COLORS PRODUCED FROM DIAZO-AMIDO COMBINATIONS OF TETRAZODIPHENYLE AND ITS HOMOLOGUES
Year: 1887

page_text: Date of Application, 6th May, 1887
Complete Left, 4th Feb., 1888
Complete Accepted, 23rd Mar., 1888
from a Soap Bath.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane in
the County of Middlesex, Fellow of the Institute of Patent Agents (a communication
to me from abroad by The Actiengesellschaft für Anilin-Fabrikation of Berlin in the
German Empire, Manufacturing Chemists) do hereby declare the nature of this
invention to be as follows:-
This invention relates to improved processes for the production of azo-colors that
dye cotton direct from a soap bath.
It is a known fact that the color "Congo" which, as described in the Specification
to patent No. 44154 is obtained by the combination of salts of tetrazo-diphenyle
with a-naphthylamine-sulpho acid, possesses this property. Now, analogous to the
reaction of tetrazodiphenyle is that of its homologues and derivatives, also of tetrazo-
stilbene, tetrazo-dimethoxyle diphenyle, and tetrazo-azo-benzole, and the present
invention consists in the application of these bases for the production of such color
by means of processes which I will proceed to describe.
A. COLORS PRODUCED FROM DIAZO-AMIDO COMBINATIONS OF TETRAZODIPHENYLE AND
ITS HOMOLOGUES.
It has been found, firstly, that instead of the salts of tetrazo-diphenyle or tetrazc-
ditolyle certain diazo-amido combinations of the said tetrazo-combination can be used
which easily split off. Such diazo-amido combinations are obtained by the reaction
of tetrazo-diphenyle or tetrazo-ditolyle upon amido-azo-benzole-sulpho-acids or
amido-azo-tolnole-sulpho-acids or amido-azo-xylole-sulpho-acids.
The combination takes place if a solution of the salt of tetrazo-diphenyle or tetrazo-
ditolyle is entered into a solution of a salt of the aforesaid amido-azo-sulpho acids in

page_text: presence of acetate of soda or of a fitting alkali. One molecule of the tetrazo
compound combines with two molecules of the amido-azo acid to form a precipitate
which, analogous to the diazo-amido combinations, easily decomposes when heated or
when standing for some time. If, however, the newly obtained precipitate is entered
into a solution of a salt of a naphthylamine sulpho acid, the tetrazo-compound splits
off the diazo-amido compound and combines with the naphthylamine-sulpho acid to
form one of the colors described in the above cited patent, while at the same time the
respective amido-azo-acid is regenerated.
If, for instance, a solution of a quantity of salt of tetrazo-diphenyle equivalent to
18.4 kg. of benzidene, is entered into a solution of 40. kg. of amido-azo-benzole-
disulphonate of soda in presence of 40 kg. of acetate of soda, a fine brownish
precipitate of a diazo-amido-combination shortly forms. After about an hour the
reaction will be completed and all the tetrazo-diphenyle be combined. If the
combination thus obtained is then entered into a solution of 70 kg. of salt of naph-
thionate, and if the reaction resulting is kept going on for 12 hours under stirring,
dark colored product of the reaction is formed which, by adding soda and by heating
it, dissolves with a yellow red color.
a
The solution contains side by side two different colors, one being the Congo produced
and the second being the regenerated acid-yellow, (amido-azo-benzole disulphonate of
soda). By an addition of hydrochloric acid the acid of the Congo color precipitates
and is then separated from the soluble amido-azo-benzole-disulpho-acid by filtration.
The precipitated acid is afterwards converted into the sodium salt and the color
precipitated by salt
9.2 kg. of benzidine are converted in the known manner into the hydrochloric
tetrazo-combination. If this latter be entered into a solution of 17.5 kg. of ẞ-naphtly-
lamine disulphonate of soda and of 20 kg. of acetate of soda in 500 litres of water,
the combination of one molecule of benzidine and of one molecule of ẞ-naphthylamine-
sulpho-acid is formed in the shape of a dark-red jelly. The reaction is complete after
having gone on for half an hour.
If, now, a solution of 8 kg. of ẞ-naphthylamine in 12 kg. of hydrochloric acid of
21° Bé. and in 500 litres of water is added, the naphthylamine combines with the
intermediate product obtained. The compound assumes a dark color and becomes
liquid by degrees. The formation of the color is complete after 12 hours.
By adding 12 kg. of soda, the sodium-salt of the acid of the color is formed which
dissolves clear by heating it and which can be precipitated from a boiling solution
by salt.
Instead of using naphthylamine in a hydrochloric aqueous solution it can also be
used as a free base in an alkaline solution.
The color dies cotton quite similar to Congo but withstands the action of free acids
better.
2) Color from benzidine + naphthylamine-disulpho-acid R + ẞ-naphthylamine-
mono-sulpho-acid.
If in Example 1 a solution of 14 kg. of ẞ-naphthylamine-mono-sulphonate of soda
in 500 litres of water is used instead of a solution of 8 kg. of ẞ-naphthylamine in
12 kg. of hydrochloric acid, a color very similar to that described in Example 1 is
obtained which also dies cotton in a bright red shade and which withstands acids.
3) Color from ẞ-naphthylamine-disulpho-acid R + phenole.
If the compound consisting of one molecule of benzidine and of one molecule of
B-naphthylamine-disulpho-acid which according to Example 1 has been obtained in

page_text: ALL COLORS PRODUCED ΠΟΛΙ TETRAZDIMNIUM
Un
WITH SALICYLIC ACID AND α-NAPHTHOLE-DISULPHO-ACID.
1) Colors from salicylic acid.
The production of the intermediate product which consists of one molecule of salt
of tetrazo-diphenyle and of one molecule of salicylic acid, and which is styled diazo-
diphenyle-azo-salicylic acid, is arrived at by the following process.
The tetrazo-diphenyle formed from 18.4 kg. of benzidine, is entered into an alkaline
solution of 13,8 kg. of salicylic acid in about 500 litres of water. After standing
for some time the diazo-diphenyle-azo-salicylic acid separates in the shape of a red-
brown precipitate which serves directly for producing the azo-colors described
hereinafter. For this purpose it is entered into the alkaline solution of one of the
naphthylamine-sulpho-acids, phenoles, or phenole-sulpho-acids mentioned below. If,
however, phenyline-diamine is used, the combination takes place in an acidulated
solution.
If 18.4 kg. of Benzidine and 13.8 kg. of salicylic acid are used there is required
for the production of the colors one or other of the following substances.
10,8 kg. of m-phenylene-diamine.
24,5"
of a-naphthylamine-sulphonate of soda.
24,5 of B-naphthylamine-sulphonate of soda.
9,4 of plienole.
"
"3
11,
"2
24,6
24,6
24,6
34,8
"3
"
""
33
of resorcine.
of a-naphthole-sulphonate of soda.
of B-naphthole-sulphonate of soda (Bayer).
of B-naphthole-sulphonate of soda (Schäffer).
of B-naphthole-disulphonate of soda, R salt.
34,8 of B-naphthole-disulphonate of soda, G salt.
"
The further treatment of thic azo-colors obtained consists in first leaving the product
of the reaction standing for about 12 hours, by then heating it up to boiling, and
finally, by separating the color with salt, filtering, pressing, and drying it.
These colors dye cotton direct from a soap-bath in the following shades:
m-phenylene-diamine
produces brown.
"
a-naphthylamine-sulpho-acid
yellow-red.
B-naphthylamine-sulpho-acid
red-yellow.
"
phenole
"2
yellow.
resorcine
"
yellow-red.
a-naphthole-mono-sulpho-acid
bluish-red.
"
B-naphthole-mono-sulpho-acid (Bayer)
22
yellow-red.
B-naphthole-mono-sulpho-acid (Schäffer)
brownish-red.
"
B-naphthole-disulpho-acid R.
brown-red.
"
B-naphthole-disulpho-acid G
27
brown-yellow.

page_text: .D. COLORS PRODUCED FROM DIAMIDO-STILBENE AND α-NAPHTHOLE-DISULPHO-ACID.
1) By the reaction of salts of tetrazo-stilbene upon a-naphthole-disulpho-acid
a color is obtained which dyes cotton direct from a soap-bath in a dark blue shade.
The production of this color is effected as follows:
28,3 kg. of hydrochloric diamido-stilbene are dissolved in 500 litres of water
mixed with 24 kg. of hydrochloric acid of 20° Bé., and converted into the tetrazo-
stilbene-chloride by entering into the mixture a solution of 13,8 kg. of nitrite
of sodium in 200 litres of water.
The solution of this tetrazo-stilbene-chloride is then entered into an alkaline
solution of 69,6 kg. a-naphthole-disulphonate of soda. -
After standing some time the mixture is heated up to boiling, and the color thus
obtained is precipitated by salt, filtered, pressed, and dried.
The color is easily soluble in water, and dyes cotton direct from a soap-bath in
a blue shade.
2) If one molecule of tetrazo-stilbene-chloride is combined with one molecule of
u-naphthole disulpho-acid, a compound is formed which still contains a free diazo-
group and which is thereby qualified to act upon naphtholes and naphthole-sulpho-acids.
This intermediate product is obtained by the reaction of tetrazo-stilbene derived
from 28,3 kg. of hydrochloric diamido-stilbene, upon an alkaline solution of 34,8 kg.
of the sodium-salt of the above-mentioned naphthole-disulpho acid, whereby the
newly formed substance separates in small brown crystals which do not dissolve
easily. If, now, this compound is combined with one molecule of naphthole, naphthole-
mono-sulpho-acid, or naphthole-disulpho-acid in an alkaline solution, azo-colors are
obtained which dye cotton direct from a soap-bath in a blue shade. If 28,3 kg. of
hydrochloric diamido-stilbene have been used, then for the production of these
azo-colors the following quantities are required:

page_text: E. COLORS PRODUCED FROM DIMETHOXYLE-DIAMIDO-DIPHENYLE, CLÈVÉS a-NAPHTHOLE-
SULPHO-ACID AND a-NAPHTHOLE DISULPHO-ACID.
1) Color from tetrazo-dimethoxyle, diphenyle acid Clèvés a-naphthole-sulpho acid.
31,7 kg. of hydrochloric-dimethoxyle-diamido-diphenyle (from nitranisol) are dis-
solved in 1000 litres of water, mixed with 36 kg. of hydrochloric acid, and converted
into the tetrazo-compound by entering into the mixture a solution of 14 kg. of nitrite
of sodium in 200 liters of water. This tetrazo-compound is then entered into an
alkaline solution of 50 kg. of Clèves naphthole-sulpho-acid in 1000 liters of water.
After several hours standing, the product of the reaction is gradually heated up
to boiling, and the color precipitated by salt, filtered, pressed, and dried. The color
dyes cotton direct from a soap-bath in a dark blue shade.
2) Color from tetrazo-dimethoxyle-diphenyle and a-naphthole-disulpho-acids.
If the solution of tetrazo-dimethoxyle-diphenyle which according to Example 1 has
been derived from 31,7 kg. of hydrochloric dimethoxyle-diamido-diphenyle, is entered
into an alkaline solution of 75 kg. of the sodium salt of a-naphthole-disulpho-acid in
1000 litres of water, a color is obtained which dyes cotton direct from a soap-bath in a
blue-shade.
This color is separated in, quite the same manner as that obtained according to
Example 1. The shade is a little greener than that of the above described color.
3) Color from tetrazo-dimethoxyle-diphenyle-Clèvé's naphthole-mono-sulpho-acid
and a-naphthole-disulpho-acid.
If instead of 50 kg. of Clèvés naphthole sulpho-acid mentioned in process 1 only
25 kg. of the same are used, and if the intermediate product thus obtained is combined
with 36 kg. of a-naphthole-disulphonate of soda a color is obtained which dyes cotton
direct from a soap-bath in a blue shade. This color can also be obtained by
combining the tetrazo-dimethoxyle-diphenyle first with the disulpho-acid and aftewards
with the mono-sulpho-acid..
F. Azo-COLORS PRODUCED FROM P-DIAMIDO-AZO-BENZOLE AND ITS HOMOLOGUES
AND DERIVATIVES.
It has been found that the diamido-azo-benzole described by Neitzki can be
converted into the tetrazo-compound by the calculated quantity (two molecules)
of nitrite of soda and, that this tetrazo-compound can be combined to form azo-colors
with two equal or different molecules of amines, phenoles, or their sulphonic or
carbonic acids. Some of these colors are valuable by their property of dyeing
non-mordanted cotton direct from a soap-bath.
In the same manner act those p-diamido-azo-combinations which are constituted
analogous to diamido-azo-benzole and which are obtained by replacing in the process
of Nietzki the aniline by toluidine, xylidine, or naphthylamine..
1) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho acid.
2,12 kg. of diamido-azo-benzole are dissolved in 5 kg. of hydrochloric acid of
20° Bé. and in 100 litres of water, and converted into the tetrazo-compound by adding
a solution of 1,38 kg. of nitrite in 20 litres of water. This compound is entered
under constant stirring into a solution of 6,5 kg. of a-naphthylamine-sulphonate
of soda and of 1,5 kg. of soda in 200 litres of water. After standing for about
12 hours, the product of the reaction is dissolved by boiling and the color is pre-
cipitated by salt, pressed and dried. It dyes cotton from an alkaline soap-bath
in a red violet shade.

page_text: 2) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho-acids.
If in Example 1 the a-naphthylamine-sulphonate of soda is replaced by 5 kg.
of a-naphthole-mono-sulphonate of soda, a color is obtained which does not dissolvo
easily, and which dyes non-mordanted cotton in a violet shade.
3) Color from p-diamido-azo-benzole + B-naphthole di-sulpho-acid.
A blue color is obtained by converting 2,12 kg. of p-diamido-azo-benzole in the
manner already described into the tetrazo-compound and by combining the latter with
an alkaline solution of 7 kg. of ẞ3-naphthole-disulphonate of soda (R salt).

page_text: AND ITS HOMOLOGUES.
It has been found, firstly, that instead of the salts of tetrazo-diphenyle or tetrazo-
ditolyle certain diazo-amido-combinations of the said tetrazo combination can be used
which easily split off. Such diazo-amido combinations are obtained by the reaction
of tetrazo-diphenyle or tetrazo-ditolyle upon amido-azo-benzole-sulpho-acids or amido-
azo-toluole-sulpho-acids or amido-azo-xylole-sulpho-acids.
The combination takes place if a solution of the salt of tetrazo diphenyle or tetrazo
ditolyle is entered into a solution of a salt of the aforesaid amido-azo-sulpho-acids
in presence of acetate of soda or of a fitting alkali. One molecule of the tetrazo-
compound combines with two molecules of the amido-azo-acid to form a precipitate
which, analogous to the diazo-amido combinations, easily decomposes when heated or
when standing for some time. If, however, the newly obtained precipitate is entered
into a solution of a salt of a naphthylamine-sulpho acid, the tetrazo-compound
splits off the diazo-amido-compound and combines with the naphthylamine-sulpho and
to form one of the colors described in the above cited patent, while at the same time
the respective amido azo-acid is regenerated. If, for instance a solution of a quantity
of salt of tetrazo-diphenyle equivalent to 18.4 kg. of benzidine, is entered into a
solution of 40 kg. of amido-azo-benzole-disulphonate of soda in presence of 40 kg. of

page_text: acetate of soda, a fine brownish precipitate of a diazo-amido-combination shortly
forms. After about an hour the reaction will be completed and all the tetrazo-
diphenyle be combined. If the combination thus obtained is then entered into a
solution of 70 kg. of salt of naphthionate, and if the reaction resulting is kept going
on for 12 hours under stirring, a dark colored product of the reaction is formed which,
by adding soda and by heating it, dissolves with a yellow red color.
The solution contains side by side two different colors, one being the Congo
produced and the second being the regenerated acid-yellow, (amido-azo-benzole-
bisulphonate of soda). By an addition of hydrochloric acid the acid of the Congo
color precipitates and is then separated from the soluble amido-azo-benzole-disulpho-
acid by filtration. The precipitated acid is afterwards converted into the sodium salt
and the color precipitated by salt.
1) Color from benzidine + ẞ-naphthylamine disulpho acid R +1ẞ-naphthylamine.
9.2 kg. of benzidine are converted in the known manner into the hydrochloric
tetrazo-combination. If this latter be entered into a solution of 17.5 kg. of
B-naphthylamine-disulphonate of soda and of 20 kg. of acetate of soda in 500 litres
of water, the combination of one molecule of benzidine and of one molecule of
B-naphthylamine sulpho-acid is formed in the shape of a dark red jelly. The reaction
is complete after having gone on for half an hour.
If, now, a solution of 8 kg. of ẞ-naphthylamine in 12 kg. of hydrochloric acid of
21° Bé. and in 500 litres of water is added, the naphthylamine combines with the
intermediate product obtained. The compound assumes a dark color and becomes
liquid by degrees. The formation of the color is complete after 12 hours.
adding 12 kg. of soda, the sodium-salt of the acid of the color is formed which
dissolves clear by heating it and which can be precipitated from a boiling solution by
salt.
By
Instead of using naphthylamine in a hydrochloric aqueous solution it can also be
used as a free base in an alkaline solution.
The color dyes cotton quite similar to Congo but withstands the action of free
acids better.
2) Color from benzidine + naphthylamine-disulpho acid R+ ß-naphthylamine-
mono-sulpho-acid.
If in Example 1 a solution of 14 kg. of B-naphthylamine-mono-sulphonate of soda in
500 litres of water is used instead of a solution of 8 kg. of B-naphthylamine in 12 kg.
of hydrochloric acid, a color very similar to that described in Example 1 is obtained
which also dyes cotton in a bright red shade and which withstands acids.
3) Color from ẞ-naphthylamine-disulpho-acid R + phenole.
If the compound consisting of one molecule of benzidine and of one molecule of
B-naphthylamine-disulpho-acid which according to Example 1 has been obtained in
shape of a dark red jelly, is entered into a solution of 5 kg. of phenole in 7 kg. of soda
lye of 40° Bé. and of 11 kg. of soda in 500 litres of water, the formation of the color
takes place instantaneously. The color can be precipitated by salt, and dyes cotton
a bright orange shade.
4) Color from benzidine ẞ-naphthylamine-disulpho-acid R + a-naphthole.
If in Example 3 the phenole is replaced by 8 kg. of a-naphthole, a color is obtained
which dyes cotton a reddish brown shade.
In all cases the benzidine can be replaced by Tolidine, and the colors then obtained
possess analogous properties to those described above.

page_text: C. MIXED AZO-COLORS PRODUCED FROM TETRAZO-DIPHENYLE OR TETRAZO-DITOLYLE
WITH SALICYLIC ACID AND a-NAPHTHOLE-DISULPHO-ACID.
1) Colors from salicylic acid.
The production of the intermediate product which consists of one molecule of salt
of tetrazo-diphenyle and of one molecule of salicylic acid, and which is styled diazo-
diphenyle-azo-salicylic acid, is arrived at by the following process.
The tetrazo-diphenyle formed from 18.4 kg. of benzidine, is entered into an alkaline
solution of 13.8 kg. of salicylic acid in about 500 litres of water. After standing for
some time the diazo-diphenyle-azo-salicylic acid separatesin the shape of a red-brown
precipitate which serves directly for producing the azo-colors described hereinafter.
For this purpose it is entered into the alkaline solution of one of the naphthylamine-
sulpho-acids, phenoles, or phenole-sulpho-acids mentioned below. If, however,
phenylene-diamine is used, the combination takes place in an acidulated solution.
If 18.4 kg. of benzidine and 13.8 kg. of salicylic acid are used there is required for
the production of the colors one or other of the following substances:
10.8 kg. of m-phenylene-diamine.
24.5 of a-naphthylamine-sulphonate of soda.
وو
24.5 of B-naphthylamine-sulphonate of soda..
""
9.4
""
11.
24.6
22
24.6
24.6
34.8
12
"
"
of phenole.
of resorcine.
of a-naphthole-sulphonate of soda.
of B-naphthole-sulphonate of soda (Bayer).
of B-naphthole-sulphonate of soda (Schäffer).
of B-naphthole-disulphonate of soda, R salt."
34.8 of ẞ-naphthole-disulphonate of soda G salt.
""
The further treatment of the azo-colors obtained consists in first leaving the product
of the reaction standing for about 12 hours, by then heating it up to boiling, and
finally, by separating the color with salt, filtering, pressing, and drying it.
These colors dye cotton direct from a soap-bath in the following shades:
produces brown.
yellow-red.
red-yellow.
m-phenylene-diamine
a-naphthylamine-sulpho-acid
39
B-naphthylamine-sulpho-acid
"
phenole
"
yellow.
resorcine
"
yellow-red.
a-naphthole-mono-sulpho-acid
bluish-red.
"
B-naphthole-mono-sulpho-acid (Bayer)
"
B-naphthole-mono-sulpho-acid (Schäffer)
yellow-red.
brownish-red.
""
B-naphthole-disulpho-acid R
B-naphthole-disulpho-acid G
2) Colors from a-naphthole-disulpho-acid.
If a solution of tetrazo-diphenyle from 18.4 kg. of benzidine, or of tetrazo-ditolyle
from 21.4 kg. of tolidine, acts upon an alkaline or acetic solution of 34.8 kg. a-naphthole-
"
"
brown-red.
brown-yellow.

page_text: These colors also dye cotton direct from a soap-bath, and yield the following shades:
phenole -
a-naphthole
a-naphthole-mono-sulpho acid
B-naphthole-disulpho acid
D. Azo-COLORS
tetrazo-diphenyle tetrazo-ditolyle
bluish-red red-brown.
-
blue-violet red-violet.
violet
blue
-
-
blue-violet.
blue.
PRODUCED FROM P-DIAMIDO-AZO-BENZOLE
AND DERIVATIVES.
AND ITS HOMOLOGUES
It has been found that the diamido-azo-benzole described by Nietzki can be con-
verted into the tetrazo-compound by the calculated quantity (two molecules) of nitrite of
soda and, that this tetrazo-compound can be confined to formazo-colors with two equal
or different molecules of amines, phenoles, or their sulphonic or carbonic acids.
Some of these colors are valuable by their property of dyeing non-mordanted cotton
direct from a soap-bath.
In the same manner act those p-diamido-azo-combinations which are constituted
analogous to diamido-azo-benzole and which are obtained by replacing in the process
of Nietzki the aniline by toluidine, xylidine, or naphthylamine.
1) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho-acid.
2.12 kg. of diamido-azo-benzole are dissolved in 5 kg. of hydrochloric acid of 20° Bé.
and in 100 litres of water, and converted into the tetrazo-compound by adding a
solution of 1.38 kg. of nitrite in 20 litres of water. This compound is entered under
constant stirring into a solution of 6.5 kg. of a-naphthylamine sulphonate of soda and
of 1.5 kg. of soda in 200 litres of water. After standing for about 12 hours, the
product of the reaction is dissolved by boiling and the color is precipitated by salt,
pressed and dried-It dyes cotton from an alkaline soap-bath in a red violet shade.
2) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho-acids.
If in Example 1 the a-naphthylamine-sulphonate of soda is replaced by 5 kg. of
a-naphthole-mono-sulphonate of soda a color is obtained which does not dissolve
easily, and which dyes non-mordanted cotton in a violet shade.
3) Color from p-diamido-azo-benzole + ß-naphthole-disulpho acid.
A blue color is obtained by converting 2.12 kg. of p-diamido-azo-benzole in the
manner already described into the tetrazo-compound and by combining the latter
with an alkaline solution of 7 kg. of B-naphthole-disulphonate of soda (R salt).
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 production of colors from diazo-amido-combinations of tetrazo-diphenyle
and its homologues, substantially as herein described under head A.
2. The production of mixed colors from benzidine or tolidine and naphthylamine
disulpho-acids, substantially as herein described under head B.
3. The production of mixed colors from tetrazo-diphenyle or tetrazo-ditolyle with
salicylic acid and a-naphthole-disulpho-acid substantially as herein described under
head C.
4. The production of azo colors from diamido-azo-benzole and its homologues
and derivatives, substantially as herein described under head D.
1000
ABEL & IMRAY,
Agents for the Applicant.

page_text: from a Soap Bath.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane in
the County of Middlesex, Fellow of the Institute of Patent Agents (a communication
to me from abroad by The Actiengesellschaft für Anilin-Fabrikation of Berlin in the
German Empire, Manufacturing Chemists) do hereby declare the nature of this
invention to be as follows :—
This invention relates to improved processes for the production of azo-colors that
dye cotton direct from a soap bath.
It is a known fact that the color "Congo" which, as described in the Specification
to patent No. 441584 is obtained by the combination of salts of tetrazo-diphenyle
with a-naphthylamine-sulpho acid, possesses this property. Now, analogous to the
reaction of tetrazodiphenyle is that of its homologues and derivatives, also of tetrazo-
stilbene, tetrazo-dimethoxyle diphenyle, and tetrazo-azo-benzole and the present
invention consists in the application of these bases for the production of such color
by means of processes which I will proceed to describe
A. COLORS PRODUCED FROM DIAZO-AMIDO COMBINATIONS OF TETRAZODIPHENYLE AND
ITS HOMOLOGUES.
It has been found, firstly, that instead of the salts of tetrazo-diphenyle or tetrazo-
ditolyle certain diazo-amido combinations of the said tetrazo-combination can be used
which easily split off. Such diazo-amido combinations are obtained by the reaction
of tetrazo-diphenyle or tetrazo-ditolyle upon amido-azo-benzole-sulpho-acids or
nmido-azo-toluole-sulpho-acids or amido-azo-xylole-sulpho-acids.
The combination takes place if a solution of the salt of tetrazo-diphenyle or tetrazo-
ditolyle is entered into a solution of a salt of the aforesaid amido-azo-sulpho acids in

page_text: presence of acetate of soda or of a fitting alkali. One molecule of the tetrazo
compound combines with two molecules of the amido-azo acid to form a precipitate
which, analogous to the diazo-amido combinations, easily decomposes when heated or
when standing for some time. If, however, the newly obtained precipitate is entered
into a solution of a salt of a naphthylamine sulpho acid, the tetrazo-compounds splits
off the diazo-amido compound and combines with the naphthylamine-sulpho acid to
form one of the colors described in the above cited patent, while at the same time the
respective amido-azo-acid is regenerated.
If, for instance, a solution of a quantity of salt of tetrazo-diphenyle equivalent to
184 kg. of benzidene, is entered into a solution of 40. kg. of amido-azo-benzole-
disulphonate of soda in presence of 40 kg. of acetate of soda, a fine brownish
precipitate of a diazo-amido-combination shortly forms. After about an hour the
reaction will be completed and all the tetrazo-diphenyle be combined. If the
combination thus obtained is then entered into a solution of 70 kg. of salt of naph-
thionate, and if the reaction resulting is kept going on for 12 hours under stirring,
dark colored product of the reaction is formed which, by adding soda and by heating
it, dissolves with a yellow red color.
a
Thesolution contains side by side two different colors, one being the Congo produced
and the second being the regenerated acid-yellow, (amido-azo-benzole disulphonate of
soda). By an addition of hydrochloric acid the acid of the Congo color precipitates
and is then separated from the soluble amido-azo-benzole-disulpho-acid by filtration.
The precipitated acid is afterwards converted into the sodium salt and the color
precipitated by salt.
B. MIXED COLORS PRODUCED FROM NAPHTHYLAMINE DISULPHO ACIDS.
1) Color from benzidine + B-naphthylamine-disulpho acid R + B-naphthylamine.
9.2 kg. of benzidine are converted in the known manner into the hydrochloric
tetrazo-combination. If this latter be entered into a solution of 17.5 kg. of ẞ-naphthy-
lamine disulphonate of soda and of 20 kg. of acetate of soda in 500 litres of water,
the combination of one molecule of benzidine and of one molecule of ẞ-naphthylamine-
sulpho-acid is formed in the shape of a dark-red jelly. The reaction is complete after
having gone on for half an hour.
If, now, a solution of 8 kg. of ẞ-naphthylamine in 12 kg. of hydrochloric acid of
21° Bé. and in 500 litres of water is added, the naphthylamine combines with the
intermediate product obtained. The compound assumes a dark color and becomes
liquid by degrees. The formation of the color is complete after 12 hours.
By adding 12 kg. of soda, the sodium-salt of the acid of the color is formed which
dissolves clear by heating it and which can be precipitated from a boiling solution
by salt.
Instead of using naphthylamine in a hydrochloric aqueous solution it can also be
used as a free base in an alkaline solution.
The color dyes cotton quite similar to Congo but withstands the action of free acids
better.
2) Color from benzidine + naphthylamine-disulpho-acid R + B-naphthylamine-
mono-sulpho-acid.
If in Example 1 a solution of 14 kg. of B-naphthylamine-mono-sulphonate of soda
in 500 litres of water is used instead of a solution of 8 kg. of B-naphthylamine in
12 kg. of hydrochloric acid, a color very similar to that described in Example 1 is
obtained which also dyes cotton in a bright red shade and which withstands acids.
3) Color from ẞ-naphthylamine-disulpho-acid R + phenole.
If the compound consisting of one molecule of benzidine and of one molecule of
B-naphthylamine-disulpho-acid which according to Example 1 has been obtained in

page_text: E. COLORS PRODUCED FROM DIMETHOXYLE-DIAMIDO-DIPHENYLE, CLÈVES' a-NAPHTHOLE-
SULPHO-ACID AND a-NAPHTHOLE DISULPHO-ACID.
1) Color from tetrazo-dimethoxyle, diphenyle acid Clèvés a-naphthole-sulpho acid.
31,7 kg. of hydrochloric-dimethoxyle-diamido-diphenyle (from nitranisol) are dis-
solved in 1000 litres of water, mixed with 36 kg. of hydrochloric acid, and converted
into the tetrazo-compound by entering into the mixture a solution of 14 kg. of nitrite
of sodium in 200 liters of water. This tetrazo-compound is then entered into an
alkaline solution of 50 kg. of Clèvés naphthole-sulpho-acid in 1000 liters of water.
After several hours standing, the product of the reaction is gradually heated up
to boiling, and the color precipitated by salt, filtered, pressed, and dried. The color
dyes cotton direct from a soap-bath in a dark blue shade.
2) Color from tetrazo-dimethoxyle-diphenyle and a-naphthole-disulpho-acids.
If the solution of tetrazo-dimethoxyle-diphenyle which according to Example 1 has
been derived from 31,7 kg. of hydrochloric dimethoxyle-diamido-diphenyle, is entered
into an alkaline solution of 75 kg. of the sodium salt of a-naphthole-disulpho-acid in
1000 litres of water, a color is obtained which dyes cotton direct from a soap-bath in a
blue-shade.
This color is separated in quite the same manner as that obtained according to
Example 1. The shade is a little greener than that of the above described color.
3) Color from tetrazo-dimethoxyle-diphenyle-Clève's naphthole-mono-sulpho-acid
and a-naphthole-disulpho-acid.
If instead of 50 kg. of Clèvés naphthole sulpho-acid mentioned in process 1 only
25 kg. of the same are used, and if the intermediate product thus obtained is combined
with 36 kg. of a-naphthole-disulphonate of soda a color is obtained which dyes cotton
direct from a soap-bath in a blue shade. This color can also be obtainied by
combining the tetrazo-dimethoxyle-diphenyle first with the disulpho-acid and afterwards
with the mono-sulpho-acid.
F. AZO-COLORS PRODUCED FROM P-DIAMIDO-AZO-BENZOLE AND ITS HOMOLOGUES
AND DERIVATIVES.
It has been found that the diamido-azo-benzole described by Niotzki can be
converted into the tetrazo-compound by the calculated quantity (two molecules)
of nitrite of soda and, that this tetrazo-compound can be combined to form azo-colors
with two equal or different molecules of amines, phenoles, or their sulphonic or
carbonic acids. Some of these colors are valuable by their property of dyeing
non-mordanted cotton direct from a soap-bath.
In the same manner act those p-diamido-azo-combinations which are constituted
analogous to diamido-azo-benzole and which are obtained by replacing in the process
of Nietzki the aniline by toluidine, xylidine, or naphthylamine.
1) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho acid.
2,12 kg. of diamido-azo-benzole are dissolved in 5 kg. of hydrochloric acid of
20° Bé. and in 100 litres of water, and converted into the tetrazo-compound by adding
a solution of 1,38 kg. of nitrite in 20 litres of water. This compound is entered
under constant stirring into a solution of 6,5 kg. of a-naphthylamine-sulphonate
of soda and of 1,5 kg. of soda in 200 litres of water. After standing for about
12 hours, the product of the reaction is dissolved by boiling and the color is pre-
cipitated by salt, pressed and dried. It dyes cotton from an alkaline soap-bath
in a red violet shade.

page_text: 2) Color from p-diamido-azo-benzole +a-naphthole-mono-sulpho-acids.
If in Example 1 the a-naphthylamine-sulphonate of soda is replaced by 5 kg.
of a-naphthole-mono-sulphonate of soda, a color is obtained which does not dissolve
easily, and which dyes non-mordanted cotton in a violet shade.
3) Color from p-diamido-azo-benzole + B-naphthole di-sulpho-acid.
A blue color is obtained by converting 2,12 kg. of p-diamido-azo-benzole in the
manner already described into the tetrazo-compound and by combining the latter with
an alkaline solution of 7 kg. of ẞ-naphthole-disulphonate of soda (R salt).
Dad thin eth M. 1907

page_text: of 40 kg. of acetate of soda, a fine brownish precipitate of a diazo-amido-combination
shortly forms. After about an hour the reaction will be completed and all the tetrazo-
diphenyle be combined. If the combination thus obtained is then entered into a
solution of 70 kg. of salt of naphthionate, and if the reaction resulting is kept going
on for 12 hours under stirring, a dark colored product of the reaction is formed which,
by adding soda and by heating it, dissolves with a yellow red color.
The solution contains side by side two different colors, one being the Congo
produced and the second being the regenerated acid-yellow, (amido-azo-benzole-
bisulphonate of sodaium). By an addition of bydrochloric acid the acid of the Congo
color precipitates and is then separated from the soluble amido-azo-benzole-disulpho-
acid by filtration. The precipitated acid is afterwards converted into the sodium salt
and the color precipitated by salt.
B. MIXED COLORS PRODUCED FROM NAPHTHYLAMINE-DISULPHO ACIDS.
1) Color from benzidine + B-naphthylamine disulpho acid R + B-naphthylamine.
9.2 kg. of benzidine are converted in the known manner into the hydrochloric
tetrazo-combination. If this latter be entered into a solution of 17.5 kg. of
B-naphthylamine-disulphonate of sodaium and of 20 kg. of acetate of sodaium in
500 litres of water, the combination of one molecule of benzidine and of one molecule
of B-naphthylamine sulpho-acid is formed in the shape of a dark red jelly. The
reaction is complete after having gone on for half an hour.
If, now, a solution of 8 kg. of ẞ-naphthylamine in 12 kg. of hydrochloric acid of
21° Bé. and in 500 litres of water is added, the naphthylamine combines with the
intermediate product obtained. The compound assumes a dark color and becomes
liquid by degrees. The formation of the color is complete after 12 hours. By
adding 12 kg. of soda, the sodium-salt of the acid of the color is formed which
dissolves clear by heating it and which can be precipitated from a boiling solution by
Balt.
Instead of using naphthylamine in a hydrochloric aqueous solution it can also be
used as a free base in an alkaline alcoholic solution.
The color dyes cotton quite similar to Congo but withstands the action of free
acids better.
2) Color from benzidine + ẞ-naphthylamine-disulpho acid R + B-naphthylamine-
mono-sulpho-acid.
If in Example 1 a solution of 14 kg. of ẞ-naphthylamine-mono-sulphonate of
sodeium in 500 litres of water is used instead of a solution of 8 kg. of B-naphthylamine
in 12 kg. of hydrochloric acid, a color very similar to that described in Example 1 is
obtained which also dyes cotton in a bright red shade and which withstands acids.
3) Color from ẞ-naphthylamine-disulpho acid R + phenole.
If the compound consisting of one molecule of benzidine and of one molecule of
B-naphthylamine-disulpho-acid which according to Example 1 has been obtained in
shape of a dark red jelly, is entered into a solution of 5 kg. of phenole in 7 kg. of soda
lye of 40° Bé. and of 11 kg. of soda in 500 litres of water, the formation of the color
takes place instantaneously. The color can be precipitated by salt, and dyes cotton
a bright orange shade.
4) Color from benzidine 3-naphthylamine-disulpho-acid R + a-naphthole.
If in Example 3 the phenole is replaced by 8 kg. of a-naphthole, a color is obtained
which dyes cotton a reddish brown shade.
In all cases the benzidine can be replaced by Tolidine, and the colors then obtained
possess analogous properties to those described above.

page_text: C. MIXED AZO-COLORS PRODUCED FROM TETRAZO-DIPHENYLE OR TETRAZO-DITOLYLE
WITH SALICYLIC ACID AND a-NAPHTHOLE-DISULPHO-ACID.
1) Colors from salicylic acid.
The production of the intermediate product which consists of one molecule of salt
of tetrazo-diphenyle and of one molecule of salicylic acid, and which is styled diazo-
diphenyle-azo-salicylic acid, is arrived at by the following process.
The tetrazo-diphenyle formed from 18.4 kg. of benzidine, is entered into an alkaline
solution of 13.8 kg. of salicylic acid in about 500 litres of water. After standing for
some time the diazo-diphenyle-azo-salicylic acid separatesin in the shape of a red-
brown precipitate which serves directly for producing the azo-colors described
hereinafter. For this purpose it is entered into the alkaline solution of one of the
naphthylamine-sulpho-acids, phenoles, or phenole-sulpho-acids mentioned below. If,
however, phenylene-diamine is used, the combination takes place in an acidulated
solution.
If 18.4 kg. of benzidine and 13.8 kg. of salicylic acid are used there is required for
the production of the colors one or other of the following substances :
10.8 kg. of m-phenylene-diamine.
24.5 "
of a-naphthylamine-sulphonate of sodaium.
24.5 of B-naphthylamine-sulphonate of sodium.
9.4 of phenole.
11.
"
"
وو
of resorcine.
24.6 of a-naphthole-sulphonate of sodium.
24.6
24.6
34.8
"
وو
"
of B-naphthole-sulphonate of sodaium (Bayer).
of B-naphthole-sulphonate of sodium (Schäffer).
of B-naphthole-disulphonate of sodium, R salt.
34.8 of B-naphthole-disulphonate of sodium, G salt.
"
"
The further treatment of the azo-colors obtained consists in first leaving the product
of the reaction standing for about 12 hours, by then heating it up to boiling, and
finally, by separating the color with salt, filtering, pressing, and drying it.
These colors dye cotton direct from a soap-bath in the following shades:
m-phenylene-diamine
produces brown.
a-naphthylamine-sulpho-acid
B-naphthylamine-sulpho-acid
phenole
resorcine
yellow-red.
دو
red-yellow.
"
yellow.
"
a-naphthole-mono-sulpho-acid
yellow-red.
bluish-red.
"
B-naphthole-mono-sulpho-acid (Bayer)
"
B-naphthole-mono-sulpho-acid (Schäffer)
B-naphthole-disulpho-acid R
yellow-red.'
brownish-red.
"
brown-red.
"
""
brown-yellow.
B-naphthole-disulpho-acid G
2) Colors from a-naphthole-disulpho-acid.
If a solution of tetrazo-diphenyle from 18.4 kg. of benzidine, or of tetrazo-ditolyle
from 21.4 kg. of tolidine, acts upon an alkaline or acetic solution of 34.8 kg. a-naphthole-
disulpho-acid brown crystalline precipitates are formed which consist of the respective
intermediate products.
They form by their combination with alkaline solutions of:
9.4 kg. of phenole.
14.4 kg. of a-naphthole.
24.6 kg. of a-naphthole-mono-sulphonate of sodaium.
34.8 kg. of B-naphthole-disulphonate of sodium.

page_text: These colors also dye cotton direct from a soap-bath, and yield the following shades:
tetrazo-diphenyle tetrazo-ditolyle
phenole
a-naphthole
a-naphthole-mono-sulpho acid
B-naphthole-disulpho acid
D. Azo-COLORS PRODUCED FROM
AND
bluish-red
blue-violet
violet
blue
-
red-brown.
.
red-violet.
->>
-
P-DIAMIDO-AZO-BENZOLE
blue-violet.
blue.
AND ITS HOMOLOGUES
DERIVATIVES.
It has been found that the diamido-azo-benzole described by Nietzki can be con-
verted into the tetrazo-compound by the calculated quantity (two molecules) of nitrite of
sodeium and, that this tetrazo-compound can be confined to formeze azo-colors with two
equal or different molecules of amines, phenoles, or their sulphonic or carbonic acids.
Some of these colors are valuable by their property of dyeing non-mordanted cotton
direct from a soap-bath.
In the same manner act those p-diamido-azo-combinations which are constituted
analogous to diamido-azo-benzole and which are obtained by replacing in the process
of Nietzki the aniline by toluidine, xylidine, or naphthylamine.
1) Color from p-diamido-azo-benzole + a-naphtholeylamine-mono-sulpho-acid.
2.12 kg. of diamido-azo-benzole are dissolved in 5 kg. of hydrochloric acid of 20° Be.
and in 100 litres of water, and converted into the tetrazo-compound by adding a
solution of 1.38 kg. of nitrite in 20 litres of water. This compound is entered under
constant stirring into a solution of 6.5 kg. of a-naphthylamine sulphonate of sodium
and of 1.5 kg. of soda in 200 litres of water. After standing for about 12 hours,
the product of the reaction is dissolved by boiling and the color is precipitated
by salt, pressed and dried-It dyes cotton from an alkaline soap-bath in a red violet
shade.
2) Color from p-diamido-azo-benzole + a-naphthole-mono-sulpho-acids.
If in Example 1 the a-naphthylamine-sulphonate of soda is replaced by 5 kg. of
a-naphthole-mono-sulphonate of sodium a color is obtained which does not dissolve
easily, and which dyes nonun-mordanted cotton in a violet shade.
3) Color from p-diamido-azo-benzole + B-naphthole-disulpho acid.
A blue color is obtained by converting 2.12 kg. of p-diamido-azo-benzole in the
manner already described into the tetrazo-compound and by combining the latter
with an alkaline solution of 7 kg. of B-naphthole-disulphonate of sodaium (R salt).
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 production of colors from diazo-amido-combinations of tetrazo-diphenyle
and its homologues, substantially as herein described under head A.
2. The production of mixed colors from benzidine or tolidine and naphthylamine
disulpho-acids, substantially as herein described under head B.
3. The production of mixed colors from tetrazo-diphenyle or tetrazo-ditolyle with
salicylic acid and a-naphthole-disulpho-acid substantially as herein described under
head C.
4. The production of azo colors from diamido-azo-benzole and its homologues
and derivatives, substantially as herein described under head D.
Dated this 4th day of Fahr 1000
ABEL & IMRAY,
Agents for the Applicants.