The Manufacture or Production of Colouring Matters Derived from Anthraquinone.
Year: 1894

page_text: Date of Application, 16th Jan., 1894
Complete Specification Left, 12th Oct., 1894-Accepted, 17th Nov., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Colouring Matters Derived from
Anthraquinone.
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 discovered some time since a process for process
for producing dyestuffs, which process consists in heating dinitro-anthraquinone,
the analogues thereof, or sulpho acids of such dinitro compounds, with concentrated
or fuming sulphuric acid, in the presence of boric acid or other substances acting
in the same or a similar manner.
Very valuable dyestuffs, distinguished for the clearness and intensity of the
shades produced therewith, are thus obtained, but the results are not satisfactory,
if boric acid, or the like, are not used; for instance, if dinitroanthraquinone is
heated alone with sulphuric acid. This advantageous action of boric acid, or the
like, is caused by the fact that the boric acid unites with the hydroxyanthra-
quinone colouring matters formed during the process, and that the resulting boric
ethers are capable of withstanding, in a higher degree, the decomposition caused
at elevated temperatures by the oxidasing agents used. But when using boric
acid or the like, the oxidation proceeds to a certain extent, that is to say, until
the valuable colouring matters are formed.
My foreign correspondents have now found, that the dinitroanthraquinone used
in the aforesaid process can be replaced by mononitroanthraquinone, or sulpho
acids thereof, or by mixtures of mononitro- and dinitroanthraquinones, or sulpho
acids thereof, or by other "nitrated derivatives of anthraquinone," or by corre-
sponding amido compounds,-dyestuff's being thus produced which are capable of
dyeing with the aid of mordants.
The colouring matters obtained in the aforesaid manner from mononitro-
anthraquinone, or mixtures of mononitroanthraquinone and dinitroanthraquinone,
or sulpho acids thereof, in general dye shades which are redder than those
produced by means of the dyestuffs from dinitroanthraquinone.
The following example is given, in order to illustrate one of the methods of
producing a dye stuff from mononitroanthraquinone, & my foreign correspondents
describe in this example the conversion of anthraquinone into mononitroanthra-
quinone, and the transformation of the latter into the coloring matter, which
processes can be practically carried out in one operation.

page_text: 200 degrees centigrade, the reaction takes place very satisfactorily.
The
resulting mass, which exhibits a dark red colour, is, after cooling, poured into
water, and the reddish-brown precipitate, which is the dye stuff, is filtered off.
The colouring matter thus obtainable is adapted in an eminent degree for dyeing
cotton. It produces, on wool mordanted with alumina salts, so called "bordeaux
shades with a bluish hue, whilst it yields violet shades with a reddish hue on wool
mordanted with chromium salts.
The 'researches of my foreign correspondents have shewn, that the nitrate of
Foda used in the above example can be replaced by the corresponding quantities
of other nitrates or uitric acid. The degree of concentration of the sulphuric
acid used can vary within wide limits; for instance, monohydrated sulphuric acid
or fuming sulphuric acid can likewise be employed.
On employing mixtures of mononitro and dinitroanthraquinone mixtures of
dyestuffs result in an analogous manner.
The reaction proceeds in a similar manner, if mononitroanthraquinone, or the
mixtures of mononitro- and dinitroanthraquinone, are replaced by the corre-
sponding quantities of sulpho acids thereof.
The process may also be carried out, if, in place of nitrating anthraquinone in
sulphuric acid solution, and converting at once the mononitroanthraquinone into the
dye stuff, with the aid of boric acid, the mononitroanthraquinone is previously
isolated, and subsequently transfor:ned into the colouring matter by means of
boric acid in sulphuric acid solution.
As above mentioned, my foreign correspondents have also found that other
"nitrated derivatives of anthraquinone," or corresponding amido compounds, can
be used with the same result in the aforesaid process, and yield valuable dye-
stuffs, when they are treated with boric acid in sulphuric acid solution.
My foreign correspondents mean by the above expression "nitrated derivatives
of anthraquinone," the following substances, for instance, nitroamidoanthra-
quinoues, such as the products resulting from dinitroanthraquinone, by a partial
reduction, if, for example, dinitroanthraquinones are slowly heated with ammonia
(which process is described in the Specification of the English Letters Patent
No. 21168, dated 21st November 1892), or if dinitroanthraquinones are reduced with
care in acid or alkaline solution, for instance, by means of sodium sulphide, as
described in the Specification of the English Letters Patent No. 13029, dated
15th July 1892; or, nitrohydroxyanthraquinones, for instance, mononitrohydroxy-
anthraquinone; or dinitroanthrachrysone, or tetranitroanthrachrysone, or nitro-
derivatives of anthrarufin and methylanthraquinone.
Other analogous or similar nitro-derivatives of anthraquinones, however, can
also be used in this process.
The researches of my foreign correspondents have further shewn, that in place
of the above defined nitro products, the corresponding amido compounds can
likewise be used, viz., such amido products as result from the nitro compounds by
reduction; for instance, diamidoanthraquinones, such as di-ortho-amidoanthra-
quinone (15), or the like, amidohydroxyanthraquinones, obtainable by reducing
nitrohydroxyanthraquinones, such as the product resulting by reducing the
aforesaid mononitrohydroxyanthraquinone, or diamiodihydroxyanthraquinones, for
instance, the diamidodihydroxyanthraquinone which my foreign correspondents
have first prepared by reducing diortho-nitroanthraquinone in alkaline solution,
and subsequently treating the first formed intermediate product, soluble in
alkali, with concentrated acids, in order to effect its conversion into the said
diamidodihydroxyanthraquinone.
Of course, the sulpho acids or other derivatives of such nitro amidoanthra-
quinones, nitrohydroxyanthraquinones, amidoanthraquinones, or amidohydroxy-
anthraquinones, can also be used; for instance, the dinitroanthrachrysone disulpho
acid.
According to the researches of my foreign correspondents, the conversion of the
authraquinone compounds into nitro-derivatives (employing concentrated sulphuric

page_text: acid as solvent), and the transformation of these nitro products into dye stuffs,
with the addition of boric acid, can be carried out in one operation.
The process in general is analogous to that described in the foregoing
Example A, and consists in heating the respective compounds with concentrated
or fuming sulphuric acid, and boric acid, until the formation of dye begins. The
reaction is complete within a comparatively short time.
On employing amido compounds in place of nitro products, the process is in
general carried out at higher temperatures (say, at from 250 to 300 degrees
centigrade).
Dyestuffs yielding somewhat redder shades than those produced by means of
the dye-stuffs obtainable with the aid of stronger acids (monohydrated sulphuric
acid, or weakly fuming sulphuric acid) result, if concentrated sulphuric acid, at
from 60 to 66 degrees Baumé, be used. In case of the use of stronger acids, the
reaction mostly proceeds at somewhat lower temperatures, but the peculiar and
profitable action of the boric acid is distinguished, whenever the conditions are
altered.
The following examples are given, in order to illustrate some methods of
converting the above-defined "nitrated derivatives of anthraquinone," or the
corresponding amido compounds, into dye-stuffs. The parts are by weight.
DYE-STUFF OBTAINED FROM NITROAMIDOANTHRAQUINONE AND CONCENTRATED
SULPHURIC ACID, IN THE PRESENCE OF BORIC ACID.
10 parts of nitroamidoanthraquinone are mixed with 10 parts of crystallised
boric acid & 200 parts of sulphuric acid (66 degrees Baumé), and the resulting
mixture is heated at from 200 to 220 degrees centigrade, until the mass has
assumed a deep bluish-violet colour. and reaction is no longer apparent. After
cooling, the mass is poured into 2,000 parts of water, and the resulting liquid is
boiled up. The dyestuff which separates is filtered off, and exhibits properties
essentially the same as the colouring matter obtainable from dinitroanthraquinone
by heating with concentrated sulphuric acid in the presence of boric acid, and, as
in the last named dye stuff, contains much hexaoxyanthraquinone, and variable
proportions of hydroxyanthraquinone colouring matters containing nitrogen,
which proportions depend on the degree of concentration of the sulphuric acid
used.
BY
PRESENCE or
COLOURING MATTER OBTAINED FROM TETRANITROANTHRACHRYSONE
MEANS OF CONCENTRATED SULPHURIC ACID, IN THE
BORIC ACID.
If. in the foregoing Example B, nitroamidoanthraquinone is replaced by
tetranitroanthrachrysone, a dyestuff results which dissolves in soda-lye, producing
a violet coloured liquid, & in concentrated sulphuric acid also, yielding a violet
coloured liquid, which, however, does not exhibit a distinct absorption spectrum.
It produces intense blackish-blue shades with the aid of chrome mordants.
5 DYE-STUFF OBTAINED FROM DI-ORTHO-AMIDO-ANTHRAQUINONE, BY MEANS
OF CONCENTRATED SULPHURIC ACID, IN THE PRESENCE OF BORIC ACID.
10 parts of di-ortho-amido-anthraquinone are mixed with 10 parts of crystallised
boric acid and 200 parts of sulphuric acid (66 degrees Baumié). The resulting
mixture is heated at from 260 to 270 degrees centigrade. The reaction, which

page_text: almost immediately begins, whilst sulphur dioxide is disengaged and the mass
assumes a blue colour, is completed in within a short time. When this stage is
arrived at, the mass, when cooled, is poured into water, and the separated precipitate
is filtered off.
.It is dissolved in boiling diluted soda-lye, and the resulting solution is filtered, in
order to remove a slight quantity of a product insoluble in alkalies, and possessing
but a slight dyeing power, and the small proportion of diamido-anthraquinone
unaltered. The dye-stuff is precipitated by adding any acid to the filtrate, and the
precipitate is filtered off.
This colouring-matter dissolves in soda-lye, producing a bluish-violet coloured
solution, whilst its solution in concentrated sulphuric acid exhibits a red colour,
with strong brownish-red fluorescence, and yields an absorption spectrum which is
very similar to that of hexaoxyanthraquinone. It produces pure blue shades with
the aid of chrome mordants.
In order to produce the dye-stuffs from the above defined "nitrated derivatives
of anthraquinone," or from corresponding amido derivatives of anthraquinone or
the like, my foreign correspondents do not limit themselves to the directions given
in the above Examples B, C, and D, as the methods of producing these colouring-
matters can be varied. For instance, the degree of concentration of the sulphuric
acid used can vary within certain limits, the concentrated sulphuric acid can be
replaced by fuming sulphuric acid; and the temperature can vary within wide
limits, according as the sulphuric acid possesses a higher or lower degree of
concentration. The boric acid can be replaced, in all cases, by such boron
compounds (for instance, salts of boric acid, boron trichloride, or the like), as yield
boric acid in the presence of sulphuric acid.
Dated this 16th day of January 1894.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Colouring Matters Derived from
Anthraquinone.
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, which process
consists in allowing sulphuric acid to act, in the presence of boric acid or other
boron compounds (which, when used together with sulphuric acid, act in a similar
manner) on diorthonitroanthraquinone, or isomeric dinitroanthraquinones, or the
crude mixture of nitroanthraquinones obtained on energetically. nitrating anthra-
quinone or anthracene, or on the sulphonic acids of these nitroanthraquinones.
My foreign correspondents have now found that the dinitroanthraquinone used
in the process described in the aforesaid Specification of Letters Patent No. 14345
of 1893, can be replaced by mononitroanthraquinone, or sulphonic acids thereof, or
by mixtures of mononitro and dinitroanthraquinones, or sulphonic acids thereof, or
by "other nitrated derivatives of anthraquinoue," or by the corresponding amido
compounds, dye-stuffs being thus produced which are capable of dyeing with the
aid of mordants.
The colouring matters obtained in the aforesaid manner from mononitroanthra-
quinone produce, on mordanted material, shades which are much redder than those
produced by the dye-stuffs from dinitroanthraquinone.
The following example is given in order to illustrate one of the methods of

page_text: producing a dye-stuff from mononitroanthraquinone, and my foreign correspondents
describe, in this example, both the conversion of anthraquinone into mononitro-
anthraquinone, and the transformation of the latter into the colouring matter, which
processes are profitably carried out in one operation.
DYE-STUFF OBTAINED FROM MONONITROANTHRAQUINONE
BY MEANS OF
SULPHURIC ACID IN THE PRESENCE OF BORIC ACID.
10 parts (the parts are by weight) of anthraquinone are dissolved in 200 parts of
sulphuric acid (66 degrees Baume), and 4.2 parts of dry nitrate of soda having been
introduced into the acid solution, the mixture is heated during from 1 to 2 hours
at from 60 to 80 degrees centigrade. The liquid containing chiefly mononitro-
anthraquinone is then mixed with 5 parts of crystallised boric acid. On further
heating, during from 1 to 2 hours, at from 190 to 200 degrees centigrade, the action
takes place very satisfactorily. When cool, the resulting dark red colored mass
is poured into water, and the reddish-brown precipitate of the dye-stuff is
filtered off.
The coloring-matter thus obtainable dissolves in solutions of sodium carbonate,
producing a yellowish-red colored liquid, in ammonia producing a bluish-red colored
solution, in soda-lye producing a violet-red coloured solution, and in concentrated
sulphuric acid producing a reddish-brown coloured solution, which exhibits a
reddish-brown fluorescence. On wool mordanted with alumina mordants, it
produces claret shades of a bluish-hue, and on wool mordanted with chromium salts,
reddish-violet shades.
The researches of my foreign correspondents have shown, that instead of nitrate
of soda in the above example, corresponding quantities of other nitrates or nitric
acid can be used. The degree of concentration of the sulphuric acid used can also
be varied within wide limits, for instance, monohydrated sulphuric acid or fuming
sulphuric acid can be used.
On using mixtures of mononitro and dinitro anthraquinone, corresponding
mixtures of dye-stuffs are formed in an analogous manner.
i
The action proceeds in a similar manner, if, in place of mononitroanthraquinone,
or mixtures of mononitro and dinitro anthraquinone, the corresponding quantities
of sulphonic acids thereof are used.
The process may also be carried out, if, instead of nitrating anthraquinone in
sulphuric acid solution, and at once converting the mononitroanthraquinone into the
dye-stuff with the aid of boric acid, the mononitroanthraquinone is previously
isolated, and subsequently transformed into the colouring matter, by means of boric
acid, in sulphuric acid solution.
The use of the nitroanthraquinones and nitroanthraquinone sulphonic acids used
in the process described and claimed in the Specification of Letters Patent No. 14345,
dated 25 July 1893, is hereby disclaimed.
As above mentioned, my foreign correspondents have also found that other
"nitrated derivatives of anthraquinone," or corresponding amido compounds, can
be used with the same result, in the aforesaid process, yielding valuable dye-stuffs
when they are treated with boric acid or the like in sulphuric acid solution.
My foreign correspondents mean by the above expression " nitrated derivatives
of anthraquinone," the following substances, for instance, nitroamidoanthraquinones,
such as the products obtained from dinitroanthraquinone by partial reduction, if,
for example, dinitroanthraquinones are slowly heated with ammonia (which process
is described in the Specification of the English Letters Patent No. 21168, dated
21st November 1892), or if dinitroanthraquinones are carefully reduced in acid
or alkaline solution, for instance, by means of sodium sulphide, as described in the
Specification of the English Letters Patent No. 13029, dated 15th July 1892; or
nitrobydroxyanthraquinones, for instance, mononitrohydroxyanthraquinone described

page_text: in the Specification of the German Patent No. 73860, dated 2nd April 1893, or
dinitroanthrachrysone described in the Specification of the German Patent
No. 71946, dated 14th January 1893, or tetranitroanthrachrysone described in the
Specification of Letters Patent No. 22443, dated 7th December 1892; or nitro
derivatives of anthrarufin and methylanthraquinone.
Other analogous or similar nitro derivatives of anthraquinones, however, can also
be used in this process.
The researches of my foreign correspondents have further shown, that in place
of the above defined nitro derivatives, the corresponding amido compounds can also
be used, viz., such amido products as are formed from the nitro compounds by
reduction, for instance, diamido anthraquinones, such as di-ortho-amido anthra-
quinone (1.5), or the like, amidohydroxyanthraquinones, obtainable by reducing
nitrohydroxyanthraquinones, such as the product formed on reducing the mono-
nitrohydroxyanthraquinone described in the aforesaid German Patent No. 73860,
or diamidodihydroxyanthraquinones, for instance, the diamido dihydroxyanthra-
quinone which my foreign correspondents have first prepared by reducing diortho-
nitroanthraquinone in alkaline solution, and subsequently treating the intermediate
product, soluble in alkali, which is first formed, with concentrated acids, in order to
effect its conversion into the said diamidodihydroxyanthraquinone.
As a matter of course, the sulphonic acids of such nitroamidoanthraquinones,
nitrohydroxyanthraquinones, amidoanthraquinones or amidohydroxyanthraquinones,
can also be used, for instance, the dinitroanthrachrysone disulpho acid which is
afforded by the process described in the German Patent No. 70806.
According to the researches of my foreign correspondents, the conversion of the
anthraquinone compounds into nitro derivatives (using concentrated sulphuric acid
as solvent), and the transformation of these nitro products into dye-stuffs in
presence of boric acid, can be profitably carried out in one operation.
The process of converting the above defined nitrated derivatives of anthra-
quinone, and the corresponding amido products, into dye-stuffs, is, in general,
analogous to that described in the foregoing first example, and consists in heating
the respective compounds with concentrated or fuming sulphuric acid and boric
acid, until the formation of dye begins. The action is then complete within a
comparatively short time.
On using the corresponding amido compounds in place of nitro compounds, the
process is in general carried out at higher temperatures (say, at from 250 to
300 degrees centigrade).
Dye-stuffs yielding somewhat redder shades than those produced by means of
the dye-stuffs obtainable with the aid of stronger acids (monohydrated sulphuric
acid, or weakly fuming sulphuric acid) are formed if concentrated sulphuric acid,
from 60 to 66 degrees Baume, be used. When stronger acids are used, the action,
-as a rule, takes place at somewhat lower temperatures, but the peculiar and
favourable action of the boric acid becomes apparent, whenever the conditions are
altered.
The following examples are given, in order to illustrate several methods of
converting the above defined "nitrated derivatives of anthraquinone," or the
corresponding amido compounds, into dye-stuffs. The parts are by weight.
DYE-STUFF OBTAINED FROM NITRO AMIDO ANTHRAQUINONE AND CONCEN-
TRATED SULPHURIC ACID IN THE PRESENCE OF BORIC ACID.
10 parts of nitro amido anthraquinone are mixed with 10 parts of crystallized 5
boric acid and 200 parts of sulphuric acid (66 degrees Beaume), and the mixture is
heated at from 200 to 220 degrees centigrade, until the mass has assumed a deep
bluish violet colour, and the action is apparently at an end. The cool mass is
poured into 2000 parts of water, and the liquid is then boiled. The dye-stuff

page_text: which separates is filtered off, and exhibits properties essentially the same as those
of the colouring matter obtainable from dinitroanthraquinone by means of the
process described in the Specification of the aforesaid Letters Patent No. 14345",
and, like the last-named dye-stuff, contains much hexahydroxyanthraquinone, and
variable proportions of hydroxyanthraquinone colouring matters containing
nitrogen, which proportions depend on the degree of concentration of the sulphuric.
acid used.
COLOURING MATTER OBTAINED FROM TETRANITROANTHRACHRYSONE BY
MEANS OF CONCENTRATED SULPHURIC ACID IN THE PRESENCE (F
BORIC ACID.
If, in the foregoing second example, nitroamidoanthraquinone is replaced by
tetranitroanthrachrysone, a dye-stuff is formed which dissolves in soda-lye,
producing a violet coloured liquid, and in concentrated sulphuric acid also yielding
a violet coloured liquid, which, however, does not exhibit a distinct absorption
spectrum. It produces intense blackish-blue shades on wool mordanted with
chromium salts.
DYE-STUFF OBTAINED FROM DI-ORTHO-AMIDO-ANTHRAQUINONE
BY MEANS
OF CONCENTRATED SULPHURIC ACID IN THE PRESENCE OF BORIC ACID.
10 parts of di-ortho-amido-anthraquinone are mixed with 10 parts of crystallised
boric acid, and 200 parts of sulphuric acid (66 degrees Baumé). The mixture is
heated at from 260 to 270 degrees centigrade. An action begins almost
immediately, sulphur dioxide being disengaged, the mass assuming a blue colour.
Wheu, after a short time, this stage is arrived at, the cooled mass is poured into
water and the precipitate is filtered off. It is dissolved in boiling diluted soda lye,
and the solution is filtered in order to remove a small quantity of a product
insoluble in alkalies, possessing but slight dyeing power, and a small proportion of
unaltered diamidoanthraquinone. The dye-stuff is precipitated by adding any
acid to the filtrate, and the precipitate is filtered off.
This colouring matter dissolves in soda lye, producing a bluish violet_coloured
solution, whilst its solution in concentrated sulphuric acid exhibits a red colour,
and a strong brownish-red fluorescence, the absorption spectrum of this solution
being very similar to that of hexahydroxyanthraquinone. The colouring matter
thus obtained produces pure blue shades on wool mordanted with chromium salts.
In order to produce the dye-stuffs from the above defined "nitrated derivatives
of anthraquinone," or from corresponding amido derivatives of anthraquinone or
the like, my foreign correspondents do not limit themselves to the directions given
in the above examples, as the methods of producing these colouring matters can be
varied. For instance, the degree of concentration of the sulphuric acid can be
varied within certain limits, and instead of concentrated sulphuric acid, moderately
fuming acid can be used; the temperature can also be varied within wide limits,
according as the sulphuric acid is of a higher or lower degree of concentration.
Instead of boric acid, any boron compounds (for instance, salts of boric acid,
boron trichloride, or the like) can be used which, in presence of sulphuric acid,
yield boric acid.
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 by
my foreign correspondents, I declare that what I claim is :-
1. The process for producing dye-stuffs capable of dyeing with the aid of
mordants, which process consists in causing concentrated monohydrated or fuming

page_text: sulphuric acid, together with boric acid or other boron compounds yielding boric
acid when used together with sulphuric acid, to act at elevated temperatures on
the following products, viz., mononitroanthraquinone, mixtures of mono and dinitro-
anthraquinone, or sulphonic acids thereof; or nitro amido anthraquinones, nitro
hydroxyanthraquinones, amidoanthraquinones, amido hydroxyanthraquinones, or
sulphonic acids thereof. (The use of the nitroanthraquinones, or nitroanthra-
quinon sulphonic acids, used in the process described and claimed in the
Specification of Letters Patent No. 14345, dated 25th July 1893, is hereby
disclaimed.)
2. As new products of manufacture, the new colouring matters produced by the
process hereinbefore defined, or by any other process affording the same result.
Dated this 11th day of October 1894.
NEWTON & SON,
Agents for the Applicant.
NEWTON & SON,
Agents for the Applicant.