Improvements in the Production of Azo Dyes.
Year: 1892

page_text: Date of Application, 12th Feb., 1892
Complete Specification Left, 11th Nov., 1892-Accepted, 17th Dec., 1892
PROVISIONAL SPECIFICATION.
Improvements in the Production of Azo Dyes.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort-on-Main,
in the Empire of Germany, Manufacturing Chemists,) do hereby declare the nature
of this invention to be as follows :—
Coloring matters which are prepared of those tetrazo-azo-compounds which
derive from the products of reaction of tetrazodiphenyle-, tetrazodiphenylesulpho-
acid and similar bodies upon alpha naphtylamine, were first described in the
Specification of a German Patent No. 40,977 in the year 1886 granted to Messrs.
Cassella & Co.
This invention relates to a new series of coloring matters of analogous constitution:
in which alpha naphtylamine is replaced by certain of its sulpho acids. Amongst
all isomeric naphtylamine sulpho acids only the two acids which Cleve has obtained.
by nitration and reduction from naphtalene beta sulphonic acid and which he has
designated by the letters "beta" and "delta," are fit for the said purpose. The
constitution of these acids has been found to be 1.6 (beta) and 1-7 (delta). The
production of coloring matters of the above mentioned constitution can be carried.
out in different AWA
The tetrazoderivative of the p. diamine is combined with one molecule of one of
the acids 1-6 or 1.7. The intermediate compound is diazotised with one molecule of
nitrite and combined with two molecules of a phenol or of an amine.
Example. 18.4 kg. of benzidine are diazotised and brought into the solution of
22-5 kg. of the acid 1.7, which is kept alkaline with carbonate of soda. The inter-
mediate compound will be formed immediately. It is diazotised again by means of
7 kg. of nitrite. The tetrazoazocompound is introduced into the alkaline solution of
50 kg. of gamma amidonaphtholsulpho acid. The thus produced coloring matter
dyes unmordanted cotton blueish-black.

page_text: III.
The tetrazocompound of the p. diamine is combined with one molecule of one of
the acids 1-6 or 17 and with one molecule of a phenol or another amine. The
mixed coloring matter thus obtained is diazotised again with one or two molecules
of nitrite and combined with one or two molecules of a phenol or of an amine,
according to the number of diazotable groups.
Example. 59 kg. of the mixed coloring matter composed of benzidine, acid 1-6 and
salicylic acid are treated in aqueous solution with muriatic acid and 7 kg. of nitrite.
The diazo-disazo-compound has a brown color and is difficultly soluble. It is brought
into the solution of 12.5 kg. of m. toluylene-diamine. The resulting coloring matter
dyes cotton a deep brown-black.
Or for instance 70 kg. of the mixed coloring matter composed of benzidine,
acid 1-7 and gamma amidonaphtholsulphonic acid (combined in alkaline solution)
are suspended in water and diazotised in presence of muriatic acid by means of
14 kg. of nitrite. In a short time the tetrazo-disazocompound will be formed. It is
of a black shade and difficultly soluble. It is added to the alkaline solution of 68 kg.
of amidonaphtholdisulpho acid H. The resulting coloring matter dyes unmordanted
cotton a blueish-black.
The processes described under I and II can also be carried out on the fibre in the
known manner. The fibre dyed with the respective derivatives of 1.6 or 17
naphtylaminesulpho acid is treated with nitrous acid and the color is developed in a
second bath containing the phenol or the amine.
Dated this 12th day of February 1892.
CAKIMAEL & CO.,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Azo Dyes.
1, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort-on-Main,
in the Empire of Germany, Manufacturing Chemists,) 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 :-
Coloring matters which are prepared of those tetrazo-azo-compounds which derive
from the products of reaction of tetrazodiphenyle-, tetrazodiphenylesulpho-acid and
similar bodies upon alpha naphtylamine were first described in the Specification of a
German Patent No. 40,977 in the year 1886 granted to Messrs. Cassella & Co.
This invention relates to a new series of coloring matters of analogous consitution
in which alpha naphtylamine is replaced by certain of its sulpho acids. Amongst
all isomeric naphtylamine sulpho acids only the two acids which Cleve has obtained
by nitration and reduction from naphtalene beta sulphonic acid and which he has
designated by the letters "beta" and "delta," are fit for the said purpose. The
constitution of these acids has been found to be 1·6 (beta) and 1-7 (delta). The
production of coloring matters of the above mentioned constitution can be carried
out in different ways.
Example. 59 kg. of the mixed coloring matter composed of benzidine, acid 1'6
and salicylic acid are treated in aqueous solution with muriatic acid and 7 kg. of
nitrite. The diazo-disazo-compound has a brown color and is difficultly soluble. It
is brought into the solution of 12.5 kg. of m. tuluylene-diamine. The resulting
coloring matter dyes cotton a deep brown-black.
Acid 1-7 and gamnia amidonaphtholsulphonic acid (combined in alkaline solution)
are suspended in water and diazotised in presence of muriatic acid by means of
14 kg. of nitrite. In a short time the tetrazo-disazo compound will be formed. It
is of a black shade and difficultly soluble. It is added to the alkaline solution of

page_text: 68 kg. of amidonaphtoldisulpho acid H. The resulting coloring matter dyes.
unmordanted cotton a blueish-black.
The processes described under I and II can also be carried out on the fibre in
the known manner. The fibre dyed with the respective derivatives of 1-6-
5 or 17 naphtylaminesulpho acid is treated with nitrous acid and the color is
developed in a second bath containing the phenol or the amine.
I name also the following coloring matters which can be similarly prepared :
CARPMAEL & Co.,
Agents for the Applicant..

page_text: Date of Application, 12th Feb., 1892
Complete Specification Left, 11th Nov., 1892-Accepted, 17th Dec., 1892
PROVISIONAL, SPECIFICATION.
Improvements in the Production of Azo Dyes.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort-on-Main,
in the Empire of Germany, Manufacturing Chemists,) do hereby declare the nature
of this invention to be as follows:-
Coloring matters which are prepared of those tetrazo-azo-compounds which
derive from the products of reaction of tetrazodiphenyle-, tetrazodiphenylesulpho-
acid and similar bodies upon alpha naphtylamine, were first described in the
Specification of a German Patent No. 40,977 in the year 1886 granted to Messrs.
Cassella & Co.
This invention relates to a new series of coloring matters of analogous constitution
in which alpha naphtylamine is replaced by certain of its sulpho acids. Amongst
all isomeric naphtylamine sulpho acids only the two acids which Cleve has obtained
by nitration and reduction from naphtalene beta sulphonic acid and which he has
designated by the letters "beta" and "delta," are fit for the said purpose. The
constitution of these acids has been found to be 1-6 (beta) and 1-7 (delta). The
production of coloring matters of the above mentioned constitution can be carried
out in different ways.
The tetrazo compound of the p. diamine (benzidine, tolidine, p. phenylenediamine,
diamidostilbenedisulpho-acid, diamidonaphtalenedisulpho-acid, etc.) is combined
with two molecules of one of the alpha naphtylaminesulpho acids 16 or 17. The
product is diazotised with two molecules of nitrite and combined with two
molecules of a phenol or of an amine.
Example. 70 kg. of the coloring matter produced from benzidine and acid 1-7 are
dissolved in water together with 14 kg. of nitrite. The solution is cooled down to
10 deg. C. and acidulated with 70 kg. of muriatic acid. After one hour the
diazotation will be terminated. Then the liquid is poured into the solution of 50 kg.
of alpha naphthol alpha sulphonate. The thus formed coloring matter dyes
unmordanted cotton blueish-black shades.
The tetrazoderivative of the p. diamine is combined with one molecule of one of
the acids 16 or 1-7. The intermediate compound is diazotised with one molecule of
nitrite and combined with two molecules of a phenol or of an amine.
Example. 18.4 kg. of benzidine are diazotised and brought into the solution of
22-5 kg. of the acid 1-7, which is kept alkaline with carbonate of soda. The inter-
mediate compound will be formed immediately. It is diazotised again by means of
7 kg. of nitrite. The tetrazoazucompound is introduced into the alkaline solution of
50 kg. of gamma amidonaphtholsulpho acid. The thus produced coloring matter
dyes unmordanted cotton blueish-black.

page_text: mixed coloring matter thus obtained is diazotised again with one or two molecules
of nitrite and combined with one or two molecules of a phenol or of an amine,
according to the number of diazotable groups.
Example. 59 kg. of the mixed coloring matter composed of benzidine, acid 1.6 and
salicylic acid are treated in aqueous solution with muriatic acid and 7 kg. of nitrite.
The diazo-disazo-compound has a brown color and is difficultly soluble. It is brought
into the solution of 12.5 kg. of m. toluylene-diamine. The resulting coloring matter
dyes cotton a deep brown-black.
Or for instance 70 kg. of the mixed coloring matter composed of benzidine,
acid 1.7 and gamma amidonaphtholsulphonic acid (combined in alkaline solution)
are suspended in water and diazotised in presence of muriatic acid by means of
14 kg. of nitrite. In a short time the tetrazo-disazocompound will be formed. It is
of a black shade and difficultly soluble. It is added to the alkaline solution of 68 kg.
of amidonaphtholdisulpho acid H. The resulting coloring matter dyes unmordanted
cotton a blueish-black.
The processes described under I and II can also be carried out on the fibre in the
known manner.
The fibre dyed with the respective derivatives of .16 or 17
naphtylaminesulpho acid is treated with nitrous acid and the color is developed in a
second bath containing the phenol or the amine.
Dated this 12th day of February 1892.

page_text: COMPLETE SPECIFICATION.
Improvements in the Production of Azo Dyes.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, (a com-
munication to me from abroad by Leopold Cassella & Co., of Frankfort-on-Main,
in the Empire of Germany, Manufacturing Chemists,) 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 :-
•
Coloring matters which are prepared of those tetrazo-azo-compounds which derive
from the products of reaction of tetrazodiphenyle-, tetrazodiphenylesulpho-acid and
similar bodies upon alpha naphtylamine were first described in the Specification of a
German Patent No. 40,977 in the year 1886 granted to Messrs. Cassella & Co.
This invention relates to a new series of coloring matters of analogous constitution
in which alpha naphtylamine is replaced by certain of its sulpho acids. Amongst
all isomeric naphtylamine sulpho acids only the two acids which Cleve has obtained
by nitration and reduction from naphtalene beta sulphonic acid and which he has
designated by the letters "beta" and "delta," are fit for the said purpose. The
constitution of these acids has been found to be 1.6 (beta) and 1.7 (delta). The
production of coloring matters of the above mentioned constitution can be carried
out in different ways.
The tetrazo compound of the p. diamine (benzidine, tolidine, p. phenylenediamine, -
diamidoaethoxydiphenyle, diamidostilbenedisulpho-acid, diamidonaphtalenedisulpho-
acid, etc.) is combined with two molecules of one of the alpha naphtylamine-
sulphoacids 1-6 or 1-7. The product is diazotised with two molecules of nitrite and
combined with two molecules of a phenol or of an amine.
Example. 70 kg. of the coloring matter produced from benzidine and acid 1-7
are dissolved in water together with 14 kg. of nitrite. The solution is cooled down
to 10 degrees C. and acidulated with 70 kg. of muriatic acid. After one hour the
diazotation will be terminated. Then the liquid is poured into the solution of
50 kg. of alpha naphtol alpha sulfonate. The thus formed coloring matter dyes
unmordanted cotton blueish-black shades.
The tetrazo derivative of the p. diamine is combined with one molecule of one of
the acids 16 or 17. The intermediate compound is diazotised with one molecule
of nitrite and combined with two molecules of a phenol or of an amine.
Example. 184 kg. of benzidine are diazotised and brought into the solution of
22.5 kg. of the acid 1-7, which is kept alkaline with carbonate of soda. The inter-
mediate compound will be formed immediately. It is diazotised again by means of
7 kg. of nitrite. The tetrazoazocompound is introduced into the alkaline solution -
of 50 kg. of gamma amidonaphtolsulpho acid. The thus produced coloring matter
dyes unmordanted cotton blueish-black.

page_text: of nitrite and combined with one or two molecules of a phenol or of au amine,
according to the number of diazotable groups.
Example. 59 kg. of the mixed coloring matter composed of benzidine, acid 1.6
and salicylic acid are treated in aqueous solution with muriatic acid and 7 kg. of
nitrite. The diazo-disazo-compound has a brown color and is difficultly soluble. It
is brought into the solution of 12.5 kg. of m. toluylene-diamine. The resulting
coloring matter dyes cotton a deep brown-black.
Or for instance 70 kg. of the mixed coloring matter composed of benzidine,
acid 17 and gamma amidonaphtholsulphonic acid (combined in alkaline solution)
are suspended in water and diazotised in presence of muriatic acid by means of
14 kg. of nitrite. In a short time the tetrazo-disazo compound will be formed. It
is of a black shade and difficultly soluble. It is added to the alkaline solution of
68 kg. of amidonaphtoldisulpho acid H. The resulting coloring matter dyes
unmordanted cotton a blueish-black.
The processes described under I and II can also be carried out on the fibre in
the known manner.
The fibre dyed with the respective derivatives of 1.6
or 17 naphtylaminesulpho acid is treated with nitrous acid and the color is
developed in a second bath containing the phenol or the amine.
Of the great number of compounds that can be prepared by the different methods
above described I name the following coloring matters as examples:

page_text: Having now particularly described and ascertained the nature of the said inven-
n and in what manner the same is to be performed I declare that what I
im is:-
1. The process of producing secondary azo coloring matters from disazocompounds
taining a naphtylaminesulpho acid 16 or 1.7, which consists in diazotising:
a.) the products obtained from one molecule of a tetrazocompound (such as
tetrazodiphenyle, tetrazoditolyle, tetrazoethoxydiphenyle, tetrazophenylene,
etc.) with two molecules of the a naphtylamine-sulpho acid 16 or 1.7, and
combining with phenols or amines, substantially as described.
b.) the intermediate products obtained from one molecule of the tetrazo-
compound and one molecule of the a naphtylaminesulpho acid 1-6 or 1.7, and
combining with phenols or amines substantially as described.
c.) the mixed coloring matters obtained from one molecule of the tetrazo
compound, one molecule of the a naphtylaminesulpho acid 1-6 or 1-7 and one
molecule of another amine or of a phenol, and combining with phenols or
amines, substantially as described.
2. As new products of manufacture the coloring matters above described.
Dated this 3rd day of November 1892.
CARPMAEL & Co.,
Agents for the Applicant.