Colouring Matters Obtainable by the Combination of Tetrazo- ditolyl or Tetrazodixylyl-salts with Alpha- and Beta-naphtyl- amine or their Mono- and Disulpho-acids, and Process for the Manufacture of the same.
Year: 1885

page_text: This Specification was, upon the 27th day of March 1890, Amended under
Sections 18 to 21 of the Patents, Designs, and Trade Marks Act, 1883.
Colouring Matters
Obtainable by the Combination of Tetrazo-
ditolyl or Tetrazodixylyl-salts with Alpha- and Beta-naphtyl-
amine or their Mono- and Disulpho-acids, and Process for
the Manufacture of the same.
I, HERBERT JOHN HADDAN, of 67, Strand, in the City of Westminster, Civil
Engineer, do hereby declare the nature of said invention for COLOURING MATTERS
OBTAINABLE BY THE COMBINATION OF TETRAZODITOLYL- OR TETRAZODIXYLYL-
SALTS WITH ALPHA- AND BETA-NAPHTYLAMINE OR THEIR MONO- AND DISULPHO-
ACIDS, AND PROCESS FOR THE MANUFACTURE OF THE SAME, a communication to
me from abroad by the Farbenfabriken vorm. Fr. Bayer and Company, a Joint
Stock Company, of Elberfeld, in the German Empire, to be as follows:-
My correspondents have discovered, that the salts of the tetrazo-ditolyls
produced from nitrotoluol, as well as those of the tetrazodixylyl from nitro xylol,
when combined with alpha and beta-naphtylamine and their mono and disulpho-
acids, produce fine colouring matters, soluble partly in water and partly in alcohol,
which colouring matters are capable of dyeing cotton in the soap-bath from
yellowish red to blueish-red, and are less subject to destruction or alteration by
dilute acids than the benzidine-dyes.
A convenient method of producing these colouring matters consists in causing
aqueous solutions of tetrazo-ditolyl- or tetrazodixylyl-salts to flow into the alpha
and beta-naphtylamine-salts or into the alcoholic solutions of the mono- and
disulpho-acids of the alpha- and beta-naphtylamine.
Instead of the aqueous solution of the naphtylamine-salts, the alcoholic solution
of the free alpha- and beta-naphtylamine may be employed, and instead of the
alcoholic solutions of the naphtylamine-sulpho-acids, the free sulpho-acids finely
suspended in water, in the latter case it is necessary to bind any free mineral acids,
which may be present, by means of salts of organic acids.
A particularly fine colouring substance is obtained by the combination of
tetrazoditolyl or tetrazodixylyl with naphtionic acid (the little soluble monosulpho-
acid of the alpha-naphtylamine). It slightly more yellow than the red colouring
רנס ...

page_text: matter obtained by Böttinger from tetrazodiphenyl with naphtionic acid, and
differs from the latter by its being less sensitive to dilute acids, and therefore
much more valuable.
This colouring matter may be produced by dissolving 100 kilos of sulphate of
tolidin (diamidoditolyl, obtained by the alcoholic reduction of nitrotoluol and
digesting the hydrazotoluol thus produced with concentrated acids) in water
containing 100 kilos of hydrochloric acid of 20° B, cooling the solution with
ice and slowly adding 44:4 kilos of natrium-nitrite dissolved in 200 liters of
water.
In this way Tetrazoditolyl-chloride is produced. This solution is now added to
112 kilos of naphtionic acid finely suspended in water, the free mineral acids are
bound or rendered harmless, for instance by natrium-acetate, and the mixture is
allowed to stand for about 24 hours. The reddish-brown precipitate thus formed
is converted into an alkali-salt.
The manufacture of colouring matters from alpha and beta naphtylamine, or
from the sulpho-acids of the beta-naphtylamine takes place in a similar manner.
The former are blueish-red and soluble in alcohol, the latter are yellowish-red
and soluble in water.
The dyes soluble in alcohol may be converted into dyes soluble in water by
treatment with fuming sulphuric acid.
DL
Manal 100%
HERBERT & Co.,
Agents,
67, Strand.

page_text: amine or their Mono- and Disulpho-acids, and Process for
the Manufacture of the same.
I, HERBERT JOHN HADDAN, of 67 Strand, in the City of Westminster, Civil
Engineer, do hereby declare the nature of this invention, a communication to me
from abroad by the Farbenfabriken vorm. Fr. Bayer and Company, a Joint Stock
Company, of Elberfeld, in the German Empire, and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement :-
My correspondents have discovered, that the salts of the tetrazo-ditolyls
produced from ortho or technical nitrotoluol, as well as those of the tetrazo-dixylil
from-nitro-xylol, when combined with alpha- end or beia-naphthylamine and or their
mono- and disulpho-acids, produce fine colouring matters, soluble partly in water and
partly in alcohol, which colouring matters are capable of dyeing unmordanted cotton
in the soap or alcoholic alkaline bath from yellowish-red to blueish-red, and are less
subject to destruction or alteration by dilute acids than the benzidine dyes.
The name of tetrazoditolyl is understood to designate the tetrazo-combinations
of the ortho- and para- tolidin, either separately or in mixture as has been
described by G. Schultz (Reports of the "German Chemical Society". Vol. XVII
1884, p. 467 and 472). The name of tetrazodixylil is understood to designate the
tetrazo combinations of the diamido dixylil.
A convenient method of producing these coloring matters consists in causing
aqueous solutions of tetrazo-ditolyl- or tetrazo dix lil salts to flow into the aqueous
solutions of the alpha- and or beta-naphthylamine-salts or into the alkaline solutions
of the mono- and or disulpho-acids of the alpha- and or beta-naphtylamines. Instead
of the aqueous solution of the naphthylamine-salts, the alcoholic solution of the
free alpha- and or beta-naphthylamine may be employed, and instead of the alkaline.
solutions of the naphthylamine-sulpho-acids, the free sulpho-acids finely suspended
in water; in the latter case it is necessary to bind any free mineral acids, which
may be present, by means of salts of organic acids.
A particularly fine colouring substance is obtained by the combination of
tetrazoditolyl or tetrazodixylil with the beta monosulpho-acid of beta-naphthylamine
(formed by heating Schäffer's beta-naphthol- beta-monosulpho-acid with ammonia).
It is slightly more yellow than the red colouring matter, obtained by Böttiger
from tetrazo-diphenyl with alpha-naphthionic-acid, and differs from the latter
essentially by its being less sensitive to diluted acids, and therefore much more
valuable.
This colouring matter may be produced by suspending in water, containing
100 kilos of hydrochloric acid at 20° Be., 100 kilos of sulphate of tolidin (diamido-
ditolyl, obtained from ordinary nitrotoluol), cooling the solution with ice and slowly
adding a solution of 44.4 kilos of natrium-nitrite in 200 litres of water.

page_text: In this way, tetrazoditolyl-chloride is produced. This solution is now added to
112 145 kilos of beta-naphthylamine- beta monosulpho-acid, finely suspended in
water; the three mineral acids are bound or rendered harmless, for instance by
natrium-acetate, and the mixture is allowed to stand for about 24 hours. The
reddish-brown precipitate thus formed is converted into an alenli- alkaline-salt. The
precipitate forms more rapidly if the temperature is raised.
In the same manner a very valuable colouring matter is obtained by the
combination of ortho-or paratetrazoditolyl salts with that ẞ naphthylamine- mono
sulpho-acid, which is formed by heating ß naphthylamine with concentrated sulphuric
acid to 200-210° Centigrade.
These colouring matters, produced by the action of tetrazoditolyl salts on
ẞnaphthylamine-sulpho acids, differ essentially from the corresponding benzidin
coloring matters.
While the latter are almost entirely nearly insoluble, even in boiling water and
cannot therefore only difficulty be fixed on cotton, the colouring matters, obtained
from tetrazoditolyl, are easily soluble in water and have the property of dyeing
unmordanted cotton in the alekaline bath magnificently blueish-red.
The production of the colouring matters from a and ẞ naphthylamine or from the
other sulpho-acids of the naphthylamine is effected by the same method of
operation and under the same phenomena.
The former are soluble in spirits and blueish-red, the latter are soluble in water
and yellowish red. For the purpose of this invention the use of the Alpha monosulpho-
acid and the gamma disulpho acid of Beta naphthylamine is disclaimed.
The colouring matters, soluble in spirits, may be converted into colouring matters
soluble in water by treatment with fuming sulphuric acid.
Having now particularly described and ascertained the nature of my said
Invention, and in what manner the same is to be performed, 1 declare that what
I claim is
1.) The new colouring matters, which are obtained by the action of tetrazoditolyl-
or-tetrazodxylil- salts on a and ẞ naphthylamine or on the mono- and disulpho-acids
of the same.
2.) The process for producing new colouring matters soluble partly in spirits and
partly in water, which process consists in causing tetrazoditolyl-and-tetrazodixylil-
salts to act on a and ẞ naphthylamine or on the salts of the same or on the mono-
and disulpho acids of the a and ẞ naphthylamine.
3.) Converting the colouring matters soluble in spirits and formed by the action
of tetrazoditolyl- and tetrazodixylil-salts on a and ẞ naphthylamine, into colouring
matters soluble in water, by sulphising sulphonating the same, substantially as
described.
Dated this 21st day of October 1885
H. J. HADDAN,
By Herbert & Co., Agents,
67, Strand.

page_text: ditolyl- or Tetrazodixylyl-salts with Alpha- and Beta-naphtyl-
amine or their Mono- and Disulpho-acids, and Process for
the Manufacture of the same.
I, HERBERT JOHN HADDAN, of 67, Strand, in the City of Westminster, Civil
Engineer, do hereby declare the nature of said invention for COLOURING MATTERS
OBTAINABLE BY THE COMBINATION OF TETRAZODITOLYL- OR TETRAZODIXYLYL-
SALTS WITH ALPHA- AND BETA-NAPHTYLAMINE OR THEIR MONO- AND DISULPHO-
ACIDS, AND PROCESS FOR THE MANUFACTURE OF THE SAME, a communication to
me from abroad by the Farbenfabriken vorm. Fr. Bayer and Company, a Joint
Stock Company, of Elberfeld, in the German Empire, to be as follows:-
My correspondents have discovered, that the salts of the tetrazo-ditolyls
produced from nitrotoluol, as well as those of the tetrazodixylyl from nitro xylol,
when combined with alpha and beta-naphtylamine and their mono and disulpho-
acids, produce fine colouring matters, soluble partly in water and partly in alcohol,
which colouring matters are capable of dyeing cotton in the soap-bath from
yellowish red to blueish-red, and are less subject to destruction or alteration by
dilute acids than the benzidine-dyes.
A couvenient method of producing these colouring matters consists in causing
aqueous solutions of tetrazo-ditolyl- or tetrazodixylyl-salts to flow into the alpha
and beta-naphtylamine-salts or into the alcoholic solutions of the mono- and
disulpho-acids of the alpha- and beta-naphtylamine.
Instead of the aqueous solution of the naphtylamine-salts, the alcoholic solution
of the free alpha- and beta-naphtylamine inay be employed, and instead of the
alcoholic solutions of the naphtylamine-sulpho-acids, the free sulpho-acids finely
suspended in water, in the latter case it is necessary to bind any free mineral acids,
which may be present, by means of salts of organic acids.
A particularly fine colouring substance is obtained by the combination of
tetrazoditolyl or tetrazodixylyl with naphtionic acid (the little soluble monosulpho-
acid of the alpha-naphtylamine). It is slightly more yellow than the red colouring

page_text: matter obtained by Böttinger from tetrazodiphenyl with naphtionic acid, and
differs from the latter by its being less sensitive to dilute acids, and therefore
much more valuable.
This colouring matter may be produced by dissolving 100 kilos of sulphate of
tolidin (diamidoditolyl, obtained by the alcoholic reduction of nitrotoluol and
digesting the hydrazotoluol thus produced with concentrated acids) in water
containing 100 kilos of hydrochloric acid of 20° B, cooling the solution with
ice and slowly adding 44.4 kilos of natrium-nitrite dissolved in 200 liters of
water.
In this way Tetrazoditolyl-chloride is produced. This solution is now added to
112 kilos of naphtionic acid finely suspended in water, the free mineral acids are
bound or rendered harmless, for instance by natrium-acetate, and the mixture is
allowed to stand for about 24 hours. The reddish-brown precipitate thus formed
is converted into an alkali-salt.
The manufacture of colouring matters from alpha and beta naphtylamine, or
from the sulpho-acids of the beta-naphtylamine takes place in a similar manner.
The former are blueish-red and soluble in alcohol, the latter are yellowish-red
and soluble in water.
The dyes soluble in alcohol may be converted into dyes soluble in water by
treatment with fuming sulphuric acid.

page_text: ditolyl or Tetrazodixylyl-salts with Alpha- and Beta-naphtyl-
amine or their Mono- and Disulpho-acids, and Process for
the Manufacture of the same.
I, HERBERT JOHN HADDAN, of 67 Strand, in the City of Westminster, Civil
Engineer, do hereby declare the nature of this invention, a communication to me
from abroad by the Farbenfabriken vorm. Fr. Bayer and Company, a Joint Stock
Company, of Elberfeld, in the German Empire, and in what manner the same
is to be performed to be particularly described and ascertained in and by the
following statement:―
My correspondents have discovered, that the salts of the tetrazo-ditolyls
produced from nitrotoluol, as well as those of the tetrazo-dixylil from nitro xylol,
when combined with alpha- and beta-naphtylamine and their mono- and disulpho-
acids, produce fine colouring matters, soluble partly in water and partly in alcohol,
which colouring matters are capable of dyeing unmordanted cotton in the soap or
alcoholic bath from yellowish-red to blueish-red, and are less subject to destruction
or alteration by dilute acids than the benzidine dyes.
The name of tetrazoditolyl is understood to designate the tetrazo-combinations
of the ortho- and para-tolidin, either separately or in mixture as has been
described by G. Schulz (Reports of the "German Chemical Society" Vol. XVII
1884, p. 467 and 472). The name of tetrazodixylil is understood to designate the
tetrazo-combinations of the diamido-dixylil.
A convenient method of producing these coloring matters consists in causing
aqueous solutions of tetrazo-ditolyl- or tetrazo-dixylil-salts to flow into the aqueous
solutions of the alpha- and beta-naphtylamine-salts or into the alkaline solutions
of the mono- and disulpho-acids of the alpha- and beta-naphtylamines. Instead
of the aqueous solution of the naphtylamine-salts, the alcoholic solution of the
free alpha- and beta-naphtylamine may be employed, and instead of the alkaline
solutions of the naphtylamine-sulpho-acids, the free sulpho-acids finely suspended
in water; in the latter case it is necessary to bind any free mineral acids, which
may be present, by means of salts of organic acids.
A particularly fine colouring substance is obtained by the combination of
tetrazoditolyl or tetrazodixylil with the beta monosulpho-acid of beta-naphtylamine
(formed by heating Schäffer's beta-naphtol- beta-monosulpho-acid. with ammonia).
It is slightly more yellow than the red colouring matter, obtained by Böttiger
from tetrazo-diphenyl with alpha-naphtionic-acid, and differs from the latter
essentially by its being less sensitive to diluted acids, and therefore much more
valuable.
This colouring matter may be produced by suspending in water, containing
100 kilos of hydrochloric acid at 20° Bć., 100 kilos of sulphate of tolidin (diamido-
ditolyl, obtained from ordinary nitrotoluol), cooling the solution with ice and slowly.
adding a solution of 44,4 kilos of natrium-nitrite in 200 litres of water.
-

page_text: In this way, tetrazoditolyl-chloride is produced. This solution is now added to
112 kilos of beta-naphylamine- beta monosulpho-acid, finely suspended in water;
the free mineral acids are bound or rendered harmless, for instance by natrium-
acetate, and the mixture is allowed to stand for about 24 hours. The reddish-
brown precipitate thus formed is converted into an alcali-salt.
In the same manner a very valuable colouring matter is obtained by the
combination of ortho- or paratetrazoditolyl salt with that ẞ naphtylamine- mono
sulpho-acid, which is formed by heating B naphtylamine with concentrated sulphuric
acid to 200-210° Centigrade.
These colouring matters, produced by the action of tetrazoditolyl salts on
B naphtylamine-sulpho acids, differ essentially from the corresponding benzidin
coloring matters.
While the latter are almost entirely insoluble, even in boiling water and cannot
therefore be fixed on cotton, the colouring matters, obtained from tetrazoditoly},
are easily soluble in water and have the property of dyeing unmordanted cotton in
the alcaline bath magnificently blueish-red.
The production of the colouring matters from a aud ẞ naphtylamine or from the
other sulpho-acids of the ẞ naphtylamine is effected by the same method of
operation and under the same phenomena.
The former are soluble in spirits and blueish-red, the latter are soluble in water
and yellowish red.
The colouring matters, soluble in spirits, may be converted into colouring matters
soluble in water by treatment with fuming sulphuric acid.
Having now particularly described and ascertained the nature of my said
Invention, and in what manner the same is to be performed, I declare that what
I claim is
1.) The new colouring.matters, which are obtained by the action of tetrazoditolyl-
or tetrazodixylil-salts on a and ẞ naphtylamine or on the mono- and disulpho-acids
of the same.
2.) The process for producing new colouring matters soluble partly in spirits and
partly in water, which process.consists in causing tetrazoditolyl- and tetrazodixylil-
salts to act on a and ẞ naphtylamine or on the salts of the same or on the mono-
and disulpho acids of the a and ẞ naphtylamine.
3.) Converting the colouring matters soluble in spirits and formed by the action
of tetrazoditolyl- and tetrazodixylil-salts on a and ẞ naphtylamine, into colouring
matters soluble in water, by sulphising the same, substantially as described.
Dated this 21st day of October 1885.