Year: 1894

page_text: Date of Application, 2nd Mar., 1894
Complete Specification Left, 3rd Dec., 1894-Accepted, 19th Jan., 1895

page_text: mentioned with 1 molecule of dioxynaphthoë mono
oxynaphthoë mono sulpho acid.
sulpho acid or amido
or 52.9 parts of tolidine
57-
"
"
61.
"
"
"
,, ethoxybenzidine
diamidodiphenolether
or the equivalent quantity of another diamine mentioned in paragraph I are
dissolved in about 400 parts of warm water and 80 parts of muriatic acid.
After cooling, another 80 parts of hydrochloric acid are added to this solution
and into this liquid a solution of 153 parts of sodium nitrite (2 mol.) of 22 per
cent. is poured.
The tetrazo solution is mixed with a muriatic solution of 35.7 parts of alpha-
naphthylamine.
The intermediate products are separated out in the form of a crystalline
mass, which is rediazotised with 76.5 parts of a solution of sodium nitrite of
22 per cent.
PRODUCTION OF COLOURING MATTERS.
After about one hour, the diazotation is terminated and the tetrazo compounds
are introduced into a sodic solution of 207 parts of dioxynaphthoë mono sulpho
acid of 81 per cent. The formation of the colouring matters begins immediately
and is terminated within about 15 hours.
The colouring matters are salted out, filtered, pressed and dried.
They dye blue-black shades on unmordanted cotton.
The tints are very fast to light and washing.
In order to produce mixed colouring matters, the intermediate products resulting
for instance from 52.9 parts of tolidine and 35.7 parts of alphanaphthylamine are
further diazotised with 76-6 parts of a solution of sodium nitrite of 22 per cent.
After one hour's rest the tetrazo solution is combined with 76-2 parts of dioxy-
naphthoë mono sulpho acid in a sodic solution.
The mass is left standing for some time until the intermediate compound is
formed and then an alkaline solution of 115 parts of a naphthol az mono sulpho
acid (Nevile & Winther) of 5-3 per cent. is slowly added.
The colouring matter is separated out in the usual manner.
on unmordanted cotton.
It dyes blue-black
Analogous results are obtained by inverse combination, that is to say, in
combining first the a naphthol az mono sulpho acid and afterwards the dioxy-
naphthoë mono sulpho acid or amido oxynaphthoë mono sulpho acid.
Instead of a, naphthol a, mono sulpho acid, the other components mentioned in
paragraph I may be used and instead of tetrazo ditolyl the other tetrazo
compounds enumerated in paragraph I may be used.
From mixed diazo colouring matters which result according to the method of
English Patent No. 14253 of 6th August 1892 :
a) from the tetrazo compounds of benzidine, diamido phenyl tolyl, tolidine,
ethoxybenzidine, dianisidine, diamido stilbene, paraphenylenediamine, para amido
azo benzol and its homologues, diamidophenyl alpha azo naphthaline as well as
from further diazotised intermediate products resulting from one molecule of a
4

page_text: COLOURING MATTER FROM 1. MOLECULE OF BENZIDINE, 1 MOL. OF DIOXY-
NAPHTHOË MONO SULPHO ACID AND 1 MOL. OF AMIDONAPHTHOL
DISULPHO ACID RR, REDIAZOTATION OF THE THUS OBTAINED
COLOURING MATTER WITH 1. MOL. OF SODIUM NITRITE AND
COMBINATION OF THE DIAZOTISED PRODUCT WITH 1 MOL. OF META-
PHENYLENE DIAMINE.
61.3 parts of benzidine are diazotised in the well known manner and the tetrazo
solution is poured into an alkaline solution of 101.9 parts of dioxynaphthoë mono
sulpho acid.
The liquid is left to rest for about hour and afterwards it is poured into a
sodic solution of 125 parts of amido naphtholdisulpho acid 2 R.
The colouring matter is precipitated with cominon salt and filtered.
The precipitate is dissolved in warm water under addition of 23 parts of sodium
nitrite.
After cooling, 270 parts of muriatic acid are slowly added. Two hours later
the diazo solution is introduced into an alkaline solution of 39 parts of meta-
phenylenediamine.
The resulting colouring matter is a brown-black powder with metallic lustre
and produces blue-black tints on unmordanted cotton.
Instead of benzidine:
76 parts of ethoxybenzidine, 81-3 parts of diamido diphenol ether, 70-7 parts of
tolidine etc., may be employed in the above example.

page_text: COLOURING MATTER FROM MOLECULE OF BENZIDINE, .1 MOL. OF AMIDO-
OXYNAPHTHOË MONO SULPHO ACID AND 1 MOL. AMIDO NAPHTHOL MONO
SULPHO ACID G, REDIAZOTATION OF THE THUS OBTAINED
MIXED
COLOURING MATTER WITH 2 MOL. OF NITROUS ACID AND COMBINATION
WITH 2 MOL. OF METAPHENYLENEDIAMINE.
The tetrazo compound obtained from 46 parts of benzidine is poured into an
alkaline solution of 76.2 parts of amido oxynaphthoë mono sulpho acid.
As soon as the intermediate product is formed, the liquid is introduced into a
solution of 65 parts of amido naphthol mono sulpho acid G. After twelve hours
time, the colouring matter is precipitated with common salt, filtered and dissolved
in warm water.
The cooled solution, mixed with 34-52 parts of sodium nitrite, is acidulated with
350 parts of muriatic acid. To the thus resulting tetrazo compound an alkaline
solution of 60 parts (2 mol.) of metaphenylenediamine is added.

page_text: COLOURING MATTER FROM 1 MOL.
OF TETRAZODIPHENYL 1 MOL. AMIDO-
NAPHTHOLDISULPHO ACID 2 R, FURTHER DIAZOTATION OF THE
RESULTING INTERMEDIATE PRODUCT WITH 1 MOL. OF SODIUM NITRITE
AND COMBINATION OF THE REDIAZOTISED PRODUCT FIRST WITH ONE
MOLECULE OF META PHENYLENEDIAMINE, THEN WITH MOL. OF
DIOXYNAPHTHOË MONO SULPHO ACID.
The solution of tetrazo diphenyl prepared with 46 parts of benzidine is added to
an alkaline solution of 85-25 parts of amidonaphtholdisulpho acid 2 R.
The liquid is mixed with 340 parts of muriatic acid and the intermediate
product is rediazotised with a solution of 17.25 parts of sodium citrite.
When the diazotation is terminated an aqueous solution of 27 parts of meta-
phenylenediamine is added to the insoluble diazo compound and the mass is left to
rest.
The product of the reaction which still contains a combinable diazo group is
coupled with an alkaline solution of 84 parts of dioxynaphthoë mono sulpho
acid or amido oxy naphthoë mono sulpho acid and produces colouring matters which
dye unmordanted cotton blue black.
Instead of 46 parts of benzidine there may be employed in the above example:
53 parts of tolidine, 58 parts of ethoxybenzidine or 61 parts of diamido diphenol
ether, or any tetrazo compound mentioned in paragraph II a; for the 27 parts of
meta phenylene diamine may be substituted 30.5 parts of meta toluylene diamine
or 275 parts of meta amido phenol or 27.5 parts of resorcin.
The amidonaphthol disulpho acid 2 R may be replaced by the other amido sulpho
acids mentioned in paragraph 11 c.
In the preceding example, amidooxynaphthoë mono sulpho acid may be used
instead of amidonaphthol disulpho acid 2 R and in this case the corresponding
quantity of any compound mentioned in paragraph II, c, and II, d, or of alpha-
naphthylamine or alpha naphthol may be employed instead of 90 parts of
dioxynaphthoë mono sulpho acid.

page_text: By the combination of intermediate products resulting from tetrazo bodies
indicated in paragraph II a and of 1 mol. of dioxynaphthoë mono sulpho acid or
amido oxy naphthoë mono sulpho acid with the azo colouring matters which derive
from diazotised amidooxynaphthoë mono sulpho acid, diazotised amido naphthol
mono sulpho acid G, or diazotised amido naphthol disulpho acid 2 R, by the com-
bination with the components enumerated in paragraph II d, or, vice versa, by the
combination of these azo colouring matters first with one molecule of the tetrazo
compounds mentioned in paragraph II a, then with 1 mol. of dioxy naphthoë
monosulpho acid, amido oxynaphthoë mono sulpho acid or amido naphthol mono
sulpho acid G.
AMIDO
NAPHTHOL
COLOURING MATTER FROM 1 MOL. OF BENZIDINE, 1 MOL. OF THE COM-
BINATION PRODUCT OF 1 MOL. OF DIAZOTISED
DISULPHO ACID 2 R WITH 1 MOL. OF METATOLUYLENE DIAMINE AND
OF 1 MOL. OF DIOXY NAPHTHOË MONO SULPHO ACID.
85-25 parts of amido naphthol disulpho acid 2 R are dissolved in warm water
added to a cooled solution of 82 parts of muriatic acid and then diazotised with a
solution of 17.25 parts of sodium nitrite.
The diazo compound is poured into an alkaline solution of 30.5 parts of meta- -
toluylene diamine.
The combination product is not isolated, but it is mixed after some hours with a
solution of tetrazo diphenyl, resulting from 46 parts of benzidine.
As soon as the intermediate compound is formed, it is combined in an alkaline
solution with 84 parts of dioxy naphthoë mono sulpho acid.
The resulting colouring matter is separated out within 12 hours.
It is a dark powder having a metallic lustre. The tints which it produces on.
cotton without a mordant, are blue-black.

page_text: and instead of the combination products resulting from 85.25 parts of amido naphthol
disulpho acid 2 R with 30-5 parts of meta toluylene diamine, or 29-7 parts of meta.
phenylene diamine, or 29-9 parts of meta amido phenol or 30.2 parts of resorcin,.
the analogous coloring inatters deriving from amidooxynaphthoë mono sulpho acid
or diazotised amido naphthol monosulpho acid G may be used.
For 46 parts of benzidine there may be taken also 53 parts of tolidine, 58 parts
of ethoxybenzidine or 61 parts of diamido diphenol ether indicated in.
paragraph II a.
Analogous colouring matters result if the above combinations are made.
COLOURING MATTERS FROM 1 MOL. OF TETRAZO DIPHENYL, 1 MOL. DIOXY-
NAPHTHOE MONO SULPHO ACID AND 1 MOL. OF THE COMBINATION:
PRODUCT OBTAINED WITH 1 MOL. OF DIAZOTISED AMIDO NAPHTHOL
DISULPHO ACID 2 R AND 1 MOL. OF META TOLUYLENE DIAMINE.
The intermediate combination product resulting from 46 parts of diazotised.
benzidine with 76-5 parts of dioxynaphthoë mono sulpho acid is poured into an.
alkaline solution of the colouring matter which is derived, according to the
preceding example, from 93.7 parts of diazotised amido naphthol disulpho acid 2 R
by combination with 33-5 parts of meta toluylene diamine. Twelve hours later on,
the new colouring matter is precipitated with common salt and dried.
It dyes on
unmordanted cotton a black of a more reddish hue than the one which is described.
in the previous example.
The mixed diazo colouring matter derived from 61.3 parts of benzidine, 102 parts.
of diazo naphthoë mono sulpho acid and 39 parts of meta phenylenediamine is
dissolved in water and after addition of a cold soda solution the liquid is mixed
with the diazo compound resulting from 79-6 parts of amido naphtholmono sulpho.
acid G.
After twelve hours repose, the liquid is heated and the colouring matter is salted.
The mixed diazo colouring matter derived from 61.3 parts of benzidine, 102 parts.
of diazo naphthoë mono sulpho acid and 39 parts of meta phenylenediamine is
dissolved in water and after addition of a cold soda solution the liquid is mixed
with the diazo compound resulting from 796 parts of amido naphthol mono sulpho.
acid G.
After twelve hours repose, the liquid is heated and the colouring matter is salted.
out.
In the dry state, it is a dark brown powder and dyes brown-black the unmordanted.
cotton.

page_text: By further diazotation of the symmetrical mixed diazo colouring-matters obtained
from the tetrazo compounds mentioned in paragraph II a and 2 mol. of any amido
naphthol sulpho acids, amido naphthol ether sulpho acids and naphthylamine sulpho
acids named in paragraph II c either of one and the same component or of different
ones with 2 mol. of nitrous acid and combination of the tetrazo compounds:
a) with 2 mol. of dioxynaphthoë mono sulpho acid or amido oxynaphthoë mono
sulpho acid,
b) with 1 mol. of dioxynaphthoë mono sulpho acid or amido oxynaphthoë mono
sulpho acid and afterwards with 1 mol. of each of the components enumerated in
paragraph II d or mixtures of these compounds or with 1 mol. dioxynaphthaline
mono sulpho acid G or 1 mol. of each of the amido naphthol sulpho acids indicated
in paragraph 1 c.
c) first with one molecule of the components mentioned in paragraph II d or
1 mol. of dioxynaphthaline mono sulpho acid G or 1 mol. of each of the amido
naphthol sulpho acids of paragraph II c and afterwards with 1 mol. of dioxy-
naphthoë mono sulpho acid or amido oxynaphthoë mono sulpho acid or with 1 mol.
of one of the other compounds of paragraph II d.
THIS
COLOURING MATTER FROM 1 MOL. OF TETRAZO-DITOLYL AND TWO MOL. OF
AMIDO NAPHTHOË MONO SULPHO ACID G, REDIAZOTATION OF
COLOURING-MATTER WITH 2 MOL. OF NITROUS ACID AND
WITH 2 MOL. OF DIOXYNAPHTHOË MONO SULPHO ACID.
COMBINATION
The solution of tetrazo ditolyl prepared with 53 parts of tolidine is introduced
into a sodic solution of 130.5 parts of amido naphthol mono sulpho acid G.
water;
After several hours rest this colouring matter (German Patent No. 55648
"Diamine black") is precipitated, filtered and redissolved in warm
34.5 parts of sodium nitrite are added and the cooled solution is acidulated with
220 parts of muriatic acid.
The resulting tetrazo compound is combined with a sodic solution of 165 parts
of dioxynaphthoë mono sulpho acid.
After twelve hours, the colouring matter is isolated according to the well known
method.
It dyes black blue on unmordanted cotton.
In place of diamine black, the symmetrical diazo colouring matters or the mixed
diazo colouring matters may be used which result, if in the above example instead
of 53 parts of benzidine, 46 parts of benzidine 57 parts of ethoxybenzidine or
61 parts of dianisidine or the respective quantities of one of the other tetrazo-
compounds mentioned in paragraph II a, are employed or if for 1305 parts of
amido naphthol mono sulplio acid G 187 parts of amido naphthol disulpho acid RR
or 187 parts of a, a, amidonaphthol ẞ, ẞs disulpho acid are substituted or if instead
of 2 mol. of dioxy naphthoë mono sulpho acid 2 mol. of amido oxynaphthoë mono
sulpho acid are used or if 1 mol. of one of these bodies is replaced by 1 mol. of any
compound named in paragraph II c or II d.

page_text: COLOURING MATTER FROM 1 MOL. OF BENZIDINE, 1 MOL. OF AMIDO NAPHTHOL
MONO SULPHO ACID G AND 1 MOL. OF α₁ aд AMIDO NAPHTHOL ẞ, ẞ, DISULPHO
ACID REDIAZOTATION OF THE THUS OBTAINED COLOURING MATTER WITH
2
MOL. OF SODIUM NITRITE AND COMBINATION OF THIS TETRAZO
COMPOUND WITH ONE MOLECULE OF META AMIDO PHENOL AND AFTER-
WARDS WITH 1 MOL. OF DIOXYNAPHTHOË MONO BULPHO ACID.
613 parts of benzidine are diazotised as usual and coupled according to the
method described in Example I with 105-6 parts of amido naphthol mono sulpho
acid G of 75.3% and 113 parts of a₁ a amido naphthol B2 B3 disulpho acid
of 83%
The isolated colouring matter is rediazotised with 2 mol. of sodium nitrite and
350 parts of muriatic acid. The thus obtained insoluble tetrazo compound is
introduced into an alkaline solution of 35.8 parts of meta amido phenol and an
alkaline solution of 113 parts of dioxynaphthoë mono sulpho acid is added.
After twelve hours rest, the liquid is heated and the colouring matter is
precipitated with common salt, filtered and dried.
It dyes on cotton blue black shades without a mordant.
Dated this 2nd day of March 1894.
ABEL & IMRAY,
Agents for the Applicant.
1, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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:-
The present invention relates to the preparation of a series of new colouring
matters dyeing violet grey to blue black tints on unmordanted cotton.
These new
dye stuffs possess a remarkable fastness against light and washing,
properties which may be still farther improved by treating with metallic salts, or,
in certain cases, by rediazotation and development on the fibre.
These new poly azo colouring matters are obtained as follows :-
From intermediate products which result from the combination of the tetrazo
bodies of benzidine, tolidine, ethoxybenzidine, diamido phenyl tolyl, diamido
stilbene, diamido diphenol ethers with one molecule of alpha-naphthylamine, by
rediazotation with one molecule of nitrous acid and combination :
a) with 2 molecules of dioxynaphthoic mono sulpho acid (English Patent
No. 14161 of 5th August 1892) or with 2 molecules of amido-oxynaphthoic mono
sulpho acid (French Patent No. 224260 of 10th September 1892)
b) with 1 molecule of one of these compounds to produce new intermediate
B

page_text: a₁ a
..
01 a
"
"
derivatives and further combination of these bodies with one molecule of one
the following components:
amido oxynaphthoic mono sulpho acid
Bamido naphthol mono sulpho acid G
В
al a
"
"
disulpho acid RR
amido naphthol ẞ, B, disulpho acid
disulpho acid
وو
a mono sulpho acid
وو
دو
(German Patent No. 53076)
(German Patent No. 53023)
(French Patent No. 210950)
"
39
228397)
"
"
210950)
a1 a
"
"
"
"
"
"
"
"
206501)
a a
"
"
Вз
27
"
"
(
"
"
"
210033)
a a
"
,,
"
"
"
a1 ag
"
"
39
"
B₁ a 3
"
"
B₁
دو
99
B, as
a1
απ
"
وو
a1
"
naphthol
"
"
a, ẞ disulpho acid
€2 mono sulpho acid
03
Ba disulpho acids
dioxynaphthaline mono sulpho acid G
naphthoë mono sulpho acid
"
(French Patent No. 229263)
39
"
(
"
"
"
227892)

page_text: In order to produce mixed colouring matters, the intermediate products resulting
for instance from 52.9 parts of tolidine and 357 parts of alpha naphthylamine are
further diazotised with 76-6 parts of a solution of sodium nitrite of 22 per cent.
After one hours rest the tetrazo solution is combined with 76°2 parts of
dioxynaphthoic mono sulpho acid in a sodic solution.
The mass is left standing for some time until the intermediate compound is
formed and then an alkaline solution of 115 parts of a, naphthol a, mono sulpho
acid (Nevile & Winther) of 5.3 per cent. is slowly added. The colouring matter
is separated out in the usual manner. It dyes blue black on uumordanted
cotton.
Analogous results are obtained by inverse combination, that is to say, in com-
bining first the a₁ naphthol a, mono sulpho acid and afterwards the dioxynaphthoic
mono sulpho acid or amido oxynaphthoic mono sulpho acid.
Instead of a naphthol a, mono sulpho acid, the other components mentioned in
paragraph Ib may be used and instead of tetrazo ditolyl the other tetrazo compounds
enumerated in nareσranh I may be used.

page_text: EXAMPLE.
COLOURING MATTER FROM 1 MOLECULE OF
BENZIDINE, 1 MOL. OF
DIOXYNAPHTHOË MONO SULPHO ACID AND 1 MOL. OF AMIDONAPHTHOL
DISULPHO ACID R R, REDIAZOTATION OF THE THUS OBTAINED
COLOURING MATTER WITH 1 MOL. OF SODIUM NITRITE AND COM-
BINATION OF THE DIAZOTISED PRODUCT WITH 1 MOL. OF META-
PHENYLENE DIAMINE.
61.3 parts of benzidine are diazotised in the well known manner and the tetrazo
solution is poured into an alkaline solution of 101.9 parts of dioxynaphthoic mono
sulpho acid.
The liquid is left to rest for about hour and afterwards it is poured into a
sodic solution of 125 parts of amido naphthol-disulpho acid 2 R.
The colouring matter is precipitated with common salt and filtered.
The precipitate is dissolved in warm water under addition of 23 parts of sodium
nitrite.
After cooling, 270 parts of muriatic acid are slowly added. Two hours later
the diazo solution is introduced into an alkaline solution of 39 parts of meta-
phenylenediamine.
The resulting colouring matter is a brown black powder with metallic lustre and
produces blue black tints on unmordanted cotton.
Instead of benzidine:
76 parts of ethoxybenzidine, 81.3 parts of diamido diphenol ether, 70-7 parts of
tolidine etc., may be employed in the above example.
For phenylenediamine :
44 parts of metatoluylenediamine, 39.3 parts of meta amido phenol, 39 6 parts of
resorcin etc., or mixtures of these bodies may be substituted and finally the amido-
naphthol disulpho acid 2 R may be replaced for instance by 87.6 parts of amido
naphthol mono sulpho acid G or 125 parts of a, a, amido naphthol B2 B3 disulpho
acid or by one of the other compounds mentioned in paragraph II c.
COLOURING MATTER FROM 1 MOL. OF TOLIDINE, 1 MOL. OF AMIDO NAPHTHOL
MONO SULPHO ACID G AND 1 MOL. OF DIOXYNAPHTHOË MONO SULPHO
ACID, REDIAZOTATION OF THE THUS OBTAINED COLOURING MATTER
WITH MOL. SODIUM NITRITE AND COMBINATION OF THE DIAZOTISED
PRODUCT WITH 1 MOL. OF META AMIDO PHENOL.
The tetrazo compound resulting from 53 parts of tolidine is added to an alkaline
solution of 59-7 parts of amidonaphthol mono sulpho acid G. After formation of the
intermediate product the latter is mixed with a solution of 83.8 parts of dioxy-
naphthoic mono sulpho acid. After twelve hours repose, the colouring matter is
precipitated with common salt, filtered, redissolved in warm water mixed with
172-5 parts of sodium nitrite and when cooled, 165 parts of muriatic acid are
introduced. The mass is stirred during 2 hours and the diazotised colouring
matter is poured into a sodic solution of 30 parts of meta amido phenol and left
standing for 12 hours.
The dry colouring matter is a brown black powder and yields deep black shades
on unmordanted cotton.
III.
From mixed diazo colouring matters resulting according to the process described
in French Patent No. 224812 of 8th October 1892 or according to the methods
iudicated in paragraph I from the tetrazo compounds mentioned in paragraph II a
with 1 molecule of amido oxynaphthoic mono sulpho acid and with 1 molecule of
the amido naphthol sulpho acids enumerated in paragraph II c by rediazotation with
From mixed diazo colouring matters resulting according to the process described
in French Patent No. 224812 of 8th October 1892 or according to the methods
iudicated in paragraph I from the tetrazo compounds mentioned in paragraph II a
with 1 molecule of amido oxynaphthoic mono sulpho acid and with 1 molecule of 5
the amido naphthol sulpho acids enumerated in paragraph II c by rediazotation with

page_text: 2 molecules of nitrous acid and combination with 2 molecules of the components
named in paragraph II d, or mixtures of these bodies, or by the combination, first
only with 1 molecule of one of these components and afterwards with a second
molecule of another of these components or with one molecule of one of the amido
naphthol sulpho acids mentioned in paragraph II e with dioxynaphthoic mono sulpho
acid or amido oxynaphthoie mono sulpho acid or vice versû.

page_text: The liquid is mixed with 340 parts of muriatic acid and the intermediate product
is rediazotised with a solution of 17-25 parts of sodium nitrite.
When the diazotation is terminated an aqueous solution of 27 parts of meta
phenylenediamine is added to the insoluble diazo compound and the mass is left
to rest.
The product of the reaction which still contains a combinable diazo group is
coupled with an alkaline solution of 84 parts of dioxynaphthoic mono sulpho acid
or amido oxy naphthoic mono sulpho acid and produces colouring matters which
dye unmordanted cotton blue black.
Instead of 46 parts of benzidine there may be employed in the above example:
53 parts of tolidine, 58 parts of ethoxy benzidine or 61 parts of diamido diphenol
ether, or any tetrazo compound mentioned in paragraph IIa, for the 27 parts of
meta phenylene diamine may be substituted 30-5 parts of meta toluylene diamine
or 27.5 parts of meta amido phenol or 27.5 parts of resorcin.
The amidonaphthol disulpho acid 2 R may be replaced by the other amido sulpho
acids mentioned in paragraph II, c.
In the preceding example, amido oxy-naphthoic mono sulpho acid may be used
instead of amido naphthol disulpho acid 2 R and in this case the corresponding
quantity of any compound mentioned in paragraph II, c, and II, d, or of alpha-
naphthylamine or alpha naphthol may be employed instead of 90 parts of
dioxynaphthoic mono sulpho acid.
COLOURING MATTER FROM 1 MOL. OF TETRAZO DIPHENYL 1 MOL. OF AMIDO
NAPHTHOIC MONO SULPHO ACID, REDIAZOTATION OF THIS INTERMEDIATE
COMPOUND AND COMBINATION OF THE REDIAZOTISED PRODUCT FIRST
ONE MOLECULE OF DIOXYNAPHTHOIC MONO SULPHO ACID THEN
WITH
WITH ONE MOLECULE OF META PHENYLENE DIAMINE.
46 parts of benzidine are diazotised and introduced into an alkaline solution of
76.2 parts of amido naphthoic mono sulpho acid. After the formation of the inter-
mediate product, the liquid is mixed with 340 parts of muriatic acid and with
an aqueous solution of 17.25 parts of sodium nitrite. As soon as the diazotation is
terminated the tetrazo compound is added:
1) to an alkaline solution of 76.5 parts of dioxynaphthoic mono sulpho acid and
half an hour afterwards, an aqueous solution of 29-7 parts of metaphenylene
diamine or meta amidophenol &c. is added. The mass is left to rest for some time
.and then the colouring matter is separated out according to the well known method.
It produces black tints on unmordanted cotton.
2) to an alkaline solution of 60 parts of meta amido phenol or of another of the
components mentioned in paragraph II d. The resulting colouring matter yields
brown black shades on unmordanted cotton.
By the combination of intermediate products resulting from tetrazo bodies
indicated in paragraph II a, and of 1 mol. of dioxynaphthoic mono sulpho acid or
amido oxynaphthoic mono sulpho acid with the azo colouring matters which derive
from diazotised amido oxynaphthoic mono sulpho acid, diazotised amido naphthol
mono sulpho acid G, or diazotised amido naphthol disulpho acid 2 R, by the
combination with the components enumerated in paragraph II d, or, vice versa, by
the combination of these azo colouring matters first with one molecule of the tetrazo
compounds mentioned in paragraph II a, then with 1 mol. of dioxynaphthoic
mono sulpho acid, amido oxynaphthoic mono sulpho acid or amido naphthol mono
.sulpho acid G.

page_text: COLOURING MATTERS FROM 1 MOL. OF TETRAZO DIPHENYL, 1 MOL. DIOXY-
NAPHTHOIC-MONO SULPHO ACID AND 1 MOL. OF THE COMBINATION
PRODUCT OBTAINED WITH 1 MOL. OF DIAZOTISED AMIDO NAPHTHOL
DISULPHO ACID 2 R AND 1 MOL. OF META TOLUYLENE DIAMINE.
The intermediate combination product resulting from 46 parts of diazotised
benzidine with 76.5 parts of dioxynaphthoic mono sulpho acid is poured into an
alkaline solution of the colouring matter which is derived, according to the
preceding example, from 93.7 parts of diazotised amido naphthol disulpho acid 2 R
by combination with 33-5 parts of meta toluylene diamine. Twelve hours later
on, the new colouring matter is precipitated with common salt and dried. It dyes
on unmordanted cotton a black of a more reddish hue than the one which is
described in the previous example.

page_text: By the combination of mixed diaze colouring matters resulting from 1 mol. of
dioxynaphthoic mono sulpho acid or ainido oxynaphthoic mono sulpho acid, 1 mol.
of one of the tetrazo compounds named in paragraph II a and from one mol. of one
of the components mentioned in paragraph II d, with one molecule of any diazo
compound resulting for instance from ß-amido-naphthol mono sulpho acid G,
B-amido oxynaphthoic mono sulpho acid and a-and-ẞ-naphthylamine mono sulpho
acids.
After twelve hours repose, the liquid is heated and the colouring matter is
AMIDO
COLOURING MATTER FROM 1 MOL. OF TETRAZO-DITOLYL AND TWO MOL. OF
NAPHTHOL MONO SULPHO ACID G, REDIAZOTATION OF THIS
COLOURING-MATTER WITH 2 MOL. OF NITROUS ACID AND COMBINATION
WITH 2 MOL. OF DIOXYNAPHTHOIC MONO SULPHO ACID.
The solution of tetrazo ditolyl prepared with 53 parts of tolidine is introduced.
into a sodic solution of 130-5 parts of amido naphthol mono sulpho acid G. After
several hours rest this colouring matter (German Patent No. 55648 " ⚫ Diamine
black") is precipitated, filtered and redissolved in warm water; 345 parts of.
sodium nitrite are added and the cooled solution is acidulated with 220 parts of
muriatic acid.

page_text: The resulting tetrazo compound is combined with a sodic solution of 165 parts of
dioxynaphthoë mono sulpho acid.
After twelve hours, the colouring matter is isolated according to the well known
method. It dyes black blue on unmordanted cotton.
In place of diamine black, the symmetrical diazo colouring matters or the mixed
diazo colouring matters may be used which result, if in the above example instead
of 53 parts of tolidine, 46 parts of benzidine 57 parts of ethoxybenzidine or 61 parts
of dianisidine or the respective quantities of one of the other tetrazo-compounds
mentioned in paragraph II a, are employed or if for 130.5 parts of amido naphthol
mono sulpho acid G 187 parts of amido naphthol disulpho acid R R or 187 parts
of a, a, amidonaphthol B₂, disulpho acid are substituted or if instead of 2 mol. of
dioxynaphthoic mono sulpho acid 2 mol, of amido oxynaphthoic mnono sulpho acid
are used or if 1 mol. of one of these bodies is replaced by 1 mol. of any compound
named in paragraph II c or II d.
COLOURING MATTER
NAPHTHOL ΜΟΝΟ
FROM 1
SULPHO
MOL. OF BENZIDINE, 1
ACID G AND 1 MOL.
MOL. OF
OF a1 a
AMIDO
AMIDO
NAPHTHOL ẞ, ẞ3 DISULPHO ACID REDIAZOTATION OF THE THUS
OBTAINED COLOURING MATTER WITH 2 MOL. OF SODIUM NITRITE AND
COMBINATION OF THIS TETRAZO COMPOUND WITH ONE MOLECULE OF
META AMIDO PHENOL AND AFTERWARDS WITH 1 MOL. OF
NAPHTHOIC MONO SULPHO ACID.
DIOXY-
61-3 parts of benzidine are diazotised as usual and coupled according to the
method described in Example I with 105-6 parts of amido naphthol mono sulpho
acid G of 753 % and 113 parts of a₁ a amido naphthol ẞ, ẞ, disulpho acid
of 83%
The isolated colouring matter is rediazotised with 2 mol. of sodium nitrite and
350 parts of muriatic acid. The thus obtained insoluble tetrazo compound is
introduced into an alkaline solution of 35.8 parts of meta amido phenol and an
alkaline solution of 113 parts of dioxynaphthoic mono sulpho acid is added.
After twelve hours rest the liquid is heated and the colouring matter is
precipitated with common salt, filtered and dried.
It dyes on cotton blue-black shades without a mordant.
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The herein described manufacture of new poly-azo-colouring matters:
a) By combining dioxynaphthoic-mono sulpho acid or amido-oxy-naphthoic
mono sulpho acid with tetrazo salts or intermediate compounds containing a
free diazo group.
b) By combining the intermediate compounds resulting from tetrazo-salts and
dioxynaphthoic mono sulpho acid or amido oxynaphthoic mono sulpho acid
and having a free diazo group with any of the dye stuff component herein
mentioned.
2. The polyazo colouring matters manufactured as above set forth.
ABEL & IMRAY,
Agents for the Applicant.