The Manufacture and Production of Blue Mordant Dyeing Colouring Matters from Dinitro-anthraquinones.
Year: 1897

page_text: The Manufacture and Production of Blue Mordant Dyeing Colouring
Matters from Dinitro-anthraquinones.
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 com-
municated to me from abroad by The Badische Anilin & Soda Fabrik, of Ludwig-
shafen-on-Rhine, in the Empire of Germany) to be as follows:
In the manufacture of blue mordant dyeing colouring matters by the treatment
of dinitro-anthraquinones with fuming sulphuric acid it is known that either the
addition of sulphur to the melt or the addition, under certain conditions of boracic
acid to the melt, will produce definite valuable results in each separate case.
My foreign correspondents have discovered that new mordant dyeing colouring-
matters can be obtained by the simultaneous use of sulphur and boracic acid in the
fuming acid melt. These new colouring matters possess valuable properties
differing, and in no way deducible, from those of the colouring matters obtained
when using either of the said materials alone.
The nature of the products obtained varies according to the strength of the
fuming acid employed and the temperature and duration of treatment."
The following examples will serve to further illustrate the nature of the inven-
tion but the details can in all cases be varied. The parts are by weight.
EXAMPLE 1.
Mix about ten parts of 1'4' dinitro-anthraquinone, ten parts of crystallised boracio
acid, two parts of sulphur and one hundred, to two hundred, parts of fuming
sulphuric acid containing about thirty to forty per cent. free anhydride (SO). Heat
the mixture for from about two, to two and a half hours at a temperature of one
hundred and twenty, to one hundred and thirty degrees Centigrade. Dilute the
melt with two thousand to three thousand parts of water, filter and wash with cold
water till neutral. The resulting colouring matter is but slightly soluble in cold
water but is readily soluble in hot water.
If under the conditions of the above example sulphur alone had been used a
reddish-blue dyestuff soluble in water would have been obtained. By the use of
boracic acid alone insoluble brown-violet colouring matters have been produced.
The new coloring matter is entirely different from these and gives a blue of a very
greenish shade possessing very valuable properties. It possesses the following
characteristics. It dissolves in concentrated sulphuric acid giving a yellow
solution; the solutions in ammonia caustic soda and aniline are blue, the alcoholic

page_text: solution is blue violet and in hydrochloric acid it dissolves giving a brownish-
yellow color. Its solubility in hot water is sufficiently great to permit of its use
in piece-dyeing by the one bath-method. The shades obtained by its use are fast
to fulling.
EXAMPLE 2,
Mix together about ten parts of dinitro-anthraquinone, ten parts of crystallised
boracic acid, two parts of sulphur, and two hundred parts of fuming sulphuric
acid containing about forty-five per cent. free anhydride (SO). Heat the mixture
for about two, to two and a half, hours at a temperature of one hundred and forty,
to one hundred and fifty, degrees Centigrade. Pour the melt into water, precipi-
tate with common salt, filter, wash and dry. The new colouring matter thus
obtained dyes a more reddish shade of blue than does the product of Example 1.
It has the character of a sulpho acid and is soluble in cold water. It dyes far
purer shades than either of the colouring matters which can be obtained under
similar conditions by the use of either boracic acid alone, or sulphur alone.
The new colouring-matter possesses the following characteristics Its solution
in concentrated sulphuric acid is blueish red; in soda, red-violet; in caustic soda,
blue; in ammonia, violet; in cold water, red. In alcohol it is practically
insoluble.
If the temperature of treatment be further raised no essentially different results
are obtained; only at temperatures of about two hundred degrees and higher
insoluble dyes of a dull shade are obtained
Instead of 14 dinitro-anthraquinone other dinitro-anthraquinones, or mixtures
thereof, and their partial reduction-products, can be used.
Dated this 12th day of July 1897.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
The Manufacture and Production of Blue Mordant Dyeing Colouring
Matters from Dinitro-anthraquinones.
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 com-
municated to me from abroad by The Badische Anilin & Soda Fabrik, of Ludwig-
shafen-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 manufacture of blue mordant dyeing colouring-matters by the treatment
of dinitro-anthraquinones with fuming sulphuric acid it is known that either the
addition of sulphur to the melt or the addition under certain conditions of boracic
acid to the melt, will produce definite valuable results in each separate case.
My foreign correspondents have discovered that new mordant dyeing, colouring-
matters can be obtained by the simultaneous use of sulphur and boracic acid in
the fuming acid melt. These new colouring matters possess valuable properties
differing and in noway deducible from those of the colouring-matters obtained
when using either of the said materials separately.
The nature of the products obtained varies according to the strength of the
"fuming acid employed and the temperature and duration of treatment.

page_text: The following examples will serve to further illustrate the manner of carrying
out the invention into practical effect but the details can in all cases be varied.
The parts are by weight.
EXAMPLE 1.
Mix about ten parts of 1'4' dinitroanthraquinone ten parts of crystallized boracic
acid, two parts of sulphur and one hundred to two hundred parts of fuming
sulphuric acid containing about thirty to forty per cent. free anhydride (SO). Heat
the mixture for from about two, to two and a half, hours at a temperature of one
hundred and twenty, to one hundred and thirty degrees Centigrade. Dilute the
melt with two thousand to three thousand parts of water, filter, and wash with cold
water till neutral. The resulting colouring-matter is but slightly soluble in cold
water, but is readily soluble in hot water.
If under the conditions of the above example sulphur alone had been used a
reddish-blue dyestuff soluble in water would have been obtained. By the use of
boracic acid alone insoluble brown-violet colouring-matters have been produced.
The new colouring-matter is entirely different from these and gives a blue of a
very greenish shade possessing very valuable properties. It possesses the follow-
ing characteristics. It dissolves in concentrated sulphuric acid giving a yellow
solution, the solutions in ammonia, caustic soda and aniline are blue, the alcoholio
solution is blue-violet and in hydrochloric acid it dissolves giving a brownish-
yellow colour. Its solubility in hot water is sufficiently great to permit of its use
in piece-dyeing by the one bath-method. The shades obtained by its use are fast
to fulling.
EXAMPLE 2.
Mix together about ten parts of dinitroanthraquinone, ten parts of crystallized
boracic acid, two parts of sulphur and two hundred parts of fuming sulphuric
acid containing about forty-five per cent. free anhydride (SO,). Heat the mixture
for from about two to two and a half, hours at a temperature of one hundred and
forty, to one hundred and fifty degrees Centigrade. Pour the melt into water
precipitate with common salt, filter, wash and dry. The new colouring-matter
thus obtained dyes a more reddish shade of blue than does the product of
Example 1. It has the character of a sulpho acid and is soluble in cold water. It
dyes far purer shades than either of the colouring-matters which can be obtained
under similar conditions by the use of either boracic acid alone, or sulphur alone.
The new colouring-matter possesses the following characteristics. Its solution
in concentrated sulphuric acid is bluish-red; in soda, red-violet; in caustic soda,
blue; in ammonia, violet; in cold water, red. In alcohol it is practically
insoluble.
If the temperature at which the reaction is effected be further raised no essen-
tially different results are obtained, only at temperatures of about two hundred
degrees and higher insoluble dyes of a dull shade are obtained.
Instead of 14 dinitro-anthraquinone other dinitro-anthraquinones, or mixtures
thereof, and their partial reduction products, can be used.
I do not claim in this specification the addition of sulphur alone or of boracic
acid alone to the melt obtained from dinitro-anthraquinone or the like and
sulphuric acid, but the invention consists in the manufacture and production of
new and entirely unexpected colouring matters obtained by the simultaneous use
of boracic acid and sulphur in the production of blue mordant dyeing colouring
matters by the treatment of dinitro-anthraquinones or partial reduction products
thereof with fuming sulphuric acid.
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 In the manufacture of blue mordant dyeing colouring matters by the treat-

page_text: ment of dinitro-anthraquinones or partial reduction-products thereof with fuming
sulphuric acid, the simultaneous use of sulphur and boracic acid in the melt sub-
stantially as hereinbefore described.
2. The manufacture of new blue mordant dyeing colouring matters from dinitro-
anthraquinones substantially as herein before described in the examples.
3. As new products of manufacture the new blue mordant dyeing colouring-
matters obtained from dinitro-anthraquinones such as result from the processes
herein before described and claimed.
Dated this 7th day of April 1898.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.