Year: 1896

page_text: WILLIAM HENRY CLAUS ALFRED REE Droylsden, Manchester Aniline Dye
Manufacturers LEON MARCHLEWSKI Chemist 25 Wellington Street, Higher
Broughton Manchester do hereby declare the nature of this invention to be as
follows:-
Our invention relates to the production of new poly-azo dyes of the following
two general formulm
To the alkaline solution of this body is gradually added the compound produced
by the action of one molecule of the chloride of tetrazodiphenyl, (tetrazoditolyl,
20 tetrazodianísyl and the like) on one molecule of amidonaphtholmonosulphonic
Ruine 821

page_text: 3. EXAMPLE.
Acetyl-p-phenylenediamine is diazotised and combined in acid solution with 2
1 mol. proportion of amidonaphtholsulphonic acid G. Next the acetyl group is
split off by saponification and the substance produced diazotised and combined in
alkaline solution with 1 mol. of the amido-azo compound, produced by coupling
amidonaphtholsulphonic acid G. with itself. The substance produced may be

page_text: again diazotised and combined with one mol. proportion of m. phenylenediamine,
m. tolaylenediamine or resorcinol.
FAVDER
Instead of using as in Example 1, amidonaphtholsulphonic acid G. as a first
component, other substances may be used, namely naphthols, phenols and their
sulpho acids, amines and their sulpho acids and the like. Take for instance
1 mol. proportion of 1:4 naphtholsulphonic acid (Neville Winter's) combined with
1 mol. proportion of tetrazodiphenyl chloride and introduce the intermediate
product formed into an alkaline solution of the amidoazo-compound obtained by
combination of diazotised amidonaphtholsulphonic acid G. with itself. The
colouring matter which is produced may be diazotised again and combined with
1 mol. proportion of m. phenylenediamine, m. toluylenediamine or resorcinol.
Dated this 13th day of August 1896.
Instead of using as in Exaniple 1, amidonaphtholsulphonic acid G. as a first
component, other substances may be used, namely naphthols, phenols and their
sulpho acids, amines and their sulpho acids and the like. Take for instance
1 mol. proportion of 1:4 naphtholsulphonic acid (Neville Winter's) combined with
1 mol. proportion of tetrazodiphenyl chloride and introduce the intermediate
product formed into an alkaline solution of the amidoazo-compound obtained by
combination of diazotised amidonaphtholsulphonic acid G. with itself. The
colouring matter which is produced may be diazotised again and combined with
1 mol. proportion of m. phenylenediamine, m. toluylenediamine or resorcinol.
Dated this 13th day of August 1896.
WILLIAM HENRY CLAUS.
ALFRED REE.
LEON MARCHLEWSKI.
WILLIAM HENRY CLAUS, ALFRED RÉE both Chemical Manufacturers, of
Droylsden, Manchester, LEON MARCHLEWSKI, Chemist, 25 Wellington Street,
Higher Broughton, Manchester, 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:-
Our invention relates to the production of polyazo dyes which possess the
property of dyeing cotton without the aid of mordants.
The intermediate products for the manufacture of the hereinafter specified
colouring matters or dyes is the amidoazo compound obtained by coupling the
diazotised gamma amidonaphtholsulphonic acid with one molecule of the same acid
in alkaline solution.
The said amidoazo compound may be prepared as follows: 24 parts (by weight)
of the gamma amidonaphtholsulphonic acid are dissolved in 700 parts of water and
the corresponding quantity of carbonate of soda. The solution is acidulated with
hydrochloric acid, and after cooling with ice there is added gradually a solution of
7-1 parts of sodium nitrite. The yellow diazo compound obtained is next introduced
into a solution of 24 parts of gamma amidonaphtholsulphonic acid in 700 parts of
water and 36 parts of sodium carbonate.
The solution of the amidoazo compound thus obtained may be further used for
the preparation of polyazo dyes.
In our Provisional Specification (Examples 1. and 3), we described the process
of production of colouring matters, which contained, besides the radicals of
paradiamines, three molecules of gamma amidonaphtholsulphonic acid; since then,
we found, however, that these colours are already subject matter of British
Patent No. 19330/90. We therefore lay no claim to the manufacture of these
dyestuffs, although our process of manufacture is different.

page_text: 23 parts of diazo-amido-diphenylchloride, prepared by the interaction of tetrazo-
diphenylchloride and benzidine hydrochloride (comp. Täuber Ber d. Deutschen
Chem. Gesellsch. 1894 p. 2627) are introduced into an alkaline solution of
49 parts of the amidoazo compound produced by combining diazotised gamma
amidonaphtholsulphonic acid with gamma amidonaphtbolsulphonic acid in alkaline
solution. The reaction takes place readily, and is completed after some hours
stirring and subsequently heating to 50 deg. C. The dye thus produced, which is
isomeric with the so-called diamine black RO., and which, contrary to expectations,
is sufficiently soluble, dyes cotton intense violet black-brown shades. The above
colour may be tetrazotised and combined with m-toluylenediamine or resorcinol,
resulting in the formation of tetrakisazo dyes. We do not claim, however, the
manufacture of these tetrakisazo dyes, as it seems probable that the said
tetrakisazo dyes are identical with substances described in the British Patent
No 9259/94
21-2 parts of tolidine are tetrazotised and introduced into the alkaline solution of
227 parts of 1:4 naphtholsulphonic acid, and to the intermediate product thus
produced there is added an alkaline solution of 49 parts of the amidoazo compound
obtained by combining diazotised gamma amidonaphtholsulphonic acid with this
acid itself. The reaction is completed after stirring some time, heating to 50 deg.,
and finally to 80 deg. C. The dye thus produced dyes cotton goods reddish blue.
The alkaline solution of this reddish blue dye resulting at the above stage, may be
acidulated with hydrochloric acid, and whilst stirring 7 parts of nitrite of soda
added in order to convert the substance into a diazo compound, the latter is
finally introduced into an alkaline solution of 12.2 parts of m-toluylenediamine, or
of the corresponding quantity of m-phenylenediamine or of resorcinol; this
diazotation and combination of the blue colour with m-diamines may also be
performed on the fibre. The shades thus produced are black-blue. The tolidine
of the above example may be substituted by the corresponding quantities of other
paradiamines, such as benzidine, dianisidine, methoxybenzidine, paraphenylene-
diamine, and the like.
Having now particularly described and ascertained the nature of our invention,
we declare that what we claim is :-
1. The production of a new diamidodisazo colour by combining in alkaline solution
one mol. of diazoamido-diphenyl chloride with one mol. of the amidoazo compound
obtained by combining the diazotised gamma amidonaphtholsulphonic acid with
the same acid in alkaline solution.
II. The production of new polyazodyestuffs by combining the intermediate
product, obtained by the action of tetrazodiphenyl, or tetrazoditolyl, or tetrazo-
dianisydyl, or tetrazomethoxydiphenyl, or diazoacetanilide (in the latter case after
splitting off the acetyl group and diazotising again) upon 1 mol. of a naphthol-
ulphonic acid, such as 1-4 naphtholsulphonic acid or naphtholdisulphonic acid R.,
with 1 mol. of the amidoazo compound produced by the action of gamma diazo
aphtholsulphonic acid upon gamma aniidonaphtholsulphouic acid in alkaline
olution.
III. Producing polyazodyestuffs by combining the diazo compounds of the

page_text: trisazo dyestuffs enumerated in Claim 2, with one mol. of m-phenylenediamine,
m-toluylenediamine, or resorcinol.
IV. As new products of manufacture, the dyestuffs herein described.
WILLIAM HENRY CLAUS.
ALFRED RÉE.
LEON MARCHLEWSKI.