The Manufacture and Production of New Mordant Dyeing Colouring- matters and of New Intermediate Products relating thereto.
Year: 1892

page_text: Date of Application, 25th Aug., 1892
Complete Specification Left, 15th May, 1893-Accepted, 1st July, 1893
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Mordant Dyeing Colouring-
matters and of New Intermediate Products relating thereto.
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
Ludwigshafen on Rhine in the Empire of Germany) to be as follows
This invention relates to the manufacture of new mordant dyeing colouring
matters and of new intermediate products as hereinafter explained.
In the first place the so-called Bohn's reaction is applied to certain dinitro-
anthra-quinones, that is these bodies are treated first with strongly fuming sulphuric
acid and subsequently with strong sulphuric acid. The first stage of the reaction
results in the formation of new intermediate products which are, in part useful
dyes and in part can be converted into useful dyes by the treatment in the second
stage with strong sulphuric acid or with reagents which act similarly in this
respect such as hydrochloric acid for example.
Also the intermediate products can be treated with caustic alkalies and subse-
quently with dilute acids to obtain useful dyes. On treatment of the said
intermediate products with ammonia or substituted ammonia compounds, new and
valuable dyes are obtained.
In the Specifications of Letters Patent Nos. 14353 and 15121 of 1888 Bohn's
reaction is for the first time described in its application to alizarine blue and
alizarine green. The reaction has also been applied to other alizarine dyes and
similar products (see Patents Nos. 8725; 12715, 17712 and 18729 of 1890
and Nos. 1883 and 4871 of 1891).
Finally nitro-anthraquinones have already been treated with sulphuric acid for
the production of colouring matters (see Liebermann Berichte &c. 3.905; 4. 231;
Boettger & Petersen ihid 4. 229; Liebermann and Hagen, ibid 15. 1801 Lifschutz
ibid 17 891). But prior to my applications for Letters Patent Nos. 19588 and
19589 both dated November 12th 1891 no successful manufacture of colouring
matter from nitro-anthraquinones had believe been effected. In the said
Specification there is described the treatment of certain di-nitro-anthraquinones
with fuming sulphuric acid containing up to about 40 per cent. free anhydride (SO)
to obtain soluble intermediate colouring matters in a manner similar to that described
in the Specification of the lapsed German Patent No. 6526 and the further treat-
ment of the said soluble intermediate colouring matters with ordinary concentrated
sulphuric acid.
According to the said Specification of the said German Patent stronger fuming
sulphuric acid is used at a lower temperature for a shorter time. My foreign
correspondents have discovered that this general principle does not apply but that
different and new intermediate products result if di-nitro-anthraquinones be
suitably treated with fuming sulphuric acid containing a high percentage of free
anhydride (by preference from 70 to 100 per cent. of SO) at a temperature not
exceeding about thirty-five to forty degrees centigrade or not exceeding that
temperature to any essential degree (see Example 1). The said new intermediate
products are themselves colouring matters but they derive their principal value
from the fact that they can be converted by appropriate treatment into new and
valuable dyes.

page_text: EXAMPLE 1.-PRODUCTION OF NEW SOLUBLE COLOURING MATTERS THE
SO-CALLED "INTERMEDIATE PRODUCTS."
Add about ten parts of the di-nitro anthra quinone selected for treatment
(say 14 dinitroanthraquinone) gradually in small portions at a time, to about from
one hundred to one hundred and fifty parts of fuming sulphuric acid. During
this mixture care must be taken to avoid all rise of temperature, subsequently the
mixture is allowed to stand for a few hours or longer. A dirty violet-red melt is
obtained; dilute this by adding twice to three times the quantity of well cooled
concentrated sulphuric acid (containing about 95 per cent. or more real acid H,SO.).
Next pour the mixture on to ice, when a red brown precipitate forms which we call
an intermediate product." To isolate this if desired separate it as quickly, and
completely, as possible from the sulphuric acid. To further purify it, dissolve it
in alcohol add water and extract with ether. Distil off the solvent when the
intermediate product will be obtained in the form of a dark powder.
In the moist state it is unstable particularly in the presence of sulphuric acid.
It is only very slightly soluble in water but is readily soluble in alcohol, glacial
acetic acid, and nitro-benzene, even in the cold. It dissolves in solutions of caustic
soda and carbonate of soda giving a blue-violet colour. In concentrated sulphuric
acid the solution is blue-green and possesses a strong brown fluorescence. This
sulphuric acid solution possesses a characteristic absorption spectrum differentiating
the product from all similar compounds.
Mix the intermediate product with water and heat to boiling add caustic soda
and then acidify at once with a little hydrochloric acid. The new colouring
natter separates out as a brown precipitate. It is with difficulty soluble in water 5
but is readily soluble in alcohol giving a violet-red solution possessing a red
fluorescence. In cold aniline it dissolves giving a blue-violet solution. It is with

page_text: difficulty soluble in nitro-benzine. Its solution in caustic soda is blue and its
solution in carbonate of soda is violet. The colouring matter also dissolves in cold
concentrated hydrochloric acid giving a red-brown colour. The concentrated
sulphuric acid solution is red with a brown fluorescence and possesses a characteristic
spectrum which fully serves to differentiate the product. The dye fixes itself on
chrome mordanted wool giving greenish-blue shades. The same colouring matter
is obtained if the above described intermediate product be treated in the isolated
form with concentrated sulphuric acid for a few hours at a temperature of about
one hundred and thirty degrees centigrade.
A similar colouring matter to that obtained as above described in Example 2 is
produced if the sulphuric acid melt containing the new intermediate product
obtained as described in Example 1 is after the dilution with concentrated sulphuric
acid treated as follows.
Instead of pouring onto ice, heat the mixture for from two to three hours at a
temperature of about one hundred and twenty, to one hundred and thirty, degrees
centigrade. Pour the whole into water, filter off the difficultly soluble product and
wash. The product so obtained differs from that above described under Example 2
in the following points. The alcoholic solution is less bluish and the glacial acetic
acid solution is of a yellow-red colour and this product does not appear to possess
a well defined absorption spectrum. It dyes chrome mordanted wool in somewhat
greener shades than does the colouring matter above described under Example 2.
EXAMPLE 4.
Mix about ten parts of a paste containing ten per cent. of the soluble inter-
mediate product with about from one hundred to one hundred and fifty parts
ammonium hydrate, containing thirty per cent. ammonia (NH3). Allow the mixture
to stand for about four or five hours either at ordinary temperature or preferably
at the temperature of boiling water stirring thoroughly from time to time. Then
dilute with water and add sufficient hydrochloric acid to produce a slightly acid
reaction; filter the violet-brown precipitate obtained and wash. For dyeing
purposes the paste thus obtained can be used directly. In the dry condition the
dye is a dark powder which is somewhat soluble in water giving a blue-violet
colour, and in alcohol giving a red-violet colour and a red fluorescence, and in
glacial acetic acid giving a violet-red colour and brown fluorescence. It gives .blue
solutions in aniline and also in sodium carbonate and hydrate. The concentrated
sulphuric acid solution is bluish-red with a red fluorescence and possesses a
characteristic absorption spectrum. The dye is readily soluble in cold strong
hydrochloric acid giving a brown-red colour.
As aforesaid analogous dyes can be obtained by using in the above example.
methylamines, aniline, ortho-toluidine and other analogues of ammonia instead of
that body.
Instead of using the 14' di-nitro anthraquinone in the preparation of the new
intermediate product similar new intermediate products can be obtained by using
other nitro-anthraquinones and the products of their partial reduction. Such
nitro-anthraquinones are for instance: alpha-di-nitro-anthraquinone and the crude
mixture of di-nitro-anthraquinones resulting from the energetic nitration of
anthraquinone and in each case as aforesaid their reduction products.
Dated this with day of A wrust 1800
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.

page_text: COMPLETE SPECIFICATION.
The Manufacture and Production of New Mordant Dyeing Colouring-
matters and of New Intermediate Products relating thereto.
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:―
This invention relates to the manufacture of new mordant dyeing colouring
matters and of new intermediate products as hereinafter explained. In the first
place the so-called Bohn's reaction is applied to certain dinitro-anthraquinones,
that is these bodies are treated first with strongly fuming sulphuric acid and
subsequently with strong sulphuric acid. The first stage of the reaction results in
the formation of new intermediate products which are, in part, useful dyes and in
part can be converted into useful dyes by the treatment in the second stage with
strong sulphuric acid or with reagents which act similarly in this respect such as
hydrochloric acid for example. Also the intermediate products can be treated with
caustic alkalies and subsequently with dilute acids to obtain useful dyes. On
treatment of the said intermediate products with ammonia new and valuable dyes
are obtained.
In the Specifications of Letters Patent Nos. 14353 and 15121 of 1888, Bohn's
reaction is for the first time described in its application to alizarine blue and
alizarine green. The reaction has also been applied to other alizarine dyes and
similar products (see the Specifications of Letters Patent Nos. 8725, 12715, 17712
and 18729 of 1890 and Nos. 1883 and 4871 of 1891).
Finally nitro-anthraquinones have already been treated with sulphuric acid for
the production of colouring matters (see Liebermann Berichte &c. 3, 905; 4, 231;
Boettger & Petersen ibid 4, 229; Liebermann and Hagen, ibid 15, 1801; Lifschütz
ibid 17; 891). But prior to the Letters Patent Nos. 19588 and 19589 of 1891
granted to me on communications from my foreign correspondents, no successful
manufacture of colouring matter from nitro-anthraquinones had been effected. In
the said Specifications there is described the treatment of certain di-nitro-anthra-
quinones with fuming sulphuric acid containing up to about 40 per cent. free
anhydride (SO) to obtain soluble intermediate colouring matters in a manner
similar to that described in the Specification of the lapsed German Patent No. 6526
and the further treatment of the said soluble intermediate colouring matters with
ordinary concentrated sulphuric acid.
According to the said Specification of the said German Patent the same result
is obtained when using stronger fuming sulphuric acid at a lower temperature for
a shorter time as when using a weaker acid at a higher temperature for a longer,
time. My foreign correspondents have discovered that this is not the case but that
different and new intermediate products result if dinitro-anthraquinones be suitably
treated with fuming sulphuric acid containing a high percentage of free anhydride
(by preference from 70 to 100 per cent. SO) at a temperature not exceeding about
thirty-five to forty degrees centigrade or not exceeding that temperature to any
essential degree (see Example 1). These said new intermediate products are
themselves colouring matters but they derive their principal value from the
fact that they can be converted by various appropriate treatments into new and
valuable dyes.
I give the following methods of converting the said new intermediate products
into valuable dyes as examples of treatments suitable for the purpose.
(1) The isolated intermediate product is treated for a short time with a hot
soļution of a caustic alkali and then the product is acidified (see Example 2).

page_text: (2) The isolated intermediate product is treated with ordinary concentrated
sulphuric acid.
These two treatments yield like products.
(3) A similar product is obtained if the fuming acid melt containing the inter-
mediate product be diluted with a sufficient quantity of ordinary concentrated
sulphuric acid and without any isolation of the intermediate product be then heated
(see Example 3).
In the above three examples the reagents employed appear to affect the inter-
mediate product in that they split off the radicle of sulphuric acid or sulpho-groups
therefrom, and any reagents which in this respect act similarly to those above
mentioned can be substituted for them.
(4) The new intermediate products can be converted into valuable dyes by
suitable treatment with strong ammonia (see Example 4).
The following examples will serve to further illustrate and explain the nature
of the invention but they are capable of great variation without departing from
the invention.
The parts are by weight.
EXAMPLE 1.-PRODUCTION OF NEW SOLUBLE COLOURING MATTERS THE
SO-CALLED "INTERMEDIATE PRODUCTS."
Add about ten parts of the di-nitro-anthraquinone selected for treatment (say
14 di-nitro-anthraquinone) gradually in small portions at a time, to about from
one hundred to one hundred and fifty parts of fuming sulphuric acid containing
about 70 to 100 per cent. free anhydride SO,. During this mixture care must be
taken to avoid all rise of temperature, subsequently the mixture is allowed to
stand for a few hours or longer. A dirty violet-red melt is obtained, dilute this by
adding twice to three times the quantity of well cooled concentrated sulphuric acid
(containing about 95 per cent. or more real acid H₂SO). Next pour the mixture
on to ice, when a red brown precipitate forms which I call an "intermediate
product." To isolate this if desired, separate it as quickly and completely as
possible from the sulphuric acid. To further purify it, dissolve it in alcohol, add
water and extract with ether. Distil off the solvent when the intermediate product
will be obtained in the form of a dark powder.
In the moist state it is unstable particularly in the presence of sulphuric acid.
It is only very slightly soluble in water, but is readily soluble in alcohol, glacial
acetic acid, and nitro-benzene even in the cold. It dissolves in solutions of caustic
In concentrated sulphuric
soda and carbonate of soda giving a blue violet colour.
acid the solution is blue green and possesses a strong brown fluorescence. This
sulphuric acid solution possesses a characteristic absorption spectrum differentiating
the product from all similar compounds.
No text detected.

page_text: the product. The dye fixes itself on chrome mordanted wool giving greenish-blue
shades.
The same colouring matter is obtained if the above described intermediate
product be treated in the isolated form with concentrated sulphuric acid for a few
hours at a temperature of about one hundred and thirty degrees centigrade.

page_text: 2. The manufacture of the new intermediate products hereinbefore described by
treating the di-nitro-anthraquinones hereinbefore defined with strongly fuming
sulphuric acid (containing about from 70 to 100 per cent. SO,) substantially as
hereinbefore described.
3. The manufacture of new mordant dyeing colouring-matters by treating the
new intermediate products with concentrated sulphuric acid substantially as
hereinbefore described.
4. The manufacture of new mordant dyeing colouring-matters by treating the
new intermediate products herein before described with a hot solution of a caustic
alkali and then acidifying the product substantially as described.
5. The manufacture of new mordant dyeing colouring-matters by treating the
new intermediate products with ammonia substantially as herein before described.
6. As new articles of manufacture the new mordant dyeing colouring-matters and
the new intermediate products such as can be obtained substantially as herein before
described.
J. H. JOHNSON & Co.,
Agents..