The Manufacture and Production of New 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
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New 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 Letters Patent dated A.D. 1888 Nos. 14353
and 15121, it is stated that certain colouring matters of the alizarine group by
suitable treatment with sulphuric acid, 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 passes 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 extremely
valuable properties.
The treatment of the nitro-anthraquinones to obtain these 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.
2nd. This product obtained as the result of the first stage of the process is
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 result if the soluble
colouring matters produced in the first stage be isolated and purified and then the
purified product be subsequently subjected to the treatment with concentrated
sulphuric acid thus employing two separate processes; instead of uniting the two
stages into one process by diluting the whole melt obtained in the first stage to the
requisite strength, and immediately proceeding with the second part of the
operation.
In the latter case products of greener shades are obtained than in the first case.
According to the present invention greenish-blue dyes are obtained by treatment
of nitro-anthraquinones with fuming and ordinary sulphuric acid in one connected
or continuous process without separation of the product obtained in the first
instance.
The production of soluble colouring matters by treatment of nitro-anthraquinones
with fuming sulphuric acid (being the first part of the process) is known and has
been described in print (German Patent No. 6526).
The following descriptions of two methods of obtaining dyes according to this
invention are merely given as examples the method of manufacture being susceptible
of variation in many respects without changing the essential characteristics of the
products obtained.
Example 1. Mix about ten parts (the parts are by weight) of alpha-dinitro-
anthraquinone with about one hundred parts of fuming sulphuric acid containing
about twelve per cent. of free anhydride, heat the mixture to a temperature of about
one hundred and sixty degrees centigrade and maintain the heat for from about one

page_text: and a half to two hours. A soluble colouring matter is produced, forming a dirty
violet solution in water; without separating this product, dilute the melt with
about two hundred parts of ordinary concentrated sulphuric acid containing about
ninety five per cent. of real acid (H₂SO₁). Now heat the mixture for about two
hours at a temperature of about one hundred and thirty degrees centigrade or until
the soluble intermediate product is converted into a practically insoluble colouring
matter of the desired shade. Allow the product to cool, pour the mass into water,
filter the precipitate and wash well with cold water. If desired, purify by
dissolving in sodium acetate or some similar solution and precipitating with an
acid.
'
The new dyestuff thus obtained is when dry a dark coloured powder which
assumes a metallic lustre ou rubbing, it is very slightly soluble in hot water, but
dissolves in alcohol giving a blue solution, in concentrated sulphuric acid giving a
reddish brown solution and in cold aniline giving a deep blue solution. It is
insoluble or nearly so in cold glacial acetic acid, in ether and benzene. In alkaline
liquids it dissolves with a blue colour. Chemical analysis shows that this dye
contains both nitrogen and sulphur.
In using this dyestuff in dyeing or printing it may be applied in the form of
paste or in the form of an alkaline salt. The dye fixes itself especially on chrome
mordanted woul giving greenish blue shades of remarkable purity and fastness.
Example 2. If in the first stage of the process according to the above example
the alpha-di-nitro anthraquinone be treated with stronger fuming sulphuric acid at
a lower temperature in a manner similar to that described in the example given in
the aforesaid German Specification No. 6526 and then with concentrated sulphuric
acid as above described in Example 1, the product finally obtained forms a
colouring matter which dyes less greenish shades of blue and appears to be a
mixture of the greenish-blue dyestuff described above and another colouring matter
of a blue colour.
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 colouring matter
soluble in water is effected, then dilute the melt with about two hundred parts of
ordinary concentrated sulphuric acid containing about ninety-five per cent. of real
sulphuric acid (H₂SO) and continue the heating at one hundred and thirty degrees
centigrade as described in the previous example.
The colouring matter so obtained is as aforesaid, a mixture of a greenish-blue and
a blue dyestuff, but these materials have similar dyeing properties and do not
interfere with one another in dyeing so that with the aid of this product less
greenish shades of blue can be obtained, which are also of extraordinary beauty
and fastness.
The manufacture of the blue colour or dye which is contained admixed in this
product is described in a separate application for Letters Patent of even date here-
with. It is produced by separating and purifying the soluble colouring, matter
resulting from the first stage of the process of Example 2 and subsequently treating
this isolated body with concentrated sulphuric acid, thus dividing the two stages of
the manufacture into distinct processes.
Instead of the alpha-dinitro-anthraquinone mentioned in the examples herein-
before described other nitro- and amido-anthraquinones can be used and analogous
results obtained.
Dated this 12th day of November 1801
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New 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 & 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 of 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 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 dinitro-
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 colouring matters are obtained.
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 the isolated product be subjected to the treatment with
concentrated sulphuric acid as described in the second stage. The treatment may
therefore be divided into two separate processes instead of diluting the whole melt
obtained in the first stage to the requisite strength, and proceeding at once with the
second part of the treatment so as to unite the two steps or stages into one connected
process but the former plan is claimed under my application for Letters Patent
No. 19589 of even date herewith this present application referring only to the latter
plan in which new products are obtained dyeing greener shades than those obtained
by the separated processes involving isolation.
According to the present invention therefore new greenish-blue colouring
matter is obtained by treatment of certain di-nitro-anthraquinones with fuming
and with ordinary sulphuric acid in one connected process without the isolation
of the product of the first stage whereby any change in the chemical nature of
the intermediate colouring matter which might take place during its isolation is
avoided.
The production of some soluble colouring matters by simply treating nitro-
anthraquinones with fuming sulphuric acid has long been known and was mentioned
in the Specification of the German Patent No. 6526 and in the Specification of the

page_text: about forty per cent. free anhydride (SO), heat the mixture to a temperature of
one hundred to one hundred and thirty degrees centigrade and maintain this heat
for about three hours or until the aforesaid colouring matter soluble in water is
obtained, then dilute the whole melt with about two hundred parts of ordinary
concentrated sulphuric acid containing about ninety five per cent. real sulphuric
acid (H₂SO) and continue the heating at one hundred and thirty degrees centigrade
as described in the previous example.
The colouring matter so obtained is, as aforesaid, a mixture, but its main con-
stituents have similar dyeing properties and do not interfere with one another in
dyeing so that with the aid of this product less greenish shades of blue can be
obtained than are obtained with the product of Example 1 and these are also of
extraordinary beauty and fastness.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what I
claim is --
(1). The manufacture of the new greenish-blue mordant dyeing colouring matter
hereinbefore described (either alone or in admixture with other colouring matters),
by treating certain di-nitro-anthraquinones, as herein explained, first with fuming
sulphuric acid, and subsequently (and without isolating the soluble colouring-matter
formed) with concentrated sulphuric acid substantially as hereinbefore described.
(2). The manufacture of the new-greenish-blue mordant dyeing colouring matter,
herein before described (either alone or in admixture with other colouring matters)
by treating the melt resulting from the action of fuming sulphuric acid on certain
di-nitro-anthraquinones as hereinbefore explained with ordinary concentrated
sulphuric acid without previous isolation of the soluble colouring matter contained
in the said melt, all substantially as herein before described.
(3). As a new product the new greenish-blue colouring matter hereinbefore
described (whether alone or in admixture with other dyes) such as can be obtained
substantially as hereinbefore described.
Dated this 10th day of September 1892.
J. H. JOHNSON & Co.,
Agents.