Improvements in the Manufacture of Azo Dyes.
Year: 1887

page_text: Date of Application, 30th Nov., 1887
Complete Left, 20th June, 1888
Complete Accepted, 20th July, 1888
Improvements in the Manufacture of Azo Dyes.
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex'
Gentleman do hereby declare the nature of this Invention which has been communi-
cated to me from abroad by the Farbenfabriken vormals Friedrich Bayer & Co. of
Elberfeld in the Empire of Germany to be as follows:-
The present Invention has for its object the manufacture or production of dyes or
dyestuffs of from yellow to brown red colour which dye cotton directly without a
mordant in an alkaline bath. The dye known in commerce as Chrysoidine combines
with Diazo compounds of Amides and their Sulpho Acids to form yellow to yellow
red dyes which dye cotton with the aid of tannin and tartar emetic or wool in an acid
bath. My foreign Correspondents have now discovered that this Chrysoidine can be
readily combined with Tetrazo compounds of diamine to form new dyes of from
yellow to brown red tint. These dyes differ advantageously from those derived from
the Diazo compounds inasmuch as they are capable of dyeing cotton in an alkaline
bath without a mordant and dye wool in an alkaline and neutral as well as in an
acid bath.
Dyes of the same colour and possessing the same properties as the above mentioned
are also obtained when in place of the Chrysoidine, the dies known as Bismarch
brown, Vesuvine, phenylene brown (Triamido-azobenzene) are employed.
The last mentioned dyes present great practical advantages over those derived from
Chrysoidine. The property of dyeing unmordanted cotton directly in an alkaline
bath and wool in an alkaline and neutral bath as well as in an acid bath is possessed
by the dyes resulting from the Diazo compounds as well as by those derived from
Tetrazo compounds.
Chrysoidine as well as the Bismarck brown compared with Tetrazo compounds
present the same qualities as ordinary Amides they are capable of readily forming
intermediate compounds which owing to the presence of a free diazo group produce
mixed dyes by acting upon amides phenoles etc.
On the other hand from these intermediate products which are not dyes in
themselves it is possible to obtain direct acting dyes by converting the free Diazo
group into the Hydroxylgroup OH by boiling with water.
The process for producing the dye from Bismarch brown and Chrysoidine with
Tetrazo compounds consists generally in mixing with or adding to an aqueous solution
of the aforesaid dye a corresponding quantity of a Tetrazo compound with the
addition of acetate of Soda

page_text: The dyes obtained from Bismarck brown and Diazo compounds are formed after
standing for about twelve hours in a hydrochloric solution, neutralising with soda and
boiling the dye solution and are then salted out.
Those Diazo or Tetrazo compounds which do not contain any sulpho or Carbo acid
group yield dyes which are soluble in spirit and which can be rendered soluble in
water by means of sulphuric acid. In Amides those which have been found suitable
for forming direct acting dyes with Bismarck brown are Aniline, Toluidine, Xylidine,
Cumidine and their nitro derivatives and amido azo Benzene, amido azo tolnol, amido
azo xytol, Alpha and Beta naphthylamine and the. Sulpho and Carbo acids thereof.
In Tetrazo compounds for Bismarck brown and Chrysoidine the compounds of
Benzidine, Tolidine, Diainido-stilbene Diamido-fluorene, Diamido-azo-benzene and the
Sulpho and Carbo acids thereof are employed.
According to this Invention yellow and reddish brown direct acting azo dyes or
dyestuffs are obtained by the action of the diazo compounds of aniline, Tolidine,
Xylidine, Cumidine amido azo benzene amido azo tolnol, alpha and beta naphthylamine
and their Sulpho and Carbo acids upon Bismarck brown or vesuvine (Triamido-azo-
benzene) and also by the action of the Tetrazo compounds of Benzidine, Benzidine
Sulphone, Tolidine Diamido stilbene and their sulpho and Carbo acids upon two
molecules of Chrysoidine and Bismarch brown. Intermediate products of the
aforesaid Tetrazo compounds are also produced with one molecule of chrysoidine and
Bismarch brown which contain a free diazo group and are capable of acting upon one
molecule of an amide, phenole or their sulpho or carbo acids to produce mixed yellow
to reddish brown direct acting dyes.
The operations hereinafter described are given merely as examples of the preparation
of these new dyes.
1. Dyes prepared from Benzidine and Chrysoidine.
About ten parts by weight of the Chrysoidine obtained from Diazo benzene Chloride
and meta phenylene diamine are dissolved in water and mixed with a Tetrazo diphenyl
solution obtained by known means from about nine parts by weight of benzidine
Sulphate. On the addition of acetate of soda a reddish brown precipitate is obtained
which is insoluble in water. This deposit is separated by filtration and dried. When
absolutely dry the product is treated with fuming sulphuric acid and is thereby
rendered. soluble in water.
2. Dyes prepared from Benzidine sulpho acid and Chrysoidine.
When a Benzidine disulpho acid is employed in place of the Benzidine used in the
preceding example a dye is obtained which is directly soluble in water.
3. Dyes prepared from Bismarck brown and alpha naphthionic acid.
About one hundred parts by weight of pure Bismarck brown, pure Triamido-azo-
benzene, are dissolved in water and mixed with the Diazo compound of about eight
and a half parts by weight of alpha naphthylamine sulpho acid.
After standing for about twelve hours soda is added to produce alkaline reaction
the liquid is then caused to boil whereupon the dye is dissolved and is salted out after
filtration.
4. Dyes prepared from Benzidine mono sulpho acid and Bismarck brown.
About one hundred parts by weight of Bismarck brown dissolved in water are mixed
with the Tetrazo compound of about eight parts by weight of Benzidine mono
sulpho acid.
On the addition of acetate of Soda the dye separates in the form of a product which
is sparingly soluble in water and dyes cotton a reddish brown.
Dated this 30th day of November 1887.

page_text: I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman, do hereby declare the nature of this Invention which has been com-
municated to me from abroad by The Farbenfabriken vormals Friedrich Bayer & Co.
of Elberfeld 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:
The present Invention has for its object the manufacture or production of dyes or
dyestuffs of a yellow to brown-red colour which dye cotton directly in an alkaline
bath without a mordant.
The dyes known in commerce as chrysoidine combine with diazo-compounds of
amines and their sulpho-acids to form yellow to yellow-red dyes, which dye cotton
with the aid of tannin and Tartar emetic or which dye wool in an acid bath.
My Foreign Correspondents have now discovered that these chrysoidines can be
readily combined with tetrazo-compounds of diamines to form new dyes varying in
tint from yellow to brown-red. These dye stuffs differ advantageously from those
derived from the diazo-compounds inasmuch as they are capable of directly dyeing
cotton in an alkaline bath without a mordant and of dyeing wool in an alkaline bath
or a neutral bath as well as in an acid bath.
Dye stuffs of the same colour and possessing the same properties as the above
mentioned are also obtained when in place of chrysoidines, the dye-stuffs known as
Bismarck brown, vesuvine or phenylene brown, (triamido-azo-benzine,) are employed.
These last mentioned dye stuffs present great practical advantages over those derived
from chrysoidine. The property of dyeing unmordanted cotton directly in an alkaline
bath and of dyeing wool in an alkaline or a neutral bath as well as in an acid bath is
possessed by the dyes formed by combining triamido-azo-benzene with the diazo-
compounds as well as by those derived from tetrazo-compounds.
Chrysoidines, as well as Bismarck brown, vesuvine or phenylene brown (triamido-
azo-benzene) combined with tetrazo-compounds present the same qualities as ordinary
amines; they are capable of readily forming intermediate compounds containing a
free diazo group which therefore produce mixed dyes when allowed to act on amines,
phenois &c. The same dye stuffs are obtained if the tetrazo-compound is at first
combined with one molecule of amines or phenols &c. and then with chrysoidines or
Bismarck brown.
These intermediate products or dye stuffs derived from Bismarck brown and
chrysoidines are not dye stuffs in themselves but direct acting dye stuffs are obtained
from them by converting the free diazo-group into the hydroxyl group OH by
boiling with water,

page_text: The process for producing the dye stuffs from Bismarck brown or chrysoidines and
tetrazo compounds consists generally in mixing with, or adding to, an aqueous
solution of the aforesaid dye stuffs a corresponding quantity of a tetrazo compound
with the addition of acetate of soda.
The dye stuffs obtained from Bismarck brown and diazo-compounds are formed
after standing for about twelve hours in a hydrochloric solution neutralising with soda,
boiling the dye stuff solution and then salting out.
These diazo- or tetrazo-compounds which do not contain any sulpho- or carbo-acid
group yield dye stuffs which are soluble in spirit and which can be rendered soluble
in water by means of sulphuric acid. The amines which have been found suitable for
forming direct acting dyes according to this invention with Bismarck brown are aniline,
toluidine, xylidine, cumidine and their nitro-derivatives and amido-azo-beuzene,
amido-azo-toluene, amido-azo-xylene-alpha- and beta-naphthylamine, the sulpho- and
carbo-acids thereof and those amines which are produced by combining alpha
naphthylamine with the diazo-compounds derived from the above mentioned amines
and the sulpho- and carbo-acids thereof.
The tetrazo-compounds which have been found suitable for the production of dyes from
Bismarck brown and chrysoidine are those derived from benzidine, benzidine-sulphone,
tolidine, tolidine-sulphone, diamido stilbene, diamidodiphenol ether, diamidofluorene,
diamido-azo-benzene, naphthylene-diamine, paraphenylendiamine, and the sulpho and
carbo acids thereof.
According to this Invention yellow to reddish-brown direct acting azo-dyes or dye
stuffs are obtained by the action of the diazo-compounds of aniline, toluidine, xylidine,
cumidine, amido-azo-benzene, amido-azo-toluene, alpha and beta-naphthylamine and
their sulpho and carbo acids upon Bismarck brown, vesuvine or phenylene brown
(triamidoazo-benzene) and also by the action of the tetrazo-compounds of benzidine,
benzidine-sulphone, tolidine, tolidine-sulphone, diamido-stilbene, diamidodiphenol
ether, naphthylenidiamine and their sulpho and carbo acids upon two molecules of
chrysoidine or of Bismarck brown, vesuvine or phenylene brown (triamidoazo-
benzene).
Intermediate products are also produced from the aforesaid tetrazo compounds and
one molecule of chrysoidine or Bismarck brown, vesuvine or phenylene brown which
contain a free diazo-group and are capable of acting upon one molecule of an amine-
phenol or the sulpho or carbo acids thereof to produce mixed yellow to reddish brown
direct acting dye stuffs which are likewise obtained by operating in the opposite
manner by combining the tetrazo compounds at first with one molecule of amines
phenols &c. and then with one molecule of Bismarck brown or chrysoidines.
The operations hereinafter described are given merely as examples of the best
mode with which I am acquainted of preparing these new dyes.
EXAMPLE 1. DYE STUFF PREPARED FROM BENZIDINE AND CHRYSOIDINE,
About ten parts by weight of the chrysoidine obtained from diazo-benzene chloride
and metaphenyline diamine are dissolved in water and mixed with a tetrazo-diphenyl
solution obtained by known means from about nine parts by weight of benzidine
sulphate. On the addition of acetate of soda a reddish-brown precipitate is obtained
which is insoluble in water. This deposit is separated by filtration and dried. When
absolutely dry the product is treated with fuming sulphuric acid and is thereby
rendered soluble in water.
EXAMPLE 2. DYE STUFF PREPARED FROM RENZIDING CHIDEA

page_text: About ten parts by weight of Bismarck brown dissolved in water are mixed with
the tetrazo-compound of about eight parts by weight of benzidine-mono-sulpho
acid.
On the addition of acetate of soda the dye stuff separates in the form of a product
which is sparingly soluble in water and dyes cotton a reddish brown.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed I declare that what 1
claim is:-
:-
1. In the production of dye-stuffs combining the diazo-compounds of aniline,
toluidine, xylidine, cummidine, or their niiro derivatives, amido-azo-benzene, amido-azo-
toluene, amido-azo-xylene, alpha- or beta-naphthylamine the sulpho and carbo acids
thereof and of those amines, which are obtained by combining alpha-naphthylamine
with the diazo compounds derived from the above mentioned amines, or the sulpho and
carbo acids thereof with the dyes known as Bismarck brown, vesuvine, or phenylene
brown (triamido-azo-benzene), substantially as hereinbefore set forth.
2. In the production of dye stuffs combining the tetrazo-compounds of benzidine,
benzidinesulphone, tolidine, tolidinesulphone, diamido stilbene, diamidodiphenol ether,
diamidofluorene, diamidoazobenzene, paraphenylendiamine, naphthylenediamine, or
the sulpho and carbo acids thereof with the dyes known in commerce as chrysoidine
and Bismarck brown, vesuvine or phenylene brown (triamidoazobenzene) substantially
as hereinbefore set forth.
3. In the production of dye stuffs combining one molecule of the tetrazo-compounds
of benzidine, benzidinesulphone, tolidine, tolidinesulphone, diamido stilbene, diamido-
fluorene, diainidobenzene, paraphenylendiamine, naphthylenediamine or the sulpho-
and carbo-acids thereof with one molecule of the dyes known in commerce as
chrysoidine and Bismarck brown (triamidoazobenzene) and with another molecule of
an aromatic amine or phenol or their sulpho or carbo acids or by combining one
molecule of the tetrazo compounds of the above mentioned paradiamines at first with
one molecule of an aromatic phenol or amine or their sulpho or carbo acids and then
with another molecule of the dye stuffs known in commerce as chrysoidine and
Bismarck brown (triamidoazobenzene) all substantially as set forth.
4. The manufacture of dye stuffs in the several manners hereinbefore described
under each of the foregoing examples.
5. As new articles of manufacture the dye stuffs hereinbefore described.