described in the aforesaid Specifications of Letters Patent Nos. 14353
and 15121 of 1888 valuable mordant dyeing coloring matters are obtained.
It is well known that nitro-anthra-quinones give colouring matter when treated
with ordinary concentrated sulphuric acid (see Liebermann, Berichte der deutschen
chemischen Gesellschaft 3, 905, 4, 231; Boettger and Petersen ibid. 4, 229 and
Liebermann and Hagen ibid. 15, 1801). In particular Lifschütz (ibid. 17, 891)
in 1884 more closely examined the complicated mixture resulting from the treat-
ment of 14 di-nitro-anthraquinone with concentrated sulphuric acid at a
temperature of about two hundred degrees centigrade and prepared from such
mixtures among other products a substance which he called "colouring matter 1b."
The properties of this substance, and in particular the spectrum which it gave, as
described by Lifschütz in the publication previously referred to, proves that the
characteristic colour so produced is identical with that of the dye resulting from
the process according to the present invention. The new process according to this
invention however results in a colouring product less contaminated with impurities
and the yield is larger.
Further nitro-anthraquinones have, as is well known, been treated with fuming
sulphuric acid (vide. infra.) so as to produce soluble colouring matters such as are
hereinafter mentioned.
My foreign correspondents have discovered that if certain di-nitro-anthra-
quinones be alternately treated first with fuming sulphuric acid and then with
concentrated sulphuric acid a valuable dye product is easily obtained in quantities
which make the result a practical success.
The said treatment is performed in two steps or stages.
1st. The di-nitro-anthraquinone selected for treatment is treated with fuming
sulphuric acid under suitable conditions until a colouring matter soluble in water is
formed.
2nd. The product obtained as the result of the first stage of the process is then
suitably treated with concentrated, or monohydrated, sulphuric acid, until the said
soluble product is converted into a mordant dyeing colouring matter which is com-
paratively insoluble in water. The products obtainable in this way constitute
valuable colouring matters.
The nature of the product obtained varies according to the strength of the
fuming sulphuric acid used in the first stage, the duration of the operation, and
the temperature at which it is carried on. Different products likewise result if the
soluble colouring matters produced as a result of the first stage of the process be
isolated and then this isolated product be subjected to the treatment with con-
centrated sulphuric acid as described in the second stage. The treatment may
therefore be divided into two separate processes and it is this treatment in two
separate processes which forms the subject matter of this present application
whereas the process which consists in diluting the whole melt obtained in the first
stage to the requisite strength, and proceeding at once with the second stage of the
treatment so as to unite the two steps or stages into one connected process forms
the subject matter of my application for Letters Patent No. 19588 of even date
herewith.
The isolation of the intermediate soluble colouring matters appears to effect a
change in its chemical nature probably by reason of the action of the water on it
and it is in consequence of this that the final dye product is different accordingly as
the intermediate soluble colouring matter is isolated or not.
The production of some soluble colouring matters by simply treating nitro-

page_text: anthraquinones with fuming sulphuric acid has long been known and was mentioned in
the Specification of German Patent No. 6526 and in the Specification of the English
Patent No. 217778. But those soluble colouring matters (Friedländer, Fortschritte
der Theerfarbenfabrikation Vol. I, p. 311, note) were not of any practical use
and the Patents referring to them were not kept in force but were allowed to
become void.
In carrying out this present invention it is found in practice that several isomeric
di-nitro anthraquinones can be used, namely 1.4¹ di-nitro-anthraquinone (see
Roemer Berichte der deutschen chemischen Gesellschaft: 16, p. 363) a-di-nitro-
anthraquinone (Boettger and Petersen, Annalen der Chemie Vol. 160 p. 147) and
mixtures thereof, also the crude mixture of di-nitro-anthraquinones resulting from
the energetic nitration of anthraquinone can be employed without previous
purification or separation of its constituents one from another, without in any way
altering the process as herein described and the products obtained are in all cases
closely analogous.
The following description of a method of obtaining a valuable mordant dyeing
colouring matter will serve as an example to illustrate the manner in which the
present invention can be carried into practical effect, but I do not limit myself to
the precise details given in this example as the process is susceptible of considerable
variation in matters of detail without departing from the nature of the invention
hereinafter claimed and the products obtained will still be of a similar nature.

page_text: a red solution. Its solutions shew most characteristic absorption spectra. Thus in
the alcoholic, ethereal and benzene solutions the spectrum consists of two sharply
defined bands in the green which are accompanied each by a weaker one and
further by some other weak lines. In the sulphuric acid solution the spectrum is
made up of two deep dark broad lines, one in the yellow, and one in the green,
and an indication of a very weak line in the red. These absorption spectra are
identical with those which Lifschütz described in differentiating his colouring
matter hereinbefore referred to. A direct optical comparison proves their
identity.
If in the foregoing example the 1'4' di-nitro-anthraquinone be replaced by the
isomeric a-dinitro-anthraquinone, a very similar colouring matter is obtained, the
solutions of which mostly shew a tint somewhat bluer or greener than are the tints
of the solutions hereinbefore described. It also dyes on mordanted wool, bluer or
greener shades and it also shews a characteristic spectrum.
Again if the crude mixture of di-nitro-anthraquinones as aforesaid be used then
a mixed product is obtained which possesses the properties of a mixture containing
both the above described coloring matters.
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 process of manufacturing valuable mordant dyeing colouring matters by
first treating di-nitro-anthraquinones, as herein explained with fuming sulphuric
acid then isolating the soluble colouring matters obtained, and afterwards converting
the said soluble colouring matters into comparatively insoluble mordant dyeing
colouring matters by the action of ordinary concentrated sulphuric acid, all sub-
stantially as herein described.
2. The process of manufacturing valuable mordant dyeing colouring matters by
treating the colouring matter soluble in water herein before described (obtained as
an isolated product as herein described under (a) in the example or in any other way)
with ordinary concentrated sulphuric acid substantially as hereinbefore described.
Dated this 10th day of September 1892.
J. H. JOHNSON & CO.,
Agents.