Manufacture of New Colouring Matters.
Year: 1894

page_text: Date of Application, 19th Mar., 1894
Complete Specification Left, 18th Dec., 1894-Accepted, 19th Jan., 1895
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, Germany, Chemical Manufacturers.]
Manufacture of New Colouring Matters.
I, CHARLES DENTON ABEL, of No. 28, Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and Chartered Patent
Agent, do hereby declare the nature of this invention to be as follows:-
The invention relates to the manufacture of new colouring matters and is based
on the following observation.
By diazotising amidonaphthol-sulpho-acids, such as for instance y amidonaphthol-
mono-sulpho-acid, amidonaphtholdisulpho-acid Specification No. 15175 of 1889,
1:8 amidonaphthol-monosulpho acid S, 1:8 amidonaphthol-disulpho-acid, Specifi-
cation No. 2984 of 1893, and the like, and reacting with the diazo compounds
obtained upon meta-diamines, such as meta-phenylene diamine, meta-toluylendiamine,
azo-colouring matters are produced which dye wool in au acidulated bath tints
varying from brown yellow to brown violet.
The constitution of these wool-dyes is represented by the general formula:
and they may hereinafter be collectively termed "dye-W."
My foreign correspondents have now discovered that the aforesaid products are
capable of uniting again with diazo bodies, the diazo group entering in these cases
most probably the meta-diamine radical; in this manner a great series of most
valuable colouring matters may be produced.
I. In the first place my foreign correspondents may react with one molecule of '
a tetrazotised paradiamine, such as benzidine, its homologues, analogues, or the
sulpho or carbo acids of such substances upon two molecules of a "dye W," the
constitution of which is represented by the formula
The colouring matters resulting in this way dye unmordanted cotton in an
alkaline or salt bath. Generally the grey tint prevails in these dyes, which
according to the "dye W" and the paradiamine used produce, on unmordanted
cotton, tints varying from grey violet to violet black or brown black.
rb037

page_text: II. Instead of combining two molecules of the same "dye W" with tetrazotised.
paradiamines my foreign correspondents may also combine with such tetrazo-
compounds two molecules of dyes W, different from each other, forming in this
way mixed tetrazo colouring matters, of the general constitution
The properties of these dyes and the tints obtained by means of them are similar
to those of the products mentioned under head I.
III. My foreign correspondents may further prepare mixed dyes of the general
composition
by combining one of the two diazo groups of tetrazotised paradiamines with one
molecule a dye W., and the other an amine, diamine, amidophenol or the carbo or
sulpho acid of these products denoted by X in the above formula. According to
the components employed, the resulting products are more or less readily soluble
in water, and dye unmordanted cotton tints varying from brown to gray-violet and
blue black, the dark tint prevailing also in these mixed colours.
IV: My foreign correspondents may also produce colouring matters derived
from the dyes W, by combining the same with simple diazo bodies, such as for
instance those derived from aniline and its homologues, the carbo and sulpho acids
of these bases, nitraniline and its homologues, the naphthylamines and their sulpho
acids etc. Moreover diaźotised amido azo bodies, such as diazotised amidoazo-
benzene, and its homologues and analogues, or sulpho derivatives thereof may be
combined with the dyes W.
The colouring matters obtained in this way dye wool in an acidulated bath
tints varying from brown, to dark violet and violet black or brown black.
V. According to the further researches of my foreign correspondents, valuable
direct dyeing dyestuffs are also obtained by combining with the dyes W. the diazo
derivatives of dehydrothio-para toluidine, dehydrothiometoxylidine, primulinė base
and similar thioamido compounds or the sulphonic acids thereof.
The colouring matters thus obtained dye unmordanted cotton tints varying from
violet to brown.
VI. Colouring matters dyeing directly unmordanted cotton may, as my foreign
correspondents have discovered, be obtained also by combining with the
dyes W. the diazo products of the following products: amidobenzene-azo-alpha-
naphthylamine, amidobenzene-azo-paroxylidine, amidobenzene-azo-betaalkyloxy-
alphanaphthylamine and analogous bodies or the sulpho and carbo acids
thereof.
In this way colouring matters are produced which dye unmordanted cotton tints
varying, according to the components employed, from gray to gray-violet; gray-
blue or black-blue.
The above mentioned colouring matters are produced by the usual methods
employed for producing diazo or tetrazo dyestuffs.
Dated this 19th day of March 1894.
ABEL & IMRAY,
Agents for the Applicant.

page_text: I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Consulting Engineer and 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 invention relates to the manufacture of new colouring matters and is based
on the following observation.
By diazotising amido-naphthol-sulpho-acids, such as for instance_y-amido-
naphthol-mono-sulpho acid, amidonaphthol-disulpho-acid Specification No. 15175
of 1889, a a-amido-naphthol-a,-monosulpho acid, a a-amidonaphthol disulpho
acid Specification No. 2984 of 1893, and the like, and reacting with the diazo
compounds obtained upon meta-diamines, such as meta-phenylene diamine, meta-
toluylendiamine, azo-colouring matters are produced which dye wool in an acidulated
bath tints varying from brown yellow to brown violet.
The constitution of these wool dyes is represented by the general formula:
and they may hereinafter he collectively termed "dye W."
My foreign correspondents have now discovered that the aforesaid products are
capable of uniting again with diazo bodies, the diazo group entering in these cases
most probably the meta-diamine radical, in this manner a great series of most
valuable colouring matters may be produced.
I. In the first place my foreign correspondents may react with one molecule of
a tetrazotised paradiamine, such as benzidine, its homologues, analogues or the
sulpho or carbo acids of such substances upon two molecules of a "dye W;" the
constitution of the dye obtained is represented by the formula
The colouring matters resulting in this way dye unmordanted cotton in an
alkaline or salt bath. Generally the grey tint prevails in these dyes, which
according to the "dye W" and the paradiamine used, produce, on unmordanted
cotton, tints varying from grey violet to violet black or brown black.
18.4 kilos. benzidine are diazotised with 13.8 kilos. nitrite of soda in the usual
way, well known to chemists. The tetrazo compound is added to an alkaline
solution of 100 kilos. of dye W and in this case we understand under dye W the
colouring matter which is obtained by the combination of diazotised y-amido-
naphtholsulphonic acid with m-toluylendiamine.

page_text: The new colouring matter is formed immediately and separated with common
salt, it dyes unmordanted cotton in neutral or alkaline bath a dark violet
black.
II Instead of combining two molecules of the same dye W with tetrazotised
paradiamines my foreign correspondents may also combine with such tetrazo 5
compounds two molecules of dyes W different from each other, forming in this
way mixed tetrazo colouring matters, of the general constitution
EXAMPLE.
The diazo solution obtained from 18.4 parts of benzidine is poured into a cold
alkaline solution of 50 parts of the soda salt of B, a-amidonaphthol-ẞ, B.-disul-
phonic acid-azo-m-toluylendiamine, the so called dye W'. After the complete
formation of the intermediate colouring matter is finished 50 parts of the soda salt 1
of a₁a-amido-a, mono-sulphonic acid azo-m-toluylendiamine, the so called dye W
are added. The new colouring matter is separated by means of common salt and
dyes wool blueish black.
III. My foreign correspondents may further prepare mixed dyes of the general
by combining one of the two diazo groups of tetrazotised paradiamines with one
molecule a dye W, and the other an amine, diamine, amidophenol or the carbo or
sulpho acid of these products denoted by X in the above formula. According
to the components employed, the resulting, products are more or less readily
soluble in water, and dye unmordanted cotton tints varying from brown to
grey-violet and blue-black, the dark tint prevailing also in these mixed
colours.
EXAMPLE:
18-4 parts benzidine are tetrazotised and the tetrazo body is added to a solution
of 50 parts of the soda salt of the y-amidonaphtholdisulphonic acid azo-m-toluylene-
diamine the intermediate colouring matter forms a violet blue precipitate. After
the complete forination is finished a solution of 12 parts of m-toluylendiamine is
added. The new colouring matter is precipitated with common salt and dyes
anmordanted cotton brown black.
IV. My foreign correspondents may also produce colouring matters derived
from the dyes W by combining the same with simple diazo bodies, such as for
instance those derived from aniline and its homologues, the carbo and sulpho acids
of these bases, nitraniline and its homologues, the naphthylamines and their sulpho
acids &c. Moreover diazotised amidoazo bodies, such as diazotised amidoazobenzene
and its homologues and analogues, or sulpho derivatives thereof may be combined
with the dyes W.
The colouring matters obtained in this way dye wool in an acidulated bath
tints varying from brown, to dark violet and violet black or brown black.

page_text: The diazo solution from 14-3 parts of a-naphthylamine prepared in the well
known manner, is added to an alkaline solution of 45-2 parts of the product obtained
by the combination of the diazo product of amido-naphtholdisulphonic acid
Specification No. 15175 of 1889 upon m-toluylendiamine.
The new dyestuff dyes wool in an acidulated bath dark brown violet.
V. According to the further researches of my foreign correspondents, valuable
direct dyeing dyestuffs are also obtained by combining with the dyes W the diazo
derivatives of dehydrothio-p-toluidine, dehydrothiometaxylidine, primuline base
and similar thio-amido compounds or the sulphonic acids thereof.
The colouring matters thus obtained dye unmordanted cotton tints varying from
violet to brown.
EXAMPLE.
f.
37-2 parts of the combination product derived from a₁ as amidonaphthol-a,-
sulphonic acid and m-toluylendiamine are allowed to act upon diazo-dehydrothio-
toluidine sulphonic acid which is obtained by diazotising 34-2 parts of dehydrothio-
toluidine sulphonic acid sodium salt. The resulting new product dyes unmordanted
cotton brown.
VI. Colouring matters dyeing directly unmordanted cotton may, as my foreign
correspondents have discovered, be obtained also by combining with the dyes W
the diazo or tetrazo products of the following products amidobenzene-azo-a
naphthylamine, amidobenzene-azo-paraxylidine, amido-benzene-azo-beta-alkyloxy
alpha naphthylamine and analogous bodies or the sulpho and carbo acids
thereof.
In this way colouring matters are produced which dye unmordanted cotton tints
varying according to the components employed, from grey to grey violet, grey blue
or black blue.
The above mentioned colouring matters are produced by the usual methods
employed for producing diazo or tetrazo dyestuffs.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:-
1. The herein described process for the production of colouring matters by the
action of one molecule of tetrazo compounds of para-diamines upon two molecules
of the so called dyes W described above.
2. The herein described process for the production of mixed azo colours by
combining one of the diazo groups of the tetrazo derivatives of para-diamines
with one molecule of the so called dye W and combining the other diazo group
with one molecule dye W different from that used in the first combination.
3. The herein described process for the production of mixed azo colours by
combining one of the two diazo groups of the tetrazo derivatives of para diamines
with one molecule of the so called dyes W and combining the other diazo group
with an amine or diamine, a phenol, an amidophenol or their sulpho and carbo
acids.

page_text: 4. The herein described process for producing colouring matters derived from
the so called different dyes W by combining one of the dyes W with the diazo
compounds of amido bodies, such as aniline, nitraniline or their homologues,
naphthylamines or their sulphonic or carbonic acids, dehydrothio-toluidine,
dehydrothioxylidine, primuline and the other members of the series of thioamido
compounds and the sulpho acids thereof, amido azo benzene its homologues,
analogues and their sulpho acids.
5. The herein described process for producing colouring matters derived from
the so called different dyes W by combining the same with the diazo or tetrazo
compounds of amido benzene-azo-a-naphthylamine, amido benzene azo-paraxylidine,
amido benzene azo-beta-alkyloxyalphanaphthylamine and analogous bodies or the
sulpho and carbo acids thereof.
6. As new manufactures, the colouring matters produced by the processes set
forth in the Claims 1, 2, 3, 4 and 5.
Dated this 18th day of December 1894.
ABEL & IMRAY,
Agents for the Applicant.