The Manufacture or Production of New Anthraquinone Dye-stuffs.
Year: 1897

page_text: [Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH BAYER &
Co., of Elberfeld, Germany.]
The Manufacture or Production of New Anthraquinone Dye-stuffs.
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 that the mono- and the disulphonic acids
of the following two anthraquinone derivatives of the formulæ
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH BAYER &
Co., of Elberfeld, Germany.]
The Manufacture or Production of New Anthraquinone Dye-stuffs.
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 that the mono- and the disulphonic acids
of the following two anthraquinone derivatives of the formulæ
(A.).
OH
OH
CO
(B.)
OH
NH₂
CO
NH₂
CO
NH₂
CO
NH₂
OH
(which contain, in either lateral nucleus, an amido group in the so-called position
para "relatively to an hydroxy group, and of which two derivatives the former (A)
may be termed paradiamido chrysazine, whilst the latter (B) is known as para-
diamido-anthrarufine) represent very valuable blue colouring matters, dyeing
unmordanted wool in acid baths beautiful even and fast shades, and yielding on
chrome-mordanted fibres, greenish-blue shades.
In the production of these new colouring matters, my foreign correspondents may.
proceed either by sulphonating chrysazine or anthrarufine, transforming the
disulpho acids, thus obtained, into the corresponding dinitro derivatives, and finally
acting on these dinitro compounds with reducing agents, as hereinafter described
under Example I; or by treating with sulphonating agents the above defined
diamido-dihydroxyanthraquinones produced in any suitable manner, as is described
under Example II.
By proceeding in the first-named manner, disulphonic acids are obtained, whereas,
in the latter case, monosulphonic acids are produced, if the sulphonation is effected
quietly.
In order to illustrate the different methods of procedure, the following examples
are given, the parts being by weight :-

page_text: are dissolved in 80 parts of fuming sulphuric acid containing 20 per cent. of SO3.
This solution is heated, at about from 100 to 120 degrees Centigrade, until a test
portion, when mixed with water, yields a clear liquid. The solution is then mixed
with 120 parts of a sulphuric acid of 66 degrees Baumé, to which mixture 52 litres
(in case the parts are kilos. by weight) of a mixture of concentrated sulphuric acid
and concentrated nitric acid (the latter containing 10.4 kilos. of pure nitric acid) is
gradually added, the temperature being kept at from 20 to 30 degrees Centigrade.
This reaction mixture is allowed to stand at ordinary temperatures, being stirred
from time to time, until a test portion, previously neutralized by means of sodium
hydroxide, exhibits a pure blue colour after the addition of stannite of sodium. If
this stage is reached, the reaction is finished, and the most part of the dinitro-
chrysazine-disulphonic acid has separated in a chrystalline state. The precipitate
is filtered off by means of an asbestos filter, and dissolved in 1500 parts of hot
water, to which solution 50 parts of potassium chloride are added. On cooling, the
potassium salt of the dinitrochrysazine disulphonic acid crystallizes from this
solution in the form of beautiful yellow crystals, which readily dissolve in water,
with a yellow colour, this colour turning into ruby on the addition of sodiumi
hydroxide, and into orange on adding caustic ammonia to the watery solution.
In order to reduce the dinitro-disulphonic acid obtained as herein before described,
5 parts of the potassium salt are dissolved in 250 parts of water.
To this liquid, a
solution prepared from 12 parts of stannous chloride, 30 litres of water, and 30 litres
(in case the parts are kilos. by weight) of concentrated hydrochloric acid is added,
with stirring. The reduction is effected immediately, the colour of the mixture
turning to blue, and, after a short while, the paradiamido chrysazine disulphonic
acid separates as a gelatinous mass, which, on being heated on a water bath, is
transformed into a precipitate composed of fine needles, which can be filtered,
washed with a small quantity of water, and dried.
In
The dyestuff thus obtained dissolves in water with comparative ease, and is
precipitated from the watery solution on the addition of mineral acids. In
concentrated hydrochloric acid, the dyestuff readily dissolves, producing a yellow
colour, and from this solution it is separated on adding an excess of water.
concentrated sulphuric acid, it dissolves with a yellow colour, which is not changed
on the addition of boric acid. If, however, the dyestuff is heated with a solution
of boric acid in sulphuric monohydrate, a dull violet red solution is obtained, which
exhibits a very characteristic absorption spectrum.
In an analogous manner, the corresponding dye-stuff from anthrarufine can be
obtained. Its properties are very similar to those of the above described colouring
matter, but it can be easily distinguished from the chrysazine derivative by the
following reaction. The yellow colour of the concentrated sulphuric acid solution
of the chrysazine derivative does not change (as before mentioned).on the addition

page_text: of boric at ordinary temperatures, but the yellow colour of the sulphuric acid
solution of the anthrarufine derivative changes into greenish-blue on adding boric
acid, and shews in this state a characteristic absorption spectrum.
My foreign correspondents do not confine themselves to the particulars given in
the above example, as these can be varied within wide limits. Thus, for instance,
instead of stannous chloride, other suitable acid or alkaline reducing agents can be
employed. Naturally, the production of the dye-stuffs can also be effected on the
fibre; for instance, by dyeing wool in acid baths with the dinitrodisulphonic acid of
chrysazine or anthrarufine, and treating the fibres thus impregnated with solutions
of suitable reducing agents.
Owing to the fact that the dye-stuffs obtained in the manner described in the
above example from chrysazine and from anthrarufine exhibit practically the same
properties, one can also employ mixtures of these two bodies in the above process
without altering thereby the result.
OH
CO
NH
CO
OH
NH₂
are heated together with 100 parts of a slightly fuming sulphuric acid (containing
from 1 to 5 per cent. of SO,), at from 100 to 130 degrees Centigrade, until the precipitate
obtained by pouring a test portion of the mixture into water, readily dissolves in a
diluted soda-lye. The mixture is then allowed to cool, and, when cool, it is poured
into water. The violet precipitate thus obtained is filtered and washed by means
of water, until the filtrate shews a neutral reaction. If necessary, the precipitate
can be purified by dissolving in caustic ammonia, or in a hot solution of acetate
of sodium, by subsequently filtering the solution thus obtained, and finally
precipitating the dye-stuff with the aid of acids.
The dye-stuff produced according to this Example II represents, in a dry state,
a dark powder, which, when rubbed, assumes a metallic lustre. It is insoluble in
glacial acetic acid, in alcohol, and in nitro-benzene, easily soluble in pyridine, and
in hot aniline, producing a blue colour. In concentrated sulphuric acid, it
dissolves with a yellow colour, which turns into violet-blue on the addition of boric
acid. In the latter state, this solution shows a characteristic absorption spectrum,
which can hardly be distinguished from that of the boric ether of the
5 paradiamidoanthrarufine. When in a pasty state, the dyestuff is soluble in
caustic ammonia, with a blue colour, soluble in soda-lye with a greenish-blue colour,
and soluble with difficulty in boiling water, with a violet colour.
On unmordanted and mordanted fibres, it yields shades exhibiting properties
very similar to those of the shades obtainable by means of the disulphonic acids
0 produced according to Example I,

page_text: The Manufacture or Production of New Anthraquinone Dye-stuffs.
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 20
particularly described and ascertained in and by the following statement :-
My foreign correspondents have found that the mono- and the disulphonic
acids of the following two anthraquinone derivatives of the formulæ

page_text: .
may proceed either by sulphonating chrysazine or anthrarufine, transforming the
disulpho acids thus obtained into the corresponding dinitro derivatives and finally
acting on these dinitro compounds with reducing agents, as hereinafter described
under Example I, or by treating with sulphonating agents the above defined
diamidodihydroxy-anthraquinones produced in any suitable manner, as described
under Example II.
By proceeding according to Example I, disulphonic acids are obtained, whereas,
according to Example II, monosulphonic acids are produced, if the sulphonation is
effected quietly. A good method of effecting the sulphonation quietly is to cause
the reaction to take place in the presence of boric acid, which body, as is already
described in Letters Patent No. 14345, dated July 25, 1893 (granted to me as a
communication from my foreign correspondents) prevents detrimental by-reactions
in the operation of sulphonating anthraquinone dervatives.
In order to illustrate the different methods of procedure, the following examples
are given, the parts being by weight :-
are dissolved in 80 parts of fuming sulphuric acid, containing 20 per cent. of SO,.
This solution is heated at about from 100 to 120 degrees Centigrade, until a test portion
when mixed with water, yields a clear liquid. The solution is then mixed with
120 parts of a sulphuric acid of 66 degrees Baumé, to which mixture 52 litres (in
case the parts are kilos. by weight) of a mixture of concentrated sulphuric acid and
concentrated nitric acid (containing 10.4 kilos. of pure nitric acid) is gradually
added, keeping the temperature at from 20 to 30 degrees Centigrade. This reaction
mixture is allowed to stand at ordinary temperature (being stirred from time to
time) until a test portion, previously neutralised by means of sodium hydroxide,
exhibits a pure blue color, after the addition of stannite of sodium. If this stage
is reached, the reaction is finished, and the most part of the dinitrochrysazine
disulphonic acid has separated in a crystalline state. The precipitate is filtered off
by means of an asbestos filter, and dissolved in 1500 parts of hot water, to which
solution 50 parts of potassium chloride are added. On cooling the potassium salt
of the dinitrochrysazine, disulphonic acid crystallises from this solution in the form
of beautiful yellow crystals, which readily dissolve in water with a yellow color,
this color turning into ruby on the addition of sodium hydroxide, and into orange
on adding caustic ammonia to the watery solution.
In order to reduce the dinitrodisulphonic acid obtained as herein before described,
5 parts of the potassium salt are dissolved in 250 parts of water. To this liquid, a
solution prepared from 12 parts of stannous chloride, 30 litres of water, and
30 litres (in case the parts are kilos. by weight) of concentrated hydrochloric acid
is added with stirring. The reduction is effected immediately, the color of the
mixture turning to blue, and, after a short while, the paradiamido-chrysazinedi-

page_text: sulphonic acid separates as a gelatinous mass, which, ou being heated on a water
bath, is transformed into a precipitate composed of fine needles, which can be
filtered, washed with a small quantity of water, and dried.
In
The dyestuff thus obtained dissolves in water with comparative ease, and is
precipitated from the watery solution on the addition of mineral acids.
concentrated hydrochloric acid, the dyestuff readily dissolves, producing a yellow
color, and from this solution it is separated on adding an excess of water. It
dissolves in alkalies with a pure greenish-blue color. In concentrated sulphuric
acid it dissolves with a yellow color, which is not changed on the addition of boric
acid. If, however, the dye-stuff is heated with a solution of boric acid in
sulphuric monohydrate, a dull violet-red solution is obtained, which exhibits a
strongly characteristic absorption spectrum.
In an analogous manner, the corresponding dye-stuff from anthrarufine can be
obtained. Its properties are very similar to those of the above described colouring-
matter, but it can be easily distinguished from the chrysazine derivative by the
following reaction. The yellow color of the concentrated sulphuric acid solution of
the chrysazine derivative does not change, as before mentioned, on the addition of
boric acid at ordinary temperatures, but the yellow colour of the sulphuric acid
solution of the anthrarufine derivative changes into greenish-blue on adding boric
acid, and shews, in this state, a characteristic absorption spectrum.
My foreign correspondents do not confine themselves to the particulars given in
the above example, as these can be varied within wide limits. Thus, for instance,
instead of stannous chloride, other suitable acid or alkaline reducing agents can be
employed.
The desired results can be effected 'direct on the fibre; for instance, by dyeing
wool in acid baths with the dinitro-disulphonic acid of chrysazine, or anthrarufine,
and treating the fibres thus impregnated with solutions of suitable reducing agents.
Owing to the fact that the dye-stuffs obtained in the manner described in the
above example from chrysazine and from anthrarufine exhibit practically the same
properties, one can also employ mixtures of these two bodies in the above process,
without altering thereby the result.
(see Berichte der "Deutschen Chemischen Gesellschaft," vol. 29, p. 2937 and
2940), are heated together with 200 parts of fuming sulphuric acid (containing
about 30 per cent. of SO₂) and 10 parts of crystalline boric acid, at from 100 to
130 degrees Centigrade, until the precipitate obtained by pouring a test portion
of the mixture into water readily dissolves in a dilute soda-lye.
The mixture is then allowed to cool, and, when cool, is poured into a large

page_text: quantity of water. The resulting mixture is heated to boiling, and filtered. The
dark violet residue remaining on the filter, which represents the new dyestuff, is
washed by means of water, until the filtrate shews a nentral reaction. If
necessary, the dye-stuff can be purified by dissolving in a dilute ammonia or
sodium carbonate solution, filtering the solution thus obtained, and finally.
precipitating the dye-stuff with the aid of acids.
The dye-stuff produced according to this example, when in a dry state, is a
dark powder, which, on being rubbed, assumes a metallic lustre. It is insoluble
in glacial acetic acid, in alcohol, and in nitrobenzene, easily soluble in pyridine, and
in hot aniline, producing a blue color. In concentrated sulphuric acid, it dissolves
with a yellow color, which turns into violet-blue on the addition of boric acid. In
the latter state, this solution shews a characteristic absorption spectrum, which
can hardly be distinguished from that of the boric ether of the paradiamido
anthrarufine.
When in a pasty state, the dye-stuff is easily soluble in caustic ammonia with a
blue color, soluble in soda lye with a greenish-blue color, and soluble with difficulty
in boiling water with a violet color.
On unmordanted and mordanted fibres, it yields shades exhibiting properties
very similar to those of the shades obtainable by means of the disulphonic
acids produced according to the above Example I.
The analytical researches of my foreign correspondents shew that the dyestuff
has a composition corresponding with the formula.
A body thus composed includes 48 per cent. of carbon, 2.85 per cent. of hydrogen,
8 per cent. of nitrogen, and 9.1 per cent. of sulphur. My foreign correspondents
have found by analysis that samples of the new dye-stuffs actually included 47.86
and 48-10 per cent. of carbon, 3.18 and 3.19 per cent. of hydrogen, 8.43 per cent.
of nitrogen, and 8.94 per cent. of sulphur.
I may here remark that my foreign correspondents do not limit themselves to
the proportions given in Example II, as these can be varied within certain limits.
My foreign correspondents particularly wish to point out that they do not lay
claim to the use, in Example II, of the diamido-dioxyanthraquinone described in
the English Letters Patent No. 9744 granted to me, and in the German Patent
No. 81694, and which, according to recent investigations, represents a mixture of
diamidoanthrarufine with certain other compounds.
If paradiamidochrysazine is employed instead of paradiamido-anthrarufine in
Example II, a result very similar to that described in this example is obtained.
On using mixtures of diamido-anthrarufine and diamido chrysazine, likewise a
similar result is obtained.
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 ine
from abroad), I declare that what I claim is :-
:-
1. The process for producing disulphonic acids of anthrarufine and chrysazine,
by treating the said bodies with sulphonating agents, substantially as hereinbefore
described.
2. Theproduction of disulphonic acids of dinitro-anthrarufine and dinitrochrysazine
by nitrating the disulphonic acids referred to in the foregoing Claim 1, substantially
as hereinbefore described.
3. Producing disulphonic acids of diamidoauthrarufine and diamido-chrysazine

page_text: by treating with suitable reducing agents the dinitro compounds referred to in
Claim 2, either in bulk, or when on the fibre, substantially as described.
4. The manufacture of diamidoanthrarufine disulphonic acid and diamido
chrysazine disulphonic acid, by first sulphonating anthrarufine and chrysazine,
secondly nitrating the disulphonic acids thus obtained, and finally reducing the
resulting dinitro compounds, substantially as hereinbefore described.
5. The use of mixtures of anthrarufine and chrysazine in the processes claimed in
the above Claims 1 and 4.
6. The process for producing diamidoanthrarufine monosulphonic acid and
diamido-chrysazine monosulphonic acid, by sulphonating diamidoanthrarufine and
diamido chrysazine substantially as herein-before described.
7. The use of mixtures of diamidoanthrarufine and diamidoanthrachrysazine in
the process claimed in the preceding Claim 6.
8. As new articles of manufacture, the new intermediate products and dye-stuffs
obtainable as above described.
Dated 1: 14th dow of Wahway 1900