Year: 1887

page_text: Date of Application, 19th Dec., 1887
Complete Specification Left, 18th Sept., 1888
Complete Specification Accepted, 19th Oct., 1888
All benzidine and tolidine-coloring matters hitherto in trade, have analogous
formulae. But benzidine-and tolidine-coloring matters of isomeric composition are
produced by combining the diazo-combinations from 2 molecules of aniline, toluidine,
nylidine, cumidine, a-and ß-naphtylamine or the diazo-combinations from 2 mole-
cules of the sulpho-acids of these amines, or the diazo-combinations from 2 molecules
of a monoamidocarbonic acid (for instance monoamidosalicylic acid) with 1 molecule
of benzidine or tolidine. The latter substances are preferably employed suspended in
alcali. The reaction requires a certain time for its completion. First brown
intermediate products are produced, which may be employed for producing mixed azo
coloring matters. Subsequently for instance 1 molecule of diazotised naphtion-acid
is added to 1 molecule of benzidine suspended in alcali and after some time 1 molecule
of diazotised B-naphtylamine-sulpho acid is added.
The member, corresponding to the congo-red, of the new group of tetrazo coloring
matters has the following constitution :

page_text: All coloring matters produced by the above reactions are of an analogous composition.
Instead of benzidine and tolidine, m-phenylendiamine, p-phenylendiamine, n-toluylen-
diamine, m-xylylendiamine and the sulpho-acids of these combinations, or dimethyl-
paraphenylendiamine, a naphtylendiamine (produced by reduction of a-dinitronaphta-
line) diamidodiphenyldicarbonic acid and its ethers, the ether of the diamidodiphenole,
diamidodieresole, the diamidofluoren and the diamidostilben may also be employed.
The coloring matters produced in the manner described are for the most part
soluble in water, especially the mixed azo-coloring matters, which are produced from
the diazo-combinations of each two different naplity laminsulpho acids, and an alcaline
solution of m-phenylendiamine or a-naphtylendiamine on the other part.
All these new coloring matters can be again diazotised and again combined with
amines and their sulpho-acids, or with phenoles (especially the naphtoles) and their
sulpho-acids, or with oxynaphtol-acids or with phenocarbonic acids (oxybenzolacids)
to form red, violet, blue and yellow coloring matters. The coloring matters produced
contain the azo-group four times; they may be named double tetrazo-coloring
matters.
Double-tetrazo-coloring matters are for instance produced which color unmordanted
cotton in the alcaline bath brimstone-yellow to gold-yellow, by combining 2 molecules
of p-diazobenzolsulpho-acid or 2 molecules of diazotised naphty laminsulpho acid with
1 molecule of benzidine or tolidine ete, diazotising again the combination produced
and thereupon introducing it into an alcaline solution of phenole or salycilic acid.
By the application of one molecule of naphtion acid and one molecule of B-naphty-
laminsulpho-acid etc mixed double tetrazo-coloring matters can be obtained.
Similar double-tetrazo coloring matters are also obtained by again diazotising, not
the substance produced by the introduction of two molecules of diazotised
monamine into an alcaline solution of diamine, but the substance produced by the
introduction of 1 molecule of diazotised diamine into an alcaline solution of 1 molecule
of diamine, subsequently introducing it into an alcaline solution of an amine or phenol
or sulpho acid thereof or into an alcaline solution of salycilic acid or into the alcaline
solution of a diamine.
13 L
17

page_text: I, RUDOLPH WORMS, of Leipzig, in the Kingdom of Saxony, Doctor of Philosophy,
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 hy the
following statement :-
Heretofore by the combination of 1 molecule of tetrazodiphenylchloride with two
molecules of naphthionic acid, Congo red is produced the constitution of which is :-
-
All benzidine and tolidine colouring matters hitherto in commercial use have
analogous formulae. But benzidine and tolidine colouring matters of isomeric
composition are produced by combining the diazo-combinations from 2 molecules of
aniline, toluidine, xylidine, cumidine, and ẞ naphthylamine or the diazo-combinations
from 2 molecules of the sulpho acids of these amines, or the diazo combinations from
2 molecules of a monoamidocarbonic acid (for instance monoamidosalicylic acid) with
1 molecule of benzidine or tolidine. The latter substances are preferably employed
suspended in alkali. The reaction requires a certain time for its completion. Fast
brown intermediate products are produced, which may be employed for producing
mixed azo colouring matters.
Subsequently, for instance, 1 molecule of diazotised naphthionic acid is added to
1 molecule of benzidine suspended in alkali, and after some time 1 molecule of
diazotised ẞ naphthylamine sulpho acid is added.
The member, corresponding to the Congo red, of the new group of tetrazo colouring
matters has the following constitution :-
All colouring matters produced by the above reactions are of an analogous compo-
sition. Instead of benzidine and tolidine, metaphenylenediamine, paraphenylenediamine,
metatoluylenediamine, metaxylylenediamine, and the sulpho acids of these combin-
ations, or dimethylparaphenylenediamine, naphthylenediamine (produced. by
reduction of a dinitronaphtbaline) diamidodiphenyldicarbonic acid and their ethers,
the ethers of the diamido diphenole, diamidodicresole, the diamidofluorene and the
diamidostilbene and their sulpho acids may also be employed.
(I
The colouring matters produced in the manner described are for the most part
soluble in water.

page_text: All these new colouring matters can be again diazotised and again combined with
amines and their sulpho-acids or with phenols (especially the naphtholes and
dinaphtholes) and their sulpho acids or with oxynaphthol acids or oxydinaphthylene-
tetra-sulpho acid or with phenolcarbonic acids (oxybenzoic acids) to form red, violet,
blue and yellow colouring matters.
The colouring matters produced contain the azo-group four times, they may be
named double tetrazo colouring matters.
Double tetrazo colouring matters are, for instance, produced which colour non-
mordanted cotton in the alkaline bath brimstone-yellow to gold yellow, by combining
2 molecules of paradiazobenzole sulpho acid or 2 molecules of diazotised naphthylamine
sulpho acid with 1 molecule of benzidine or tolidine etc, diazotising again the
combination produced and thereupon introducing it into an alkaline solution of
phenole or salicylic acid.
By the application of 1 molecule of naphthionic acid and, 1 molecule of ẞ naphthy-
lamine sulpho acid etc, mixed double tetrazo colouring matters can be obtained.
Similar double tetrazo colouring matters are also obtained by again diazotising,
not the substance produced by the introduction of 2 molecules of diazotised monamine
into an alkaline solution of diamine, but the substance produced by the introduction
of 1 molecule of diazotised diamine into an alkaline solution of 1 molecule of diamine,
subsequently introducing it into an alkaline solution of an amine or phenol or sulpho
acid thereof or into an alkaline solution of an oxynaphthoic acid or phenolcarbonic
acid or into a solution of dimethylaniline, diethylaniline, or diphenylamine or into the
alkaline solution of a diamine.
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 combination of one molecule or of two molecules of the diazo combination
of the following bodies, ciz :-
A. Aniline, toluidine, xylidine.
B. The sulpho acids of these.
C. The nitro derivatives of the bodies A, and the sulpho acids of these nitro-
products.
D. Cumidine, naphthylamine, amidophenol, and homologues, amidocarbonic acids,
amido-oxycarbonic acids, nitro derivatives (not including nitroamidobenzoic
acid) and sulpho acids of all these; amidoazobenzol and homologues, amido-
azonaphthaline, chrysoidine, saffranine, and the sulpho acids of all these
bodies.
E. Phenylenediamine and homologues.
F. Alkylised phenylene diamines and homologues, naphthylenediamine, diamido-
diphenols and homologues, and the ethers, diamidofluorene, diamido-oxysulpho
benzide and homologues with the chloro derivatives, diamidodiphenyl-ketone,
diamido dibenzyl-diamido diphenyl-dicarbonic acid, benzidine sulphon and the
sulpho acids of all these bodies, further the diamidodiphenylaethan, diamido-
triphenylmethan, and their sulpho acids and the diamidostilbene.
G. Diamidostilbene disulphonic acid.
H. Benzidine, tolidine, and their sulphonic acids with
(1) benzidine, tolidine.
(2) benzidine, tolidine sulpho acids.
(3) diamido diphenols and homologues and the ethers, diamidostilbene,
diamidofluorene, diamido-oxysulphobenzide and homologues with the chloro-
derivatives diamidodiphenylketone, diamidodibenzyldiamidodiphenylcarbonic
_acid benzidine-sulphon-dimethylphenylenediamine and homologues, naphthy
lenediamine, diamidodiphenylaethan, diamidotriphenylmethan, and sulpho
acids of all these bodies.
(4) Phenylenediamine and homologues.
(5) Sulpho acids of the phenylenediamine and its homologues.

page_text: But it is to be understood that no claim is herein mane to the nomes amready know,
obtained by the combination of the bodies in class A with the bodies in 4.
Of those in class B with those in 1.
of those in class E with those in 4 & 5.
of those in class G with those in 4.
of those in class H with those in 4 & 5.
2. The production of azo colouring matters by diazotation of the bodies (1 mole-
cule) mentioned in the preceding claim, including those bodies that are therein
excepted as being already known, as these have not been used for the production
of colouring matters in the way herein described, and combination with (2 molecules)
amines, phenols, diphenols, their sulpho and carbonic acids.
3. The production of azo colouring matters from the intermediate products that
are formed by the combination of the diazo combinations of the bodies obtained
according to claim 1 (including those not therein claimed as being already known,
but which have not been used for the production of colouring matters in the way
herein described) with first one molecule only of amine, phenol and their sulpho
acids and carbonic acids, and subsequent combination with a second molecule of
the same or a different amine, phenol, diphenol or the sulpho or carbonic acids
of same.
Dated this 10th day of Santambor 1998
ABEL & IMRAY,
Agents for the Applicant.