Improvements in the Production of Polyazo Dyestuffs.
Year: 1896

page_text: Date of Application, 10th Feb., 1896
Complete Specification Left, 9th Nov., 1896-Accepted, 12th Dec., 1898
PROVISIONAL SPECIFICATION.
Improvements in the Production of Polyazo Dyestuffs.
I, SYDNEY PITT of Sutton in the County of Surrey, Gentleman, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by Leopold Cassella & Co. of Frankfort-on-Main in the Empire of Germany)
to be as follows:-
In the general processes protected by the British Patents No. 1669989, 5141°³,
9529, 25018 amines or phenols such as m. phenylenediamine and m. toluylene-
diamine, resorcine are used as end components.
Further investigation has proved that these amines or phenols can be replaced
by their monoazo derivatives. By thus introducing further, what may be termed
lateral, azo groups, an increase of their tinctorial power is obtained. A suitable
selection of the azo rest combined with the m. diamine, or the resorcine offers
besides the possibility of rendering the resulting products more easily soluble and
even of giving to them new dyeing properties. Thus if for instance sulphonated
chrysoidines (from diazotised sulphanilic acid, naphtionic acid, amidonaphtolsulpho
acid &c. and m. phenylenediamine) are used, products result which are very much
more easily soluble than those from m. diamine itself; if however on the other
hand carbonic acids of chrysoidine for instance (from diazotised diazosalicylic acid
&c. and m. phenylenediamine) are used, coloring matters result which with chrome
mordants can be fixed perfectly fast to washing.
in which P represents the rest of a paradiamine and the complex - N = N
- ROH, the diazo compound of an amidophenol - or amidonaphtolsulpho or
carbonic acid.
Benzidine, tolidine, diamidodiphenolether, diamidodiphenylamine, and p. pheny-
lenediamine have been found especially useful as paradiamines and y amidonaphtol-
sulpho acid, 28 amidonaphtol 3.6 disulpho acid, amidosalicylic acid, and
p. amidophenolsulpho acid as the amidophenol compound (R).
The succession in which the four components of the dyestuff molecule can be
combined with each other may be varied. For instance the diazophenol can be
first combined with the m. diamine and then either the intermediate body from
paradiamine and y acid can be allowed to react, or the tetrazotised paradiamine
can be first added and at the end the y acid.
The process is illustrated by the following examples, the parts being by weight.

page_text: is brought to complete solution, then the intermediate body is added which is
obtained in the known manner by tetrazotising 244 parts of dianisidine and
combining with 24 parts of y amidonaphtolsulpho acid in alkaline solution. Whilst
the liquor is gradually discolored, a black precipitate forms. The dyestuff thus
obtained dyes unmordanted cotton a deep black and is fixed with chrome mordants. 5
2ND EXAMPLE.
20 parts of diamidodiphenylamine are tetrazotised and mixed with a solution
(rendered alkaline by means of soda) of 38 parts of the dyestuff which results from
combining the diazo compound of y amidonaphtolsulpho acid and m. phenylene-
diamine in molecular proportion. A difficultly soluble intermediate body is thus
formed.
To this the solution of 24 parts of y amidonaphtolsulpho acid is added, this
mixture is left standing for 12 hours, it is then heated to 60° C. and the dyestuff
which has separated is filtered off.
It dyes unmordanted cotton a deen black fast to washing and light
Dyestuffs composed of one molecule of paradiamine, two molecules of amido-
naphtolsulpho acid (asymmetrically combined) and one or two molecules of
chrysoidine.
The method of producing these combinations corresponds to the instructions
given in British Patents No. 95290 and 2501894. It is illustrated by the following
examples.
3RD EXAMPLE.
20 parts of diamidodiphenylamine are tetrazotised and combined with 24 parts of
y amidonaphtolsulpho acid in alkaline solution to form the simple intermediate
body which is then further diazotised with 7 parts of nitrite of soda and once more,
combined with 24 parts of y amidonaphtolsulpho acid in alkaline solution to form
the non-symmetrical intermediate body. Thereupon there are then added 36-6 parts
of the dyestuff, which is obtained by combining equal molecules of diazotised
naphtionic acid and m. phenylenediamine. The formation of the dyestuff is
terminated after a few hours. The dyestuff thus produced dyes unmordanted cotton
jet black.
4TH EXAMPLE.
38.2 parts of the body, which is obtained by saponifying the product resulting
from combining p. diazoacetanilide and y amidonaphtolsulpho acid, are tetrazo-
tised in a muriatic acid solution with 14 parts of nitrite of soda and combined
with 24 parts of y amidonaptolsulpho acid in alkaline solution to form the non-
symmetrical intermediate product. This is again diazotised with 7 parts of
nitrite of soda and then introduced into the alkaline solution of 60 parts of the
dyestuff which results from the combination of p. diazosalicylic acid with m. pheny-
lenediamine in molecular proportion.
The dyestuff forms in a few hours. It dyes animal as well as vegetable fibre by
the aid of chrome mordants a fast black.
If in these examples diamidodiphenylamine, respectively p. phenylenediamine is
replaced by other paradiamines such as for instance dianisidine or if the chrysoidines
mentioned above are replaced by other dyestuffs such as for instance by the
combinations from diazotised sulphauilic or y amidonaphtolsulpho acid, products
result which behave quite similarly aud also dye unmordanted cotton a jet black.
In an analogous manner other combinations are obtained.

page_text: yaz
estuns.
I, SYDNEY PITT, of Sutton, in the County of Surrey, Gentleman, do hereby
declare the nature of this invention (which has been communicated to me from
abroad by Leopold Cassella & Co., of Frankfort-on-Main, 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:-
In the general processes protected by the British Patents No. 166998, 5141°³,
95290, 25018, ainines or phenols such as m. phenylenediamine and m. toluylene-
diamine, resorcine are used as end components.
Further investigation has proved that these amines or phenols can be replaced
by their monoazo derivatives. By thus introducing further, what may be termed
lateral, azo groups, an increase of their tinctorial power is obtained. A suitable
selection of the azo rest combined with the m. diamine, or the resorcine offers
besides the possibility of rendering the resulting products more easily soluble
and even of giving to them new dyeing properties. Thus if for instance sulphonated
chrysoidines (from diazotised sulphanilic acid, naphtionic acid, amidonaphtolsulpho
acid, etc. and m. phenylenediamine) are used, products result which are very much
more easily soluble than those from m. diamine itself; if however on the other
hand carboxylic acids of chrysoidine, for instance (from diazotised diazosalicylic
acid, etc. and m. phenylenediamine) are used, coloring matters result which with
chroine mordants can be fixed perfectly fast to washing.
in which P represents the rest of a paradiamine and the complex - N = N
-R OH, the diazo compound of an amidophenol-or amidonaphtolsulpho or
carboxylic acid.
Benzidine, tolidine, diamidodiphenolether, diamidodiphenylamine, and p. pheny-
lenediamine have been found especially useful as paradiamines, and y amidonaph-
tolsulpho acid, 2-8 amidonaphtol-3-6 disulpho acid, amidosalicylic acid and
p. amidophenolsulpho acid as the amidophenol compound-(R).
The succession in which the four components of the dyestuff molecule can be
combined with each other may be varied. For instance the diazophenol can be
first combined with the m. diamine and then either the intermediate body from
paradiamine and y acid can be allowed to react, or the tetrazotised paradiamine can
be first added and at the end the y acid.
The propose is illustrated be the falle

page_text: Whilst the liquor is gradually discolored, a black precipitate forins. The dyestuff
thus obtained dyes unmordanted cotton a deep black and is fixed with chrome
mordants.
2ND EXAMPLE.
20 parts of diamidodiphenylamine are tetrazotised and mixed with a solution 5
(rendered alkaline by means of soda) of 38 parts of the dyestuff which results from
combining the diazo compound of y amidonaphtolsulpho acid and m. phenylene-
diamine in molecular proportion. A difficultly soluble intermediate body is thus
formed. To this the solution of 24 parts of y amidonaphtolsulpho acid is added;
this mixture is left standing for 12 hours, it is then heated to 60° C. and the dyestuff 1
which has separated is filtered off.
It dyes unmordanted cotton a deep black fast to washing and light.
The method of producing these combinations corresponds to the instructions given
in British Patents No. 95294 and 25018. It is illustrated by the following
examples.
3RD EXAMPLE.
20 parts of diamidodiphenylamine are tetrazotised and combined with 24 parts
of y amidonaphtolsulpho acid in alkaline solution to form the simple intermediate
body which is then further diazotised with 7 parts of nitrite of soda and once more
combined with 24 parts of y amidonaphtolsulpho acid in alkaline solution to form
the non-symmetrical intermediate body.
Thereupon there are then added 36'6 parts of the dyestuff which is obtained by
combining equal molecules of diazotised naphtionic acid and m. phenylenediamine.
The formation of the dyestuff is terminated after a few hours.
The dyestuff thus produced dyes unmordanted cotton jet black.
4TH EXAMPLE.
38-2 parts of the body, which is obtained by saponifying the product resulting
from combining p. diazoacetanilide and y amidonaphtolsulpho acid, are tetrazotised
in a muriatic acid solution with 14 parts of nitrite of soda and combined with
24 parts of y amidonaphtolsulpho acid in alkaline solution to form the non-sym-
metrical intermediate product. This is again diazotised with 7 parts of nitrite of
soda and then introduced into the alkaline solution of 60 parts of the dye-
stuff which results from the combination of p. diazosalicylic acid with m. pheny-
lenediamine in molecular proportion. The dyestuff forms in a few hours. It dyes
animal as well as vegetable fibre by the aid of chrome-mordants a fast black.
If in these examples diamidodiphenylamine, respectively p. phenylenediamine is
replaced by other paradiamines such as for instance dianisidine or if the chrysoi-
dines mentioned above are replaced by other dyestuffs such as for instance by the
combinations from diazotised sulphanilic or y amidonaphtolsulpho acid, products
result which behave quite similarly and also dye unmordanted cotton a jet black.
In an analogous manner other combinations are obtained.
Having now particularly described and ascertained the nature of my said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:
1. The manufacture of poly-azo-dyestuffs by combining one molecule of a tetrazo

page_text: compound with one molecule of gamma amidonaphtolsulpho acid and one molecule
of an hydroxylated chrysoidine or vice-versa substantially as described.
2. The manufacture of poly-azo-dyestuffs by diazotising the intermediate
compounds formed by the action of a tetrazo-compound upon gamma-amidonaph-
tolsulpho acid in an alkaline solution, combining again with one molecule of the
amidonaphtolsulpho acid and finally combining, either directly, or after a further
diazotation with a chrysoidine substantially as described.
3. The new coloring matters hereinbefore described.