anufacture of New "6 Coupled Tetrazo Compounds," and of Complex Poly Azo Colouring Matters resulting therefrom.
Year: 1895

page_text: Date of Application, 30th July, 1895
Complete Specification Left, 10th Aug., 1895-Accepted, 9th Nov., 1895
Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, of Basle, Switzerland, Chemical Manufacturers.]
anufacture of New "6 Coupled Tetrazo Compounds," and of Complex
Poly Azo Colouring Matters resulting therefrom.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, in the County of
ondon, Chartered Patent Agent, do hereby declare the nature of this invention
be as follows:-
66
The present invention relates to the manufacture of new coupled tetrazo
mpounds" and their conversion into new complex poly azo colouring matters.
hese poly azo colouring matters are produced by the combination of one
olecule of "coupled tetrazo ho lies" obtained by the coupling of two molecules
identical or different tetrazo bodies with one molecule of such compounds as
e capable of being combined with two molecules of a diazo compound-with
o identical or different molecules of amines, phenols, amido phenols as well as
ith their sulpho carboxyl or nitro derivatives.
For the preparation of the said coupled tetrazo compounds there are preferably
ployed
a) Two molecules of the following tetrazo bodies deriving from:
Benzidine, methylbenzidine, tolidine, ethoxybenzidine, diamidostilbene
diamido diphenol alkyl-ethers, diamido diphenylamine, diamido ditolylamine,
diamido carbazol, diamido azo benzol, and its homologues, diamido benzol
azo naphthaline, diamido benzol azo p-cresol ethers, benzidine mono- and
disulpho acid, benzidine sulphone, to liline sulphone and their sulpho acids,
diamidostilbene disulpho arid, 1.5 naphthylene diamine 3.7 disulpho acid
and diamido diphenylamine mono sulpho acid, p-phenylene diamine,
p-toluylene diamine, and
b) One molecule of the following components:
1. Dioxynaphthoic niono sulpho acid (English Patent 14161-5 August
1892).
2. Amido oxy naphthoic mono sulpho acid (French Patent No. 224260).
3. Dioxynaphthaline sulpho acid G.
4. 1.8 dioxynaphthaline 3.6 disulpho acid.
5. 1.8 amidonaphthol 3.6 disulpho acid.
6. 1.8 diamido naphthaline 3.6 disulpho acid.
7. ẞ amido naphthol disulpho acid R R (French Patent No. 201742).
8. Amido naphthol mono sulpho acid G (German Patent No. 53076).
9. Toluylene diamine mono sulpho acid
(CH,NH,NH,SO H 1:2:6:4),
as well as the simple and mixed dis-azo colouring matters which are obtained from
one molecule of a tetrazo compound of series a) and from two identical or different
molecules of the components of series b) or from one molecule of one of these
components and from another molecule of the compounds which are enumerated in
the paragraph hereinafter marked c).

page_text: 1.6.4 dioxynaphthaline sulpho acid dioxynaphthoic acid S and L
(German Patent No. 69357).
1.7.2 dioxynaphthoic acid resulting by the treatment of 1.7.2.4 dioxy-
naphthoic mono sulpho acid with diluted sulphuric acid.
Dioxynaphthoic mono sulpho acid (English Patent No. 14161º).
Amidooxynaphthoic mono sulpho acid (French Patent No. 224260).
1.7.2.4 dioxynaphthoic mono sulpho acid.
1.5 amido naphthol 7 mono sulpho acid.
Amido naphthol mono sulpho acid 7.1.4 obtained from 1.7.4 dioxy-
naphthaline sulpho acid by the action of ammonia.
1.5 amido naphthol 3.7 disulpho acid trihydroxynaphthaline mono sulpho
acid 1.3.8.6.
Chrysoidine and its analogues as well as their sulpho or carboxylic acids.
Bismarck brown R and J and their sulpho acids and
The mono azo colouring matters deriving from amido-naphthol- and dioxy-
naphthaline disulpho acid 1.8.3.6.
foreign correspondents have further observed that those of the coupled
o bodies, which result from two molecules of the tetrazo compounds
oned in series a) and from one molecule of naphthylene diamine disulpho
1.8.3.6 or amido naphthol disulpho acid 1.8.3.6 are converted into new
unds by the action of nitrous acid.
tetrazo bodies resulting according to this process from naphthylene diamine
ho acid 1.8.3.6 correspond to the general formula :
In these formulæ P signifies the radicle of a paradiamine named in paragraph a).
The compounds expressed by the first formula may be combined in the same way
as the "coupled tetrazo bodies" with two molecules of one of the above mentioned
components.
The compounds which are meant by the second formula have the property of
combining themselves with three identical or different molecules of the components
indicated in series c).
The new complex poly azo colouring matters which are obtained according to the
above described methods, may be generally employed for dyeing unmordanted
cotton, yielding brown violet, blue, gray or black shades.
According to the nature of the components which are used, the resulting new
dye-stuffs will be suitable for dyeing other fibres as for instance wool &c. and may be
fixed on the fibre according to their constitution either by treatment with metallic
salts or by diazotising and developing on the fibre.

page_text: WITH 2 MOLECULES OF AMIDOOXYNAPHTHOIC MONOSULPHO ACID.
18.4 kilos. of benzidine are diazotised in the usual manner.
The tetrazo compound is poured into a cooled alkaline solution of 16 kilos. of
1.8 amido naphthol 3.6 disulphonate of soda.
The coloration of the mixture which first is violet turns into black and the
intermediate product, which still contains two diazo groups susceptible of being
combined, separates out in the form of insoluble black flakes.
The mass is left to stand for 2 or 3 hours until tetrazo diphenyl has disappeared
and then the product of the reaction thus obtained is introduced into an alkaline
solution of 28.3 kilos. of amido-oxynaphthoic mono sulpho acid.
The product of the reaction is left standing for twelve bours and, after heating,
the coloring matter is precipitated by addition of common salt, filtered, pressed
and dried.
It is a black powder with metallic lustre and dyes violet-black on unmordanted
cotton.
By diazotation and developement on the fibre, for instance, with metaphenylene-
diamine, this dye is transformed into deep black.
COMBINATION OF THE INTERMEDIATE PRODUCT OBTAINED FROM 2 MOLE-
CULES OF TETRAZO DITOLYL AND 1 MOLECULE OF 1.8 AMIDONAPHTHOL
DISULPHONIC ACID WITH 2 MOLECULES OF AMIDO NAPHTHOL SULPHO
ACID G.
The coupled tetrazo compound obtained according to the first example by com-
bination of 2 molecules of tetrazo ditolyl (from 21 kilos. of tolidine) with 1 molecule
of 1.8 amidonaphthol 3.6 disulphonic acid is introduced into the alkaline solution of
24 kilos. of amido naphthol sulphonic acid G.
After stirring during twelve hours the mass is heated and the coloring matter is
precipitated with common salt, filtered, pressed and dried.
The dye stuff is a black powder and produces blue-black tints on unmordanted
cotton which are transformed into black by diazotation and developement on the
fibre.
EXAMPLE 3.
Instead of allowing the two molecules of the tetrazo compound to act first in
alkaline solution upon one molecule of the component as indicated in the
1st example, the following method may be adopted.
First 1 molecule of the
tetrazo compound is combined with 1 molecule of the component in acetic solution
and then the second molecule of the tetrazo compound is allowed to act in alkaline
solution.
In order to produce, for instance, the coloring matter from one molecule of

page_text: The resulting new intermediate product, which is formed after some hours,
contains three diazo groups and is combined with three identical molecules or with
three molecules mixed with the components mentioned in series c).
Amido naphthol sulpho acid G combined in alkaline solution produces coloring
matters which dye blue-black on untnordanted cotton.
By varying the tetrazo compounds and the components mentioned in the above
six examples with the compounds enumerated in the beginning of this description all
possible coupled tetrazo bodies as well as the complex poly azo coloring matters
hereinbefore defined are obtained in an analogous inanner.
Dated this 30th day of July 1895.
ABEL & IMRAY,
Agents for the Applicant.
Manufacture of New "Coupled Tetrazo Compounds," and of Complex
Poly Azo Colouring Matters resulting therefrom.
I, Oliver IMRAY, of No. 28 Southampton Buildings, 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 manufacture of new coupled tetrazo
compounds" and their conversion into new complex poly azo colouring matters.
These poly azo colouring matters are produced by the combination of one molecule
of "coupled tetrazo bodies" obtained by the coupling of two molecules of identical
or different tetrazo bodies with one molecule of such compounds as are capable of
being combined with two molecules of a diazo compound-with two identical
or different molecules of amines, phenols, amido phenols as well as with their sulpho
carboxyl or nitro derivatives.
For the preparation of the said coupled tetrazo compounds there are preferably
employed
a) Two molecules of the following tetrazo bodies deriving from:
Benzidine, methylbenzidine, tolidine, ethoxybenzidine, diamidostilbene
diamido diphenol alkyl-ethers, diamido diphenylamine, diamido ditolylamine,
diamido carbazol, diamido azo benzol, and its homologues, diamido benzol
azo naphthaline, diamido benzol azo p-cresol ethers, benzidine mono- and
disulpho acid, benzidine sulphone, tolidine sulphone and their sulpho acids,
diamidostilbene disulpho acid, 1.5 naphthylene diamine 3.7 disulpho acid and
diamido diphenylamine mono sulpho acid, p-phenylene diamine, p-toluylene
diamine, and
b) One molecule of the following components:
1. Dioxynaphthoic mono sulpho acid (English Patent, 14161-5 August
1892).
2. Amido oxy naphthoic mono sulpho acid (French Patent No. 224260).
3. Dioxynaphthaline sulpho acid Ġ.
4. 1.8 dioxynaphthaline 3.6 disulpho acid.
5. 1.8 amidonaphthol 3.6 disulpho acid.
6. 1.8 diamido naphthaline 3.6 disulpho acid.
7. ẞ amido naphthol disulpho acid R R (French Patent No. 201742).
8. Amido naphthol mono sulpho acid G (German Patent No. 53076).
9. Toluylene diamine mono sulpho acid
(CH.NH.NHSOH 1:2:6:4),

page_text: 1,7
"
4.
"
1.6.4 dioxynaphthaline sulpho acid dioxynaphthoic acid S and L (Gerinan
Patent No. 69357).
1.7.2 dioxynaphtheic acid resulting by the treatment of 1.7.2.4 dioxy-
naphthoic mono sulpho acid with diluted sulphuric acid.
Dioxynaphthoie mono sulpho acid (English Patent No. 14161).
Amidcoxynaphthoic mono sulpho acid (French Patent No. 224260).
1.7.2.4 dioxynaphthoic mono sulpho acid.
1.5 amido naphthol 7 mono sulpho acid.
Amido naphthol mono sulpho acid 7.1.4'obtained from 1.7.4 dioxynapthalive
sulpho acid by the action of ammonia.
1.5 ainiao naphthol 3.7 disulpho acid trihydroxynaphthalene mono sulpho
acid 1.3.8.6.
Chrysoidine and its analogues as well as their sulpho or carboxylic acids.
Bismarck brown R and J and their sulpho acids and
The mono azo colouring matters deriving from amido-naphthol- and dioxy-
naphthalene disulpho acid 1.8.3.6.
foreign correspondents have further observed that those of the coupled
o bodies, which result from two molecules of the tetrazo compounds mentioned
ies a) and from one molecule of naphthylene diamine disulpho acid 1.8.3.6
do naphthol disulpho acid 1.8.3.6 are converted into new compounds by the
of nitrous acid.
tetrazo bodies resulting according to this process from naphthylene diamine
ho acid 1.8.3.6 correspond to the general formula ⚫
.
In these formulæ P signifies the radicle of a paradiamine named in paragraph a).
The compounds expressed by the first formula may be combined in the same way
as the "coupled tetrazo bodies" with two molecules of one of the above mentioned
components.
The compounds which are meant by the second formula have the property of
combining themselves with three identical or different molecules of the components
indicated in series Le

page_text: The new complex poly azo coleuring matters which are obtained according to
the above described methods, may be generally employed for dyeing unmordanted
cotton, yielding brown violet, blue, gray or black shades.
According to the nature of the components which are used, the resulting new
dye-stuffs will be suitable for dyeing other fibres as for instance wool &c. and may
be fixed on the fibre according to their constitution either by treatment with
metallic salts or by diazotising and developing on the fibre.
WITH 2 MOLECULES OF AMIDOOXYNAPHTHOIC MONOSULPHO ACID.
18.4 kilos. of benzidine are diazotised in the usual manner.
The tetrazo compound is poured into a cooled alkaline solution of 16 kilo. of
1.8 amido naphthol 3.6 disulphonate of soda.
The coloration of the mixture which first is violet turns into black and the
intermediate product, which still contains two diazo groups susceptible of being
combined, separates out in the form of insoluble black Hakes.
The mass is left to stand for or 3 hours until tetrazo diphenyl has disappeared
and then the product of the reaction thus obtained is introduced into an alkaline
solution of 28'3 kilos. of amido-oxy-naphthoic mono sulpho acid.
The product of the reaction is left standing for twelve hours and, after heating,
the coloring matter is precipitated by addition of common salt, filtered, pressed and
dried.
It is a black power with metallic lustre and dyes violet-black on unmordanted
cotton.
By diazotation and development on the fibre, for instance, with metaphenylene-
diamine, this dye is transformed into deep black.
COMBINATION OF THE INTERMEDIATE PRODUCT OBTAINED FROM 2 MOLECULES
OF TETRAZO DITOLYL AND 1 MOLECULE OF 18 AMIDONAPHTHOL DISUL-
PHONIC ACID
MOLECULES
WITH TWO
OF AMIDO
SULPHO
NAPHTHOL
ACID G.
The coupled tetrazo compound obtained according to the first example by combi-
nation of 2 molecules of tetrazo ditolyl (from 21 kilos. of tolidine) with 1 molecule
of 1.8 amido-naphthol 3.6 disulphonic acid is introduced into the alkaline solution
of 24 kilos. of amido naphthol sulphonic acid G.
After stirring during twelve hours the mass is heated and the colouring matter
is precipitated with common salt, filtered, pressed and dried.
The dye stuff is a black powder and produces blue black tints on unmordanted
cotton which are transformed into black by diazotation and development on the
fibre.

page_text: Instead of allowing the two molecules of the tetrazo compound to act first in
alkaline solution upon one molecule of the component as indicated in the 1st example.
the following method may be adopted. First 1 molecule of the tetrazo compound
is combined with 1 molecule of the component in acetic solution and then the second
molecule of the tetrazo compound is allowed to act in alkaline solution.
In order to produce, for instance, the coloring matter from one molecule of tetrazo
diphenyl, 1 molecule of 1.8 amido naphthol 3.6 disulpho acid, 1 molecule of tetrazo
ditolyl and 2 molecules of 1.8 amido naphthol 3.6 disulphonic acid, the following
process is adopted.
The tetrazo solution resulting from 9-2 kilos. of benzidine is mixed with a
cooled solution of 16 kilos. of amido naphthol disulphonic acid containing acetate
of soda.
After some time the tetrazo solution from 10.6 kilos. of tolidine is added to the
mixture which has previously been made alkaline.
The mass is left to rest during 3 to 4 hours when the formation of the intermediate
product is complete and then a solution of 32 kilos. of 1.8 amido naphthol 3.6 disul-
phonic acid is introduced into it.
The coloring matter is separated according to the usual process.
ou unmordanted cotton.
It dyes blue
COMBINATION OF THE COLORING MATTER RESULTING FROM THE COUPLING
OF MOLECULE OF TETRAZO DIPHENYL AND 2 MOLECULES OF 1.8 AMIDO
NAPHTHOL 3.6 DISULPHO ACID WITII 2 MOLECULES OF TETRAZO
DIPHENYL AND COUPLING WITH 2 MOLECULES OF AMIDO NAPHTHOL
SULPHO ACID G.
The blue coloring matter which results by the combination of 9.2 kilos. of
diazotised benzidine with 32 kilos. of 1.8 amido naphthol 3.6 disulpho acid is
treated directly in alkaline solution with a tetrazo solution obtained from 184 kilos.
of benzidine.
The resulting intermediate product which has a dark-black color is formed at once
and is separated in the form of insoluble flakes.
After resting two hours an alkaline solution of 26 kilos. of amiño naphthol
sulphonic acid G is added to the mixture.
Twelve hours later the mass of the reaction is heated and the new coloring matter
is precipitated with common salt.
It produces blue black tints on unmordanted cotton, tints which may be
transformed into black by diazotation and development on the fibre with any
amines or phenols.
DIAZOTATION OF THE INTERMEDIATE PRODUCT OBTAINED FROM TWO
MOLECULES OF DIANISIDINE AND ONE MOLECULE OF NAPHTHYLENE
DIAMINE DISULPHO ACID 1.8.3.6 AND FURTHER COMBINATION WITH TWO
MOLECULES OF AMIDO NAPHTHOL DISULPHO ACID.
Two molecules of dianisidine are diazotised in the usual way.
In this solution
a cooled neutral solution of one molecule naphthylene diamine disulphonic acid 1.8.6.3
is introduced and afterwards an excess of carbonate of soda is slowly added. The
mass is left to stand during some hours.
As soon as the "coupled tetrazo body is forined the mass of the reaction is
acidulated and one molecule of nitrous acid introduced into it.

page_text: Some hours later the nitrous acid has disappeared and the resulting new tetrazo
body is combined with 2 molecules of amido naphthol disulpho acid 1.8.3.6. in an
alkaline solution.
The colouring matter is isolated by precipitation with common salt and filtered.
It dyes unmordanted cotton very intense and fast blue shades.
Instead of coupling two molecules of a tetrazo boly, there may be employel for
instance two molecules of p-diazo acetanilid obtaining analogous coupled tetrazo
bodies by saponifications of the acetyl group and by diazotation with three molecules
of nitrous acid.
The "coupled tetrazo body" obtained according to Example 1 from two
olecules of tetrazo diphenyl and one molecule of amido naphthol disulphonic
eid 1.8.3.6 is exposed to the action of one molecule of nitrous acid.
The resulting new intermediate product, which is formed after some hours,
ontains three diazo groups and is combined with three identical molecules or with
ree molecules mixed with the components mentioned in series c).
Amido naphthol sulpho acid G combined in alkaline solution produces colouring
atters which dye blue-black on unmordanted cotton.
By varying the tetrazo compounds and the components mentioned in the above
x examples with the compounds enumerated in the beginning of this description
1 possible coupled tetrazo bodies as well as the complex polyazo coloring matters
ereinbefore defined are obtained in an analogous manner.
Having now particularly described and ascertained the nature of the said
vention and in what manner the same is to be performed I declare that what
claim is :-
I. The manufacture of "coupled tetrazo bodies"
A. By combination of two identical or different molecules of tetrazo derivatives
of aromatic paradiamido compounds such as:
S
benzidine, methyl benzidine, tolidine, ethoxybenzidine, diamidostilbene,
alkyl ethers of diamido phenol, diamudodiphenyl amine, diamido
ditolylamine, diamido carbazol, diamido azo benzol and its homo-
logues, dianiido benzolazonaphthaline, diamido benzol azo para cresol
ethers, mono and disulpho benzidine, benzidine sulphone and tolidine
sulphone and their mono- and disulpho-derivatives, disulphodiamido
stilbene, naphthylenediamide disulpho acid 1.5.3.7 and diamido-
diphenylamine mono sulpho acid
with one molecule of one of the following components susceptible of
combining simultaneously with two diazo groups belonging to different
molecules that is to say:
Τ
mono sulpho dioxy naphthoic acid, mono sulpho amido oxy naphthoic
acid, dioxynaphthaline sulpho acid G, dioxynaphthaline disulpho
acid 1.8.3.6, amido naphthol disulpho acid 1.8.3.6, diamido naphthaline
disulpho acid 1.8.3.6, amido naphthol disulpho acid RR, amido
naphthol mono sulpho acid G, mono sulpho toluylene diamine
(CH, NH, NH. SO,II 1.2.6.4), naphthalene diamine sulpho
acid 2:3:6, amido naphthol sulpho àcid 2:3 : 6.
-
-
-
B. By the combination of one molecule of simple or mixed tetrazo coloring
matters which result from the coupling of one molecule of the tetrazo
derivative of one of the diamido compounds S, bracketted together in A,
and of two identical or different molecules of the compounds T, bracketted
together in A, with two molecules of one of the tetrazo derivatives of the
diamido compounds S, bracketted together in A.

page_text: C. By the combination of one molecule of mixed tetrazo coloring matters
resulting from the combination of one molecule of one of the tetrazo bodies
derived from the diamido compounds S, bracketted together in A, of one
molecule of one of the bodies T, bracketted together in A, and of one
molecule of an aromatic amine, phenol, amido phenol or their sulpho-nitro-
carboxyl or sulpho carboxyl derivatives and especially of the compounds
named under C in the beginning of the Specification with two molecules of
one of the tetrazo derivatives of the diamido compounds S, bracketted
together in A.
II. The transformation of the coupled tetrazo bodies, which result from two
molecules of the tetrazo compounds mentioned in series a) and from one molecule
of naphthalene diamine disulpho acid 1.8.3.6 into new diazo compounds by the
action of nitrous acid.
III. The transformation of the coupled tetrazo bodies, which result from two
molecules of the tetrazo compounds mentioned in series a) and from one molecule
of amido naphthol disulpho acid 1.8.3.6 into new diazo compounds by the action of
nitrous acid.
IV. The production of complex polyazo colouring matters:
(1) By the combination of one of the "coupled tetrazo compounds" obtained
as set forth in A in the Claim I with two identical or different molecules of
aromatic amines &c. &c.
(2) By the combination of one molecule of one of the " coupled tetrazo
compounds" obtained according to B of Claim I with two molecules of
aromatic amines &c. &c.
(3) By the combination of one molecule of one of the "coupled tetrazo bodies"
obtained according to C of Claim I with an aromatic amine &c. &c.
V. The production of complex polyazo colouring matters by the combination of
one molecule of the diazo compounds obtained according to Claim II with two
identical or different molecules of aromatic amines, phenols, amido phenols or
their sulpho-nitro-carboxyl or sulpho-carboxyl derivatives and especially of the
compounds mentioned under 6) and c) in the beginning of the Specification.
VI. The production of complex polyazo colouring matters by the combination
of one molecule of the diazo compounds obtained according to Claim III with
three identical or different molecules of aromatic amines, phenols, amido phenols
or their sulpho-nitro-carboxyl or sulpho-carboxyl derivatives and especially of the
compounds mentioned under 6) and c) in the beginning of the Specification.
VII. As new products the "coupled tetrazo bodies" obtained according to
Claim I and the diazo compounds obtained according to Claims II and III.
VIII. As new colouring matters the complex poly azo colouring matters
obtained according to Claims IV. V. and VI.
Dated this 10th day of August 1895.
ABEL & IMKAI,
Agents for the Applicant.