The Manufacture or Production of Colouring Matters.
Year: 1894

page_text: Date of Application, 30th June, 1894
Complete Specification Left, 26th Mar., 1895-Accepted, 27th Apr., 1895
TRUVIOIONAL DOITICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & CO., of-Elberfeld, Germany.]¯
==
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
My foreign correspondents have found some time ago that dye-stuffs_of_the
anthracene series, capable of dyeing with the aid of mordants, are obtained on
allowing concentrated or fuming sulphuric acid to act in the presence of boric acid
or other boric compounds (which, when used with sulphuric acid, act in a similar
manner) on di-ortho-nitro anthraquinone, or isomeric dinitro anthraquinones, or the
crude mixture of nitro anthraquinones obtained on energetically nitrating anthra-
quinone or anthracene, or on the sulphonic acids of these nitro anthraquinones.
My foreign correspondents have now found that colouring matters producing
much greener shades are obtained on heating the aforesaid nitro-anthraquinone
compounds with sulphuric acid and boric acid, or other boron compounds (which,
when used with sulphuric acid, act in a similar manner) in the presence of amines or
diamines of the benzene or naphthalene series, such as aniline, toluidine, phenylene
diamine, toluylene diamine, naphthylamine, naphthylene diamine, or the like, or
substitution derivatives of these amido compounds, or salts of the amido products
hereinbefore defined.
The action of these amido compounds during the said operation is not yet
perfectly clear, but according to the researches of my foreign correspondents, it
seems to be excluded that they act merely as reducing agents, and it is very
probable that the amido compounds used combine with the anthraquinone nucleus.
The method of producing these new colouring matters, in general, consists in
stirring the dinitro-anthraquinones, or the other nitro-anthraquinone products
hereinbefore defined, into concentrated sulphuric acid, and subsequently adding
boric acid, or another suitable boron compound, and the amido product or a salt
thereof. In view of this process for producing the new dye-stuffs herein before
defined, the method is materially different from that described in the French
Patent No. 227,003, as the latter process consists in acting with concentrated or
fuming sulphuric acid on the finished products obtained by condensing aromatic
bases with dinitro anthraquinone, or analogues thereof.
A special characteristic of the new process hereinbefore defined, is the
simultaneous use of boric acid or other suitable boron compounds, as dye-stuffs of
technical value are obtained only when using these agents, whereas colouring
matters possessing less technical value, and chemically different, result, if these
agents be not used..
The new process is illustrated by the following example. The parts are by
weight.
COLOURING-MATTER OBTAINED FROM DI-ORTHO-NITRO ANTHRAQUINONE BY
MEANS OF SULPHURIC ACID, BORIC ACID, AND ANILINE.
2.5 parts of aniline are added to a mixture prepared from 10 parts of di-ortho-
nitro anthraquinone, 200 parts of sulphuric acid (66 degrees Baume), and 5 parts of
crystallized boric acid. The mass, while being stirred, is heated during about one
[Pins71

page_text: bour and a half, at from 180 to 200 degrees. After cooling, the mass is poured
into water, and the resulting liquid is heated to boiling point. The colouring
matter which separates as a dark violet precipitate is filtered off. Its properties
are enumerated in the following table, which also contains the properties of the
dye-stuff produced from di-ortho-nitro anthraquinone sulphuric acid (66 degrees
Baumé) and aniline, that is to say, without an addition of boric acid or another
suitable boron compound.
Oye stuff from di-ortho-
nitro anthraquinone,
sulphuric acid (66 de-
grees Beaumé), and
aniline.
Colouring-matter obtained
from di-ortho-nitro-an-
thraquinone, sulphuric
acid (66 degrees Beaumé),
aniline, and boric acid.
Colour of the solution in
pure concentrated sul-
phuric acid
dull
yellowish brown.
This colour turns into
reddish-brown on the
addition of boric acid.
dull reddish brown. This
colour is changed into 2
intense violet on adding
boric acid. The result-
ing solution shews a
characteristic absorption
The process proceeds in an analogous manner, if the di-ortho-nitro anthraquinone
used in the foregoing example is replaced by corresponding quantities of isomeric
dinitro anthraquinones, or the crude mixture of nitro anthraquinones obtained on
energetically nitrating anthracene or anthraquinone, or nitro anthraquinone
sulphonic acids.
In order to produce these new dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the said example, as these can be varied. For
instance, the process can be carried out at lower temperatures, say, at from 140 to
160 degrees Centigrade. In this case, the process will require a somewhat longer

page_text: time. Weaker sulphuric acid (such as sulphuric acid of 62 degrees Beaumé), or
stronger acid (such as monohydrated sulphuric acid), or weak fuming sulphuric
acid, can be employed in place of sulphuric acid (66 degrees Beaumé) used in the
foregoing example. In case weaker acid is used, dye-stuffs result which produce
somewhat redder shades, whilst when using stronger acid, colouring matters are
produced which yield somewhat greener shades. The aniline used in the said
example can be replaced by its homologues or analogues, such as ortho toluidine,
paratoluidine, xylidine, alpha-naphthylamine, beta naphthamine, or the like, or by
aromatic diamines, such as meta phenylene diamine, para phenylenediamine,
toluylene diamine, naphthylene diamine, or the like, or derivatives of these or
analogous amido products. Instead of boric acid prescribed in the above example,
other boron compounds (for instance, salts of boric acid or boron trichloride or the
like) may be used, which, in the presence of sulphuric acid, yield boric acid.
Colouring matters are thus obtained which in general possess properties similar to
those of the dye-stuff obtainable as described in the above example.
1
Ր .
1001
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
My foreign correspondents have described in the Specification of Letters Patent
No. 14345, dated 25th July 1893, a process for producing dye-stuffs of the
anthracene series, capable of dyeing with the aid of mordants, which process
consists in allowing concentrated or fuming sulphuric acid to act in the presence
of boric acid, or other boron compounds (which, when used with sulphuric acid,
act in a similar manner), on di-ortho-nitro-anthraquinone, or isomeric dinitro
anthraquinones, or the crude mixture of nitro anthraquinones obtained on
energetically nitrating anthraquinone or anthracene, or on the sulphonic acids of
these nitro anthraquinones.
My foreign correspondents have now found, that colouring matters producing
much greener shades are obtained on heating the aforesaid nitro anthraquinone
compounds with sulphuric acid and boric acid or other boron compounds (which,
when used with sulphuric acid, act in a similar manner) in the presence of amines
of the benzene series, such as aniline, toluidine, or the like, or salts of these or the
like amido products.
The action of these amido-compounds during the said operation is not yet
perfectly clear, but according to the researches of my foreign correspondents, it
is improbable that they act merely as reducing agents, and it is very probable that
the amido compounds used combine with the anthraquinone nucleus.
The method of producing these new colouring-matters in general consists in
stirring the dinitro anthraquinones, or the other nitro anthraquinone products
hereinbefore defined, into concentrated sulphuric acid, and subsequently adding
boric acid, or another suitable boron compound, and the amido product or a salt
thereof. The method is consequently materially different from that described in
the French Patent No. 227,003, dated, 9th January 1893, as the latter process
consists in acting with concentrated or fuming sulphuric acid on the finished
products obtained by condensing aromatic bases with dinitro anthraquinone or
analogues thereof.
A special feature of the new process hereinbefore defined, is the simultaneous

page_text: use of boric acid, or other suitable boron compounds, as dye-stuffs of technical
value are obtained only when these agents are used, colouring-matters being formed
which differ chemically from the said new dye-stuffs, and which are of less
technical value, if these agents (viz., boric acid or the like) be not used.
The new process is illustrated by the following example. The parts are by
weight:
COLOURING-MATTER OBTAINED FROM DI-ORTHO-NITRO-ANTHRAQUINONE
MEANS OF SULPHURIC ACID, BORIC ACID, AND ANILINE.
BY
25 parts of aniline are added to a mixture prepared from 10 parts of di-ortho-
nitro anthraquinone, 200 parts of sulphuric acid (66 degrees Baumé), and 5 parts
of crystallized boric acid; and the mass is heated during about one hour and a half,
at from 180 to 200 degrees, being kept well stirred. When cool, the mass is
poured into water, and the liquid is heated to the boiling point. The colouring-
matter which separates as a dark violet precipitate is filtered off, pressed, and
dried. Its properties are enumerated in the following table, which also contains
the properties of the dye-stuff produced from di-ortho-uitro anthraquinone, sulphuric
acid (66 degrees Baumé), and aniline, that is to say without an addition of boric
acid or another boron compound.
1
yellowish brown.
This colour turns into
eddish-brown on
the
ddition of boric acid.
dull reddish brown. This 3
colour is changed into
intense violet on adding
boric acid. The solution
then shews a charac-
teristic absorption spec- 3
trum.

page_text: The process proceeds in an analogous manner on substituting for the di-ortho-
nitro anthraquinone used in the foregoing example, corresponding quantities of
isomeric dinitro anthraquinones, or the crude mixture of nitro anthraquinones
obtained on energetically nitrating anthracene or anthraquinone, or nitro anthra-
quinone sulphonic acids.
In order to produce these new dye stuffs, my foreign correspondents do not limit
themselves to the directions given in the said example, as these can be varied.
For instance, the process can be carried out at lower temperatures, say, at from 140.
to 160 degrees Centigrade. In this case, the process will require a somewhat longer
time. Weaker sulphuric acid (such as sulphuric acid of 62 degrees Baumé), or
stronger-acid (such as moño hydrated sulphuric acid), or weak fuming sulphuric
acid, can be used in place of the sulphuric acid (66 degrees Baumé) used in the
foregoing example. In case weaker acid be used, dye-stuffs are formed which
produce somewhat redder shades, whilst on using stronger acid, colouring matters
are produced which yield somewhat greener shades. Instead of the aniline used in
the said example, its homologues, such as ortho-toluidine, para-toluidine, or the
like, or salts thereof, can be used. The colouring-matters obtained from di-ortho-
nitro-anthraquinone, sulphuric acid, boric acid, and, on the one hand, ortho
toluidine, on the other hand. para-toluidine, possess the properties mentioned in the
following table :-
:-
anthra-
Colouring matter from
di-ortho-nitro
quinone, sulphuric acid,
boric acid, and ortho-
toluidine.
Colouring matter from
di-ortho-nitro anthra-
quinone, sulphuric acid,
boric acid, and para-
toluidine.
Instead of the boric acid prescribed in the above. example, other boron com-
pounds (for instance, salts of boric acid, boron trichloride, or the like) may be
used, which, in the presence of sulphuric acid, yield boric acid.
In all cases, colouring-matters are formed which in general possess properties
similar to those of the dye-stuffs hereinbefore enumerated.
Having now particularly described and ascertained the nature of the said inven
tion and in what manner the same is to be performed, as communicated to me
from abroad, I declare that what I claim is :-
1. For the production of dye-stuffs of the anthracene series, capable of dyeing

page_text: with the aid of mordants from di-ortho-nitro-anthraquinone, or other nitro-
anthraquinones, or nitro-anthraquinone sulphonic acids, and concentrated or fuming
sulphuric acid, and boric acid or other boron compounds (which, when used with
sulphuric acid, act in a similar manner), the simultaneous use of aromatic amines,
or salts thereof.
2. The process for producing dye-stuffs of the anthracene series capable of
dyeing with the aid of mordants, which process consists in allowing concentrated
or fuming sulphuric acid to act at elevated temperatures on di-ortho-nitro anthra-
quinone, or isomeric dinitro-anthraquinones, or the crude mixture of nitro-anthra-
quinones obtained on energetically nitrating anthraquinone or anthracene, or on
the sulphonic acids of these nitro-anthraquinones in the presence of aromatic
amines (such as aniline, orthotoluidine, paratoluidine, or the like), or salts thereof,
and boric acid, or other boron compounds which, when used with sulphuric acid,
act in a similar manner.
3. As new products of manufacture, the new dye-stuffs produced by the process
hereinbefore defined, or by any other process affording the same result.
Dated this 26th day of March 1895.
NEWTON & SON,
Agents for the Applicant.