The Manufacture or Production of New Anthraquinone Dye-stuffs.
Year: 1899

page_text: Date of Application, 1st Dec., 1899
Complete Specification Left, 28th Aug., 1900-Accepted, 20th Oct., 1900
The Manufacture or Production of New Anthraquinone Dye-stuffs.
Communicated from abroad by THE FARBENFABRIKEN VORMALS FRIEDRICH
BAYER & Co., of Elberfeld, Germany.
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 amido anthraquinones, and
derivatives thereof, as, e.g., the amido-anthraquinones sulphonic acids, the amido
oxyanthraquinones, and their sulphonic acids, readily react with formic aldehyde
and sulphites, probably a methylsulphonic group being introduced into the amido
groups. The products thus obtained are acid dyestuffs of great power, which dye
wool, in acid baths, from red to greenish-blue shades.
The said reaction takes place probably as follows: into each amido group, a
methyl sulphonic group is introduced. So, e.g., the 1.5 diamido-anthraquinone
yields a sulphonic acid having probably the formula-
The process for producing the said dye-stuffs, in general, consists in treating
the above defined starting materials, in a suitable manner, with a watery solution
of formic aldehyde, and sulphites or bi-sulphites, profitably in the presence of
a small quantity of hydrochlorie or sulphuric acid, at ordinary cr higher tem-
peratures.
In order to illustrate the process more fully, the following examples are given,
the parts being by weight.
EXAMPLE A.
A mixture prepared from 100 parts of a 10 per cent. paste of 1-5-diamido-
anthraquinone, 300 parts of water, 10 parts of a 40 per cent. formic aldehyde
solution, 20 parts of a 40 per cent. sodium bisulphite solution, and 40 parts of a
33 per cent. fuming hydrochloric acid, is heated with continuous stirring at about
from 50 to 60 degrees Centigrade, until the diamidoanthraquinone has dissolved

page_text: almost entirely with a red color. Subsequently the liquid is filtered. From the
filtrate, the new dye-stuff is precipitated by the addition of common salt, filtered
off, pressed, and dried.
The product thus obtained is a brownish-red powder, which, in contradistinc-
tion with 1-5-diamidoanthraquinone, is readily soluble in water, yielding a red
solution, and dyes unmordanted wool, in acid baths, fine blueish-red shades fast
to alkali. It dissolves in concentrated sulphuric acid with an intense blue color,
in contradistinction with 1-5-diamidoanthraquinone, which dissolves in sulphuric
acid with a yellow color. On being heated with strong mineral acids, the com-
pound is split up, 1-5-diamidoanthraquinone being regenerated.
According to analytical researches, the new compound has most probably the
following formula:
The process proceeds in an analogous manner if, instead of the above used
1-5-diamidoanthraquinone, 1-8 or 1-7 diamidoanthraquinones, or other amido-
anthraquinones, or sulphonic acids of the amido compounds, are employed.
EXAMPLE B.
If para-diamidoanthrarufin is treated in the same manner as described in the
Example A, until a test portion clearly dissolves in caustic soda-lye with a.
greenish blue color, a dye-stuff is produced which is difficulty soluble in cold
water, and more soluble in hot water. The new compound differs from the para-
diamidoanthrarufin by being readily soluble in alkalies with a beautiful greenish-
blue color, and by dyeing unmordanted wool, in acid baths, fine and clear blue
shades. The process proceeds in an analogous manner if, instead of the para-
diamidoanthrarufin, other of the above defined compounds are used, such, for
instance, as diamidoanthrarufin monosulphonic acid, para-diamidochrysazin, and
its mono- or disulphonic acid, or the like.
Also, the known mixtures of dye stuffs containing the isomer diamidodioxy-
anthraquinonemonosulphonic acids can be employed.
These mixtures are
obtained by heating dinitro-anthraquinone with sulphur and fuming sulphuric
acid (containing from 10 to 30 per cent. of SO3), with or without the presence of
boric acid.
EXAMPLE C.
A mixture prepared from 100 parts of a watery paste of diamidoanthrarufin-
disulphonic acid (containing 20 per cent. of this acid) see Letters Patent
No. 120117, 15 parts of a 40 per cent. formic aldehyde solution, and 20 parts of
a 40 per cent. sodium bi-sulphite solution, is stirred, for a short while, at above
50 degrees Centigrade, until the reaction mixture is transformed into a pure
greenish-blue and clear solution. On mixing this solution with an excess of a
40 per cent. sodium bisulphite solution, and allowing the same to stand for a while
at ordinary temperature, a dark blue crystalline precipitate is separated there-
from, which is filtered off, dried, and pulverized.
The dark-blue powder thus obtained represents the new dve-stuff. From the
diamidoanthrarufin-disulphonic acid, the new coloring matter is distinguished
by the following reactions. It is soluble in cold water with much greater readiness
than the said acid. Whilst the diamidoanthrarufindisulphonic acid dissolves in
water with a pure blue color, and is precipitated from this solution by the addi-
tion of strong hydrochloric acid (the color of the solution being at the same time
changed into violet), the watery solution of the new dye-stuff is greener, and
exhibits no considerable change by the addition of hydrochloric acid.
A mixture prepared from 100 parts of a watery paste of diamidoanthrarufin-
disulphonic acid (containing 20 per cent. of this acid) see Letters Patent
No. 120117, 15 parts of a 40 per cent. formic aldehyde solution, and 20 parts of
a 40 per cent. sodium bi-sulphite solution, is stirred, for a short while, at above
50 degrees Centigrade, until the reaction mixture is transformed into a pure
greenish-blue and clear solution. On mixing this solution with an excess of a
40 per cent. sodium bisulphite solution, and allowing the same to stand for a while
at ordinary temperature, a dark blue crystalline precipitate is separated there-
from, which is filtered off, dried, and pulverized.
The dark-blue powder thus obtained represents the new dve-stuff. From the
diamidoanthrarufin-disulphonic acid, the new coloring matter is distinguished
by the following reactions. It is soluble in cold water with much greater readiness
than the said acid. Whilst the diamidoanthrarufindisulphonic acid dissolves in
water with a pure blue color, and is precipitated from this solution by the addi-
tion of strong hydrochloric acid (the color of the solution being at the same time
changed into violet), the watery solution of the new dye-stuff is greener, and
exhibits no considerable change by the addition of hydrochloric acid.

page_text: The shades obtained on unmordanted wool, in acid-baths, by means of the new
dye-stuff, are very bright, and a greener blue than those producible with the aid
of diamido-anthrarufin disulphonic acid.
When heated with a 15 per cent. hydrochloric acid, the new dye-stuff is split
up, diamido-anthrarufin-disulphonic acid being separated.
By concentrated sulphuric acid, the new coloring matter is dissolved with a
yellow color, which is changed into greenish-blue on the addition of boric acid.
The absorption spectrum of this greenish-blue solution is identical with that of
the boric ethers of the diamido anthrarufin disulphonic acid.
As a matter of course, my foreign correspondents do not intend to confine them-
selves to the particulars given in the above examples, as these are merely typical,
and can be varied within wide limits.
Dated this lot dove of Donember 1800
NEWTON & SON,
Agents for the Applicant.
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
particularly described and ascertained in and by the following statement:-
My foreign correspondents have found that the amido anthraquinones, and
derivatives thereof as for example the amidoanthraquinonesulphonic acids, the
amidooxvanthraquinones and their sulphonic acids readily react with formic
aldehyde and sulphites probably a methylsulponic group being introduced into
the amido groups. The products thus obtained are acid dyestuffs of great power
which dye wool in acid baths from red to greenish-blue shades.
The said reaction takes places probably as follows: into each amido group a
methylsulphonic group is introduced. Thus for example the 1.5-diamido-anthra-
quinone yields a sulphonic acid having probably the formula:
The process for producing the said dye-stuffs in general consists in treating
the above defined starting materials in a suitable manner with a watery solution
of formic aldehyde and sulphites or bi-sulphites profitably in the presence of
a small quantity of hydrochloric or sulphuric acid at ordinary or higher tem-
peratures.
In order to illustrate the process more fully the following examples are given,
the parts being by weight.

page_text: EXAMPLE A.
A mixture prepared from 100 parts of a 10 per cent, paste of 1-5 diamido-
anthraquinone, 300 parts of water, 10 parts of a 40 per cent. formic aldehyde
solution, 20 parts of a .40 per cent, sodium bisulphite solution and 40 parts of a
33 per cent. fuming hydrochloric acid, is heated with continuous stirring at about
from 50 to 60 degrees Centigrade until the diamidoanthraquinone has dissolved
almost entirely, with a red color. Subsequently the liquid is filtered. From the
filtrate the new dye-stuff is precipitated by the addition of common salt, filtered
off, pressed and dried.
The product thus obtained is a brownish-red powder which in contradistinction
to 1-5 diamidoanthraquinone is readily soluble in water yielding a red solution and
dyes unmordanted wool in acid baths fine, blueish-red shades fast to alkali. It
dissolves in concentrated sulphuric acid with an intense blue color in contradis-
tinction to 1.5-diamido anthraquinone, which dissolves in sulphuric acid with a
yellow color. On being heated with strong mineral acids the compound is split
up. 1.5-diamidoanthraquinone being regenerated.
According to analytical researches the new compound has most probably the
following formula:
The process proceeds in an analogous manner if instead of the 1.5-diamido-
anthraquinone 1.8 or 1.7-diamidoanthraquinones or other amidoanthraquinones
or sulphonic acids of these amido compounds are employed.
EXAMPLE B.
If para-diamido anthrarufine is treated in the same manner as described in
Example A, until a test portion dissolved in caustic soda lye gives a clear solu-
tion with a greenish-blue color, a dye stuff is produced which is soluble with
difficulty in cold water but more soluble in hot water. The new compound
differs from the para-diamido-anthrarufine by reason of its ready solubility in
alkalies with a beautiful greenish-blue color and of its capacity for dyeing un-
mordanted wool in acid baths fine and clear blue shades. The process proceeds
in an analogous manner if instead of the para-diamidoanthrarufine other of the
above defined compounds are used such for instance as diamidoanthrarufine mono-
sulphonic acid, para-diamidochrysazine and its mono or disulphonic acid, or the
like.
The known mixtures of dye-stuffs containing the isomeric diamidodioxyanthra-
quinonemonosulphonic acids can also be employed. These mixtures are obtained
by heating dinitro anthraquinone with sulphur and fuming sulphuric acid (con-
taining from 10 to 30 per cent. of SO3) with or without the presence of boric acid.
EXAMPLE C.
A mixture prepared from 100 parts of a watery paste of diamido anthrarufine
disulphonic acid (containing 20 per cent. of this acid), see Letters Patent
No. 120117, 15 parts of a 40 per cent. formic aldehyde solution and 20 parts of a
40 per cent. sodium bisulphite solution is stirred for a short while at about
50 degrees Centigrade until the reaction mixture is transformed into a pure
greenish blue clear solution. On mixing this solution with an excess of a
40 per cent. sodium bisulphite solution and allowing the same to stand for a
while at ordinary temperature a dark blue crystalline precipitate is separated
therefrom which is filtered off and dried and pulverized.
The dark blue powder thus obtained represents the new dve-stuff. The new

page_text: coloring matter is distinguished from the diamido anthrarufine disulphonic acid
by the following reactions. It is soluble in cold water with much greater readi-
ness than the said acid. Whilst the diamidoanthrarufinedisulphonic acid dis-
solves in water with a pure blue color and is precipitated from this solution by
the addition of strong hydrochloric acid (the color of the solution being at the
same time changed into violet), the watery solution of the new dye-stuff is
greener and exhibits no considerable change on the addition of hydrochloric acid.
The shades obtained on unmordanted wool in acid baths by means of the new
dye-stuff are very bright and are more greenish-blue than those producible with
the aid of diamidoanthrarufine disulphonic acid.
When heated with a 15 per cent. hydrochloric acid the new dye-stuff is split up,
diamido-anthrarufine disulphonic acid being separated.
By concentrated sulphuric acid the new coloring matter is dissolved with a
yellow color which is changed into greenish-blue on the addition of boric acid.
The absorption spectrum of this greenish-blue solution is identical with that
of the boric ether of the diamidoanthrarufinedisulphonic acid.
As a matter of course my foreign correspondents do not intend to confine them-
selves to the particulars given in the above examples, as these are merely typical
and can be varied within wide limits.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, as communicated to
me from abroad, I declare that what I claim is:-
1. The process for the production of new dye-stuffs of the anthracene series
which process consists in treating with formic aldehyde in the presence of sul-
phurous acid or its salts amidoanthraquinones or derivatives thereof, such as
amido-anthraquinones, amidoanthraquinone sulphonic acids, amidooxyanthra-
quinones, amidooxyanthraquinone sulphonic acids, or the like, substantially as
hereinbefore described.
2. As new articles of manufacture the products obtainable by the process
hereinbefore described and claimed.