The Manufacture or Production, of New Azo Dye-stuffs for Cotton.
Year: 1899

page_text: PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN VORMALS FRIEDRICH BAYER & Co.,
of Elberfeld, Germany.]
The Manufacture or Production, of New Azo Dye-stuffs for Cotton.
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 disulphonic acids of dioxydinaphthyl-
are valuable intermediate products for the preparation of dye-stuffs.
It may be remarked that, according to the researches of my foreign correspondents,
the dioxydinaphthylamine disulphonic acids can be prepared by heating certain
betaamidonaphtholsulphonic acids, such as betal-amido-alpha3 naphthol-beta4-
sulphonic acid, betal-amido alpha 3 naphthol-alpha 4 sulphonic acid, or the like, with
sulphurous acid, or with salts of this acid.
According to recent researches of my foreign correspondents, these dinaphthyl-
amine sulphonic acids are capable of combining with one, and likewise with two,
inolecules of diazo compounds, new valuable azo dye-stuffs being thus obtained,
which dye unmordanted cotton, from red to blue bright and fast shades.
In order to combine one molecule of the said dinaphthylamine disulphonic acids
only with one molecule of a diazo compound, the reaction is preferably performed in
a slightly acid solution, whilst the combination with two molecules of diazo compounds
In the latter case, the same or two
is profitably performed in an alkaline solution.
different diazo compounds may be used.
In the following table, the shades produced on unmordanted cotton by several of
the new dye stuffs obtainable according to the new process are given.
The dye-stuff produced by the combination of one molecule of the dioxydinaphthyl.

page_text: amine disulphonic acid obtained from betal-amido-alpha 3 napthol-beta 4 sulphonic
acid, and having most probably the formula-
DYE-STUFF PREPARED FROM
ONE MOLECULE OF A DIOXYDINAPHTHYLAMINE DISUL-
PHONIC ACID AND ONE MOLECULE OF DIAZO-BENZENE-CHLORIDE.
9.3 kilos. of aniline are diazotized in the usual way by means of sodium nitrite and
hydrochloric acid. The diazosolution thus obtained is allowed to run, while cooling
and stirring, into a concentrated solution of 46.1 kilos. of the dioxydinaphthylamine
disulphonic acid (having the above mentioned formula), which solution has been
mixed with a sufficient quantity of sodium acetate, and has been rendered slightly acid
by means of acetic acid. The formation of the dyestuff begins immediately, and wili
be finished after having been stirred for about 12 hours. The reaction mass is then
heated, and the dyestuff thus produced is precipitated by the addition of common
salt, filtered off, pressed, and dried. It dyes cotton, in slightly alkaline baths, red
shades.
DYE-STUFF PREPARED FROM ONE MOLECULE OF A DIOXYDINAPHTHYLAMINE DISUL-
PHONIC ACID AND TWO MOLECULES OF DIAZO-BENZENE CHLORIDE.
18.6 kilos. of aniline are diazotised in the usual way by means of hydrochloric acid
and sodium nitrite. The solution of the diazo compound thus obtained is stirred,
while cooling, into a concentrated solution of 46.1 kilos. of the dioxydinaphthylamine
disulphonic acid (having the above mentioned formula), which is mixed with such a
quantity of sodium carbonate, that the reaction mass will remain alkaline throughout
the whole reaction. Stirring is continued for about 12 hours until the reaction is
finished. The mixture is then heated, and the dyestuff thus produced is precipitated

page_text: DYE-STUFF PREPARED FROM ONE MOLECULE OF A
DIOXYDINAPHTHYLAMINE
DISUL-
PHONIC ACID AND 1 MOLECULE OF ANILINE AND 1 MOLECULE OF ALPHA-
NAPHTHYL AMINE.
The combination of the dioxydinaphthylamine disulphonic acid (having the above
mentioned formula) with diazo benzene chloride, is performed as is described in the
Example A. When the reaction is finished, the mass is rendered alkaline by means
of a sufficient quantity of sodium carbonate. Subsequently, a diazo solution prepared
from 14.3 kilos. of alphanaphthylamine is added, with stirring and cooling. After
the reaction is finished, which will be the case after about 12 hours, the reaction mass
is heated to about 80 degrees Centigrade, and the dye stuff thus produced is pre-
cipitated by the addition of common salt, pressed, and dried. It dyes cotton,
reddish-violet shades.
The process proceeds in an analogous manner, if other of the above mentioned
components are used.
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.
D
The Manufacture or Production of New Azo-Dyestuffs for Cotton.
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 disulphonic acid of dioxydi-
naphthylamine, which has the formula-
is a valuable intermediate product for the preparation of dye-stuffs.
It may be remarked that according to the researches of my foreign correspondents,
5 the said dioxydinaphthylamine disulphonic acid having the above given formula can
be prepared by heating betal-amido-alpha3-naphthol-beta4-sulphonic acid with.
sulphurous acid, or with salts of this acid.

page_text: According to recent researches of my foreign correspondents, this dioxydi-
naphthylamine disulphonic acid is capable of combining with one and likewise with
two molecules of diazo-compounds, new valuable azo-dyestuffs being thus obtained
which dye unmordanted cotton from red to blue bright and fast shades.
In order to combine one molecule of the said dinaphthylamine disulphonic acid
with only one molecule of a diazo compound, the reaction is preferably performed in
a slightly acid solution, whilst the combination with two molecules of diazo com-
In the latter case, the same
pounds is profitably performed in an alkaline solution.
or two different diazo compounds may be used.
In the following table, the shades produced on unmordanted cotton by several of
the new dyestuffs obtainable according to the new process, are given.
The dyestuff produced by the combination of one molecule of the dioxydinaphthyl-
amine disulphonic acid obtained from betal-amido-alpha3-naphthol-beta4-sulphonic
acid, and having most probably the formula-
DYESTUFF PREPARED FROM ONE MOLECULE OF DIOXYDINAPHTHYLAMINE DISULPHONIC
ACID AND ONE MOLECULE OF DIAZO BENZENE CHLORIDE.
9.3 kilos. of aniline are diazotized in the usual way by means of sodium nitrite and
hydrochloric acid. The diazo solution thus obtained is allowed to run, while cooling
and being stirred, into a concentrated solution of 46.1 kilos. of the dioxydinaphthyl-
amine disulphonic acid (having the above mentioned formula), which solution has
been mixed with a sufficient quantity of sodium acetate, and has been rendered
slightly acid by means of acetic acid. The formation of the dye-stuff begins
immediately, and will be finished after having been stirred for about 12 hours. The
reaction mass is then heated, and the dye-stuff thus produced is precipitated by the

page_text: DYESTUFF PREPARED FROM ONE MOLECULE OF DIOXYDINAPHTHYLAMINE DISULPHONIC
ACID AND 2 MOLECULES OF DIAZO BENZENE CHLORIDE.
18.6 kilos. of aniline are diazotized in the usual way by means of hydrochloric acid
and sodium nitrite. The solution of the diazo-compound thus obtained is stirred,
while cooling, into a concentrated solution of 46-1 kilos. of the dioxydinaphthylamine
disulphonic acid (having the above mentioned formula), which is mixed with such a
quantity of sodium carbonate, that the reaction mass will remain alkaline throughout
the whole reaction.
Stirring is continued for about 12 hours, until the reaction is finished. The
mixture is then heated, and the dyestuff thus produced is precipitated by means of
common salt, filtered off, pressed, and dried. It dyes unmordanted cotton, bright
blueish-red shades.
DYE-STUFF PREPARED FROM ONE MOLECULE OF DIOXYDINAPHTHYLAMINE DISULPHONIC
ACID AND ONE MOLECULE OF ANILINE AND ONE MOLECULE OF ALPHANAPHTHYL-
AMINE.
The combination of the dioxydinaphthylamine disulphonic acid (having the above
mentioned formula) with diazo-benzene chloride, is performed as is described in
Example A. When the reaction is finished, the mass is rendered alkaline by means
of a sufficient quantity of sodium carbonate. Subsequently, a diazo solution prepared
from 14.3 kilos. of alphanaphthylamine is added with stirring & cooling. After the
reaction is finished, which will be the case after about 12 hours, the reaction mass is
heated at about 80 degrees Centigrade, and the dyestuff thus produced is pre-
cipitated by the addition of common salt, pressed, and dried.
violet shades.
It dyes cotton, reddish-
The process proceeds in an analogous manner if other of the above mentioned
components are used.
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 inven-
tion, 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 azo-dye-stuffs for cotton, which process
consists in combining one molecule of the alpha3-dioxy-betal-dinaphthylamine-beta4-
disulphonic acid, having most probably the following formula :—

page_text: with either one or two molecules of the same diazo compound, or with two molecules
of two different diazo compounds, substantially as herein before described.
2. As new articles of manufacture, the colouring matters obtainable by the process
herein before described and claimed.