Year: 1899

page_text: Date of Application, 28th Mar., 1899
Complete Specification Left, 28th Dec., 1899-Accepted, 10th Feb., 1900
I, THOMAS RICHARD SHILLITO, of 15, Tooks Court, London, E.C., Patent Agent, do
hereby declare the nature of this invention-a communication to me from abroad by
Messieurs John Rudolf Geigy & Co., of Basle, Switzerland, Colour Manufacturers-to
be as follows:-
The present invention refers to a new proceeding which consists in the reaction of
two molecules of p-nitrotoluenesulphonic acid with one molecule of p-phenylene-
diamine or p-toluylenediamine in presence of caustic alkali lye of a concentration of
from 10 to 15 per cent. and at a temperature of for instance 70° to 90° C. without
boiling the mass.
The colouring matters thus obtained dye unmordanted cotton gold yellow to reddish
orange shades.
For instance :-
I. 100 kilos. of p-nitrotoluenesulphonic acid are dissolved in 400 liters of hot
water, then a solution of 24 kilos. of p-phenylenediamine in 200 liters of boiling
water is added and afterwards, at a temperature of 70° C., 300 kilos. of caustic soda
lye of 40° Bé. and the mass stirred for about three hours whilst the temperature is
slowly raised to about 90° C. Then the caustic soda is nearly saturated with hydro-
chloric acid and the colouring matter salted out, filtered off, pressed, and dried. It
dyes unmordanted cotton reddish orange shades.
II. If in this example instead of p-phenylenediamine there are used 24 kilos. of
p-amidophenol and proceeded with in the same manner, a colouring matter is formed
which dyes unmordanted cotton, in a bath acidulated with acetic acid, fine gold yellow
shades but not fast to the action of alkali. This colouring matter and also the
analogous product derived from o-amido-p-cresol may be transformed into products
fast to alkali by means of alkylation or benzylation.
For instance :-
III. 30 kilos. of the colouring matter of Example II. are dissolved in 100 liters of
boiling water with 10 kilos. of caustic soda lye of 40° Bé., then the solution is, with
addition of 12 kilos. of ethylbromide, treated in an autoclave for about four hours at
a temperature of 105° to 100° C. Then the ethylated colouring matter is filtered off,
pressed and dried. It dyes unmordanted cotton bright gold yellow shades.
New azo colouring matters are obtained if the described products of condensation
of 2 molecules of p-nitrotoluenesulphonic acid and 1 molecule or 2 molecules of
p-phenylenediamine or p-toluylenediamine are further diazotised and combined with
amines or phenols or with their derivates.
Orange colours are obtained by combination with phenol, cresol, salicylic acid,
cresotinic acid, m-phenylenediaminedisulpho acid, m-toluylenediaminesulpho acid,
nitro-m-phenylenediamine, nitrometatoluylenediamine, dehydrothio-p-toluidinesul-
pho acid. The colouring matters obtained from phenol and cresol may be alkylated
as described in Example III.
Yellowish brown and reddish brown to red colours are obtained with meta-
phenylenediamine, metatoluylenediamine, metaamidophenol, resorcin, guaiacol pyro-
gallic acid, metaamidophenolsulpho acid, metaphenylenediaminemonosulpho acid,

page_text: dimethylaniline, diethylaniline, a naphtylamine, ẞ naphtylamine, and their sulpho
acids, a naphtol, ß naphtol, dioxynaphtalines and their sulpho acids, B1 a 4 amido-
naphtol, 83 sulpho acid and its alkylated derivates and also the phenylated acid.
Violet colours are obtained from the mono and disulpho acids of a 1 24 amido-
naphtol.
Olive colours are formed by combination of the said diazo compounds with the
monoazo colours from a 1 a 4 amidonaphtolmono or disulphonic acids such as p-nitro-
anilineazo acid H.
For instance :-
IV. 60 kilos. of the colouring matter produced according to Example I. are dis-
solved in about 400 liters of boiling water, then left to stand until cold, ice and
35 kilos. of hydrochloric acid of 21° Bé. added thereto, and then diazotised by gradual
addition of 7 kilos. of nitrite of sodium. After stirring for about three hours the
diazo compound is left to run into a solution of 9.5 kilos. of pnenol with 5 kilos. of
caustic soda and 30 kilos. of carbonate of sodium in 200 liters of water, then heated
to boiling, salted out, pressed and dried. It dyes unmordanted cotton bright orange
shades. When treated with ethyl chloride or ethyl bromide according to Example III.,
the ethylated colouring matter is obtained.
V. The same diazo compound is combined in alkaline solution with 45 kilos. of the
well known azo colour from diazotised p-nitraniline with a 1 a 4 amidonaphtol B2 B3
disulpho acid (produced in acid solution). This colouring matter dyes olive
shades.
Instead of the products of condensation from p-nitrotoluenesulpho acid there may
be used the products of condensation of p-dinitrodibenzyldisulpho acid with p-pheny-
lenediamine, p-toluylenediamine, in-phenylenediamine, m-toluylenediamine or with
an amine and a p-diamine such as the compounds which are obtained by condensa-
tion of 1 molecule of p-dinitrodibenzyldisulpho acid first with one molecule of the
following compounds anilinetoluidine, xylidine, cumidine, amidophenolether,
amidocresolether, m-phenylenediamine, m-toluylenediamine, p-amidophenol,p-amido-
o-cresol, p-amido-salicylic acid, p-amido-o-cresotinic acid, sulfanilic acid, toluidine-
sulpho acid, amidobenzoic acid, p-amidobenzaldehydenaphtylaminesulpho acids,
dehydrothio-p-toluidinesulpho acid, primuline, ẞ1 a4 amidonaphtol 83 sulpho
acid and then secondly with 1 molecule of p-phenylenediamine or p-toluylenedia-
mine.
For instance :-
VI. 70 kilos. of the colouring matter from 1 molecule of p-dinitrodibenzyldisulpho
acid molecule of m-toluylenediamine + 1 molecule of p-phenylenediamine are
dissolved in about 500 liters of boiling water. After cooling and addition of ice,
45 kilos. of hydrochloric acid of 21° Bé. are added and then diazotised with 14 kilos.
of nitrite of sodium. The formation of the tetrazo compound finished, it is left to
run into a solution of 54 kilos. of dimethyl ẞ1 a4 amidonaphtol ẞ 3 sulpho acid with
50 kilos. of carbonate of sodium in about 500 liters of water. The mass is then heated
to boiling, the colouring matter salted out, filtered off, pressed and dried. It dyes
unmordanted cotton yellowish brown shades.
Dated this 28th day of March 1899.

page_text: Rudolph Geigy & Co., of Basle, Switzerland, Colour Manufacturers-to be particularly
described and ascertained in and by the following statement :-
This invention relates to a new proceeding which consists in the reaction of two
molecules of p-nitrotoluenesulpho acid with one molecule of p-phenylenediamine or
p-toluylenediamine, p-amidophenol, p-amidoorthocresol, p-amidosalicylic acid or
p-amido-ortho-cresotinic acid in presence of caustic alkali lye of a concentration of
from 10 to 15 per cent., and at a temperature of, for instance, from 70° to 90° C.,
without boiling the mass.
The colouring matters thus obtained dye unmordanted cotton gold yellow to reddish
orange shades.
For instance :-
I. 100 kilos. of p-nitrotoluenesulphonic acid are dissolved in 400 liters of hot water;
then a solution of 24 kilos. of p-phenylenediamine in 200 liters of boiling water is
added and afterwards at a temperature of 70° C., 300 kilos. of caustic soda lye of
40° Bé, and the mass stirred for about 3 hours whilst the temperature is slowly
raised to about 90° C. Then the caustic soda is nearly saturated with hydrochloric
acid and the colouring matter salted out, filtered off, pressed and dried. It dyes
unmordanted cotton reddish orange shades.
11. If in this example, instead of p-phenylenediamine there are used 24 kilos. of
p-amidophenol and proceeded with in the same manner, a colouring matter is formed
which dyes unmordanted cotton, in a bath acidulated with acetic acid, fine gold
yellow shades, but not fast to the action of alkali.
This colouring matter and also the analogous product derived from o-amido-p-
cresol may be transformed into products fast to alkali by means of alkylation or
benzylation.
For instance :-
III. 30 kilos. of the colouring matter of Example II. are dissolved in 100 liters of
boiling water with 10 kilos. of caustic soda lye of 40° Bé., then the solution is, with
addition of 12 kilos. of ethylbromide, treated in an autoclave for about 4 hours at a
temperature of 105°-100° C. Then the ethylated colouring matter is filtered off,
pressed and dried. It dyes unmordanted cotton bright gold yellow shades.
New azo colouring matters are obtained if the products of condensation of 2 mole-
cules of p-nitrotoluenesulphonic acid and 1 or 2 molecules of p-phenylenediamine or
p-toluylenediamine are further diazotised and combined with amines or phenols or
with their derivates.
Orange colours are obtained by combination with phenol, cresol, salicylic acid,
cresotinic acid, m-phenylenediaminedisulpho acid, m-toluylenediaminesulpho acid,
nitro-m-phenylenediamine, nitrometatoluylenediamine,
sulpho acid.
dehydrothio-p-toluidine-
The colouring matters obtained from phenol and cresol may be
alkylated as described in Example III.
Yellowish brown and reddish brown to red colours are obtained with metapheny-
lenediamine, metatoluylenediamine, metnamidophenol, resorcine, guaiacol, pyrogallic
acid, metaamidophenolsulpho acid, metaphenylenediaminemonosulpho acid, dimethyl-
aniline, diethylaniline, a-naphtylamine, B-naphtylamine, and their sulpho acids,
a-naphtol, B-naphtol, dioxynaphtalines and their sulpho acids, B1 a 4 amidonaphtol
B3 sulpho acid and its alkylated derivates and also the phenylated acid.
Violet colours are obtained from the mono and disulpho acids of a 1 a 4 amido-
naphtol.
Olive colours are formed by combination of the said diazo compounds with the
monoazo colours from a 1 a 4 amidonaphtol mono- or disulpho acids such as p-nitro-
aniline-azo-acid H.
For instance:―
IV. 60 kilos. of the colouring matter produced according to Example I. are
dissolved in about 400 liters of boiling water, then allowed to stand until cold, ice
and 35 kilos. of hydrochloric acid of 21° Bé. added thereto and then diazotised by
gradual addition of 7 kilos, of nitrite of sodium. After stirring for about three hours

page_text: the diazo compound is left to run into a solution of 9.5 kilos. of phenol with 5 kilos.
of caustic soda and 30 kilos. of carbonate of sodium in 300 liters of water, then heated
to boiling, salted out, pressed and dried... It dyes unmordanted cotton bright orange
shades. When treated with ethyl chloride or ethyl bromide according to Example III.,
the ethylated colouring matter is obtained.
V. The same diazo compound is combined in alkaline solution with 45 kilos. of the
well known azo colours from diazotised p-nitraniline with al a4 amidonaphtol 82 83
disulpho acid (produced in acid solution. This colouring matter dyes olive shades.
Instead of the products of condensation from p-nitrotoluenesulpho acid, there may
be used the products of condensation of p-dinitrodibenzyldisulpho acid with p-pheny-
lenediamine, p-toluylenediamine m-phenylenediamine, m-toluylenediamine, or with
an amine, and a p-diamine, such as the compounds which are obtained by condensa-
tion of 1 molecule of p-dinitrodibenzyldisulpho acid first with one molecule of the
following compounds-aniline toluidine, xylidine, cumidine, amidophenolether,
ainidocresolether, m-phenylenediamine, m-toluylenediamine, p-amidophenol, p-amido-
o-cresol, p-amido-salicylic acid, p-amido-o-cresotinic acid, sulfanilic acid, toluidine-
sulpho acid, amidobenzoic acid, p-amidobenzaldehyde, naphtylaminesulpho acids,
dehydrothio-p-toluidinesulpho acid, primuline, ẞ 1 a 4 amidonaphtol 83 sulpho acid
and then secondly with one molecule of p-phenylenediamine or p-toluylene-
diamine.
For instance :-
VI. 70 kilos. of the colouring matter from 1 molecule of p-dinitrodibenzyldisulpho
acid + 1 molecule of m-toluylenediamine + 1 molecule of p-phenylenediamine are
dissolved in about 500 liters of boiling water. After cooling and addition of ice,
45 kilos. of hydrochloric acid of 25° Bé. are added and then diazotised with 14 kilos.
of nitrite of sodium. The formation of the tetrazo compound finished, it is left to
run into a solution of 54 kilos., of dimethyl-82 a 4 amidonaphtol 84 sulpho acid
with 50 kilos. of carbonate of sodium in about 500 liters of water. The mass is then
heated to boiling, the colouring matter salted out, filtered off, pressed and dried. It
dyes unmordanted cotton yellowish brown shades.
Having now particularly described and ascertained the nature of 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 the production of colouring matters which consists in the
condensation of two molecules of paranitrotoluenesulpho acid with one molecule
of one of the following substances :-paraphenylenediamine, paratoluylenediamine,
paraamidophenol, paraamidoorthocresol, paraamidosalicylic acid or paraamidoortho-
cresotinic acid, by means of caustic alkali lye, substantially as described.
2. The process for the production of colouring matters by alkylation or benzylation
of the products obtained according to Claim 1 and derived from paraamidophenol or
paraamidoorthocresol, substantially as described.
3. The process for the production of new azo colouring matters by diazotation of
the products of condensation of two molecules of paranitrotoluenesulpho acid and
one or two molecules of paraphenylenediamine or paratoluylenediamine and combina-
tion of the diazo compounds thus obtained with amines or phenols or with their
derivates, substantially as described.
- 4. The process for the production of colouring matters by alkylation or benzylation
of the products obtained according to Claim 3 and derived from phenol or orthocresol,
substantially as described.
. 5. The process for the production of new azo colouring matters by means of the
products of condensation of paradinitrodibenzyldisulpho acids with amines according
to the process of Claims 3 and 4, substantially as described.
Dated this 28th day of December 1899.
MUALA