Year: 1896

page_text: Date of Application, 20th Nov., 1896
Complete Specification Left. 20th Aug., 1897-Accented. 2nd Oct.. 1897
This product dyes unmordanted cotton in slaty-blue shades. It may be further
tetrazotised and combined with the following substances: metaphenylene diamine,
meta toluylene diamine, resorcinol, sulpho acids of naphthylamines and naphthols,
such as naphthionic acid and 1: 4 naphthol-sulphonic acid, with amido-naphthol-
5 mono and disulphonic acid, such as gamma-amido-naphthol-sulphonic acid, H-amido-
nanhthol-disulphonic acid and the like

page_text: 2. EXAMPLE.
Instead of using in the first example alphanaphthylamine, other substances may be
used, that is all substances which are capable of combining with 1 mol. of
tetrazodiphenyl (and similar tetrazo compounds), leaving one diazo group of the
latter intact, according to the chemical nature of these substances, the last stage of
the first example may or may not be performed. For instance
a. Tetrazo-ditolyl is combined with one inol. of salicylic acid and the intermediate
product thus produced (2 nol.) combined in alkaline solution with 1 mol. of the
amido-azocompound G. 2. The constitution of this azo-compound may be expressed
by the following formula:
b. Tetrazodianisidyl is combined with 1 mol. of 1:4 amido-naphthol-sulphonic
acid and the intermediate product (2 mol.) is combined in alkaline solution with
1 mol. of the amido-azocompound G. 2. The colouring matter which dyes in reddish
blue shades, possesses, we believe, the following formula:
c. Tetrazodiphenyl is combined in alkaline solution with 1 mol. of gamina-amido-
naphthol-sulphonic acid and 2 mol. of the sparingly soluble intermediate product
thus produced, introduced into an alkaline solution of 1 mol. of the amido-azo-

page_text: compound G. 2. A black colouring matter is formed possessing,
ing formula;
we believe, the follow-
This product may be tetrazotised and combined with toluylenediamine, resorcinol,
61: 4 naphthol-sulphonic acid and the like. This tetrazotation and combination with
final components may be performed on the fibre.
3. EXAMPLE,
2 mol. of acet-para-phenylenediamine are diazotised and combined in alkaline
solution with 1 mol. of the amido-azocompound G. 2. The intermediate product must
be boiled with alkalies in order to split off the acetyl groups and the saponified product
may be combined after tetrazotation with amines, phenols, naphthylamine-sulphonie
acids, naphthol-sulphonic acids or amido-naphthol-sulphonic acids.
When for
instance 1:4 naphthol-sulphonic acid is used, a blue colouring matter is
produced.
4. EXAMPLE.
In our Provisional Specification 18020/96, a compound has been described, which
is produced by the action of diazo-amido-diphenyl upon the amido-azocompound
produced by combining gamma-amnido-naphthol-sulphonic acid with itself in alkaline
solution. This compound may be combined in neutral or slightly acid solution with
the dinzo compound derived from acetyl-para-phenylenediamine and the intermediato
body thus produced, may be, after diazotation, combined in alkaline solution with the
amido azocompound G. 2. taking 2 mol, of the former and 1 mol. of the latter.
compound produced is saponified and the resulting colour dyes cotton black.
The same product may be prepared in the following way:
Gamma-amido-naphthol-sulphonic acid is diazotised and combined in alkaline
solution with itself. As soon as the reaction has taken place, the liquid is slightly
acidified with hydrochloric acid and sodium acetate added and then mixed with
1 mol. of diazotised acetyl-para-phenylenediamine. The amido disazo-compound
produced, is next introduced into an alkaline solution of tetrazodiphenyl taking
1 mol. of each substance and the diazo-polyazo-compound obtained, finally introduced
into au alkaline solution of the amido-azocompound G. 2. taking 2 mol. of the former
and 1 mol. of the latter. The product may finally be saponified.
5. EXAMPLE.
2 mol. of diazo-amido-diphenyl are introduced into an alkaline solution of 1 mol.
of the amido-azo-compound G.2. The produced compound dyes cotton goods in
slaty blue shades. It inay be converted into other dyes by the following process;
The alkaline solution is acidified by means of hydrochloric acid, and the
triamidotriazo-compound tetrazotised by adding 2 mol. of sodium nitrite.
produced tetrazo-compound may be combined with 2 mol. of amines, phenols,
naphthols, amidonaphthols and sulpho-acids thereof, and also with the amido-azo

page_text: compound G. 2. In the last case, the obtained substance would appear to possess the
following constitution:
The same colours may be also obtained by the action of 2 mol. of tetrazodiphenyl
(tetrazo-diphenyl and the like) on 1 mol. of the amido-azocompound G. 2. in alkaline
solution. After stirring some time, 2 inol. of the final components (such as 2 mol.
of 1:4 naphtholsulphonic acid or 2 mol. of meta-toluylenediamine and the like) or
Imol. of the amido-azocompound G. 2. are added and whilst the solution is kept
alkaline, it is stirred for several hours and heated to about 80° C.; finally the colours
may be salted out, filterpressed and dried.

page_text: As soon as the formation of this product is completed, 2 mol. of a diazo-compound
for instance of diazotised p-amido-acetanilide, is added and finally the acetyl group
split off by boiling the alkaline solution for some time.
Tetrazodiphenyl is combined with 1 mol. of alpha-naphthylamine and the thus
obtained produce diazotised in the well known manner. Next an amine or phenol or
amido-phenol or a sulphoncid thereof in the proportion of 1 nol. is added and after
short stirring, 2 mol. of the so produced substance are introduced into the alkaline
solution of 1 mol. of the amido-azocompound G. 2. If phenylenediamine is used,
the produced dye possesses probably the following formula:
Gamma-amido-naphthol-sulphonic acid is diazotised and combined with 1 mol, of &
metadiamine such as meta-phenylenediamine or with 1 mol. of a naphthylamine sulpho-
acid or naphthol sulphoacid, 1 mol. of the substance thus obtained is allowed to act on
1 mol. of a tetrazo-compound and finally 2 mol, of this intermediate product allowed to
act upon 1 mol. of the amido-azocompound G. 2. If in this example 1 : 4 naphthol
sulphonic acid be used for the naphthol-sulphoacid and diazotised benzidine for the
tetrazo-compound, the dye obtained possesses probably the following formula;

page_text: different.
We may mention that in all the above enumerated examples, the amido-
azocompound G. 2. can be substituted by the following substances:
1. Amido-azocompounds produced by interaction of (a) diazotised amido-naphthol-
gamma-sulphonic acid and H-amido-naphthol-disulphonic acid in acid solution
(b) diazotised amido-naphthol-gamma-sulphonic acid and I-amido-naphthol-sulphonic
acid (English Patent 2370/93) in acid solution (c) diazotised amido-naphthol-gainina-
sulphonic acid and amido-naphthol-sulphonic acid S.
2. Amido-azocompounds produced by the action of diazotised H-amido-naphthol-
disulphonic acid, or diazotised I-amido-naphthol-sulphonic acid, or diazotised S-amido-
naphthol-sulphonic acid, upon gamma-amido-naphthol-sulphonic acid in acid
solution.
3. The amido-azocompounds produced by interaction of diazotised H-amido-
naphthol-disulphonic acid upon the same acid in acid solution, of diazotised I-amido-
naphthol-sulphonic acid upon the same acid in acid solution, of diazotised
S-amido-naphthol-sulphonic acid upon the same acid in acid solution.
Dated this the 19th day of November 1896.
WILLIAM HENRY CLAUS.
ALFRED RÉE.
LEON MARCHLEWSKI.
WILLIAM HENRY CLAUS ALFRED REE both Chemical Manufacturers of Clayton, 25
Manchester late of Droylsden, Manchester, and LEON MARCHLEWSKI Chemist of
25 Wellington Street Higher Broughton, Manchester, do hereby declare the nature of

page_text: 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 azo colouring matters which dye cotton without the aid of
mordants; their constitution may be expressed by the following general formula:
in which D. represents the radical of a tetrazolisable para-diamine, X. an amine,
phenol, amidophenol, naphthol, ainidonaphthol, or sulpho or carboxy acid thereof;
N. atoms of nitrogen and G 2 amidonzo compounds, produced by combining diazotised
amidonaphtholsulpho acids with unidonaphtholsulpho acids in acid solution.
The colouring matter of the above general formula inay be produced according to
different methods, namely:
1. Two molecules of a tetrazotised paradiamine are allowed to act in alkaline
solution upon one mol. of the amidoazo compound (+ 2 and the intermediate product,
having the formula:
2. One mol, of a paradiamine (benzidine, tolidine, dianisidine and the like) is
combined in acid or alkaline solution with one nol. of a substance capable of forming
azo bodies with diazo compounds. Two mols. of the intermediate product obtained
are then allowed to act upon one inol. of the amidoazo compound G 2.
3. One inol. of a tetrazotised paradiamine is allowed to act in alkaline solution
upon one inol. of an amidonaphthiolsulphonic acid. The intermediate product obtained
is diazotised and combined in acid solution with I mol. of an amidonaphtholsulphonic
acid. The intermediate product obtained is allowed to act upon one mol, of a
tetrazotised paradiamine and, finally, one mol. of the resulting tetrazo compound
combined with two mols. of an amine, phenol, amidophenol, naphthol, amidonaphthol,
or sulpho or carboxy acid thereof.
These 3 methods are the most suitable, although not the only possible oues, and
amongst these, the method No. 2. is, in the majority of cases, preferable to methods
Nos. 1. and 3., although, in some cases, method No. 1 affords better results than
method No. 2.
Amongst the amidoazo compounds G2, the following one is of special interest:
The amnidoazo compound obtained by combining the diazotised gamma-amido-
naphtholsulphonic acid with amido-naphtholdisulphonic acid I in acid solution. The
production of this amidonzo compound is carried out as follows: 26'1 parts of gamma-
amidonaphtholsulphonate of soda are dissolved in 520 parts of water, the solution
cooled with ice and acidified with 52 parts of hydrochloric acid of 28° B. To this
solution is gradually added a 10% solution of 7 parts of sodium nitrite. The diazo
compound produced is next introduced into the cooled solution of 31.9 parts of
amido-naphtholdisulphonicacid H. in 650 parts of water. There is gradually formed

page_text: a violet compound, and in order to complete its formation, a solution of 50 parts of
sodium acetate is added.
In order to illustrate the working of our invention the following examples may be
given :
EXAMPLE 1.
Two molecules of a tetrazotised paradiamine are combined in alkaline solution
with 1 mol. of the orthoamidonzo compound produced by combining diazotised
gamma-amidonaphtholsulphonic acid with amidonaphtholdisulphonic acid H. in acid
solution, and the intermediate compound obtained, which still contains 2 free diazo
groups, coupled with 2 mols. of an amine, phenol, naphthol, amido-naphthol, or
sulpho or carboxy acid thereof.
For instance: 36-8 parts of benzidine are tetrazotised in the well-known manner
by means of nitrous acid; and the tetrazo compound obtained introduced into the
strongly alkaline solution of 56-9 parts of the above-named ortho-amidoazo
compound. The mixture is left to stand for about balf-an-hour, when it will be
found that all the tetrazo compound has disappeared. There is formed the following
black insoluble intermediate product.-

page_text: the ortho-amidoazo compound (comp. Example 1.) is quickly filtered off and allowed
to act in slightly alkaline solution upon 245 parts of netatoluylenediamine. The
mixture is stirred for some time at ordinary temperatures and finally at
50° and 80° C. The colouring matter produced dyes cotton violet brown. Similar
colouring matters, varying in shade according to the nature of the end component
used, are obtained by substituting the toluylenediamine of the above example by
22 parts of resorcinol, or 41-5 parts of the chrysnidine obtained by combining
p-diazo-benzene sulphonic acid with metatoluylenediamine.
36.8 parts of benzidine are tetrazotised in the well-known manner, and the solution
obtained int reduced into a cold solution of carbonate of soda, To this slightly
O alkaline solution there is added 52.2 parts of gainina-amidounphtholsulphonate of
soda. As soon as the intermediate product is formed, there is added a mixture of a
solution of 56.9 parts of the ortho-puido compound (obtained by combining diazotised
B

page_text: gamma-amidonaphtholsulphonic acid with amidonaplitholdisulphonic acid H. in acid
solution) with the solution of 30 parts of carbonate of Foda in about 200 parts of
water. The mixture is stirred for some time at ordinary temperature, and finally
heated up slowly to 50° and 80° C. The colouring matter produces dyes cotton
reddish black-blue shades. It may be dinzotised on the fibre or in substance and
combined with m-toluylenediamine, resorcinol or beta-naphthol. The shades produced
are dark blue and violet, black-brown.
The gamma-amidonaphtholsulphonic acid of this example may be substituted by
the equivalent quantities of other components suitable for making azo colours. If,
for instance, alpha-naphthylamine is combined in acid solution with tetrazodiphenyl
and the intermediate product allowed to re-act on the ortho-amidoazo compound
mentioned, a greyish-blue colouring matter is produced, which, when diazotised on
the fibre and combined with m-toluylenediamine, produces a fast brown colouring
matter.
In order to illustrate the working of the last of the two mentioned methods for
producing colouring matters in question, the following example may be given:
EXAMPLE 6.
18.4 parts of benzidine are tetrazotised, and the tetrazo compound obtained
introduced into a cold solution of carbonate of soda.. To this solution is added
26-1 parts of gamma-amidonaphtholsulphonate of soda. As soon as the forination of
the intermediate product is completed, the liquid is acidified and treated with a
10% solution of 7 parts of sodium nitrite. The tetrazo compound obtained is inixed
with a solution of 31.9 parts of amidonaphtholdisulphonic acid H. and about 70 parts
of acetato of sodium in about 638 parts of water. The combination takes place slowly.
As soon as it is completed, the mixture is made alkaline and the solution obtained by
tetrazotising 18-7 parts of benzidine added. The intermediate product, which still
contains two free diazo groups, may be finally combined with two mol. of an end
component, as in the manner previously described.
EXAMPLE 7.
Instead of using, as in the foregoing examples, simple azo-colour end components
or chrysoidines, certain other azo bodies may be applied. For instance: 36-8 parts
of benzidine are tetrazolised in the well-known manner and combined in alkaline
Bolution with 56-9 parts of the amidoazo compound obtained by coupling diazotised
gamma-amido-naphtholdisulphonic acid with amidonaphtholdisulphonic acid H. As
soon as the formation of the intermediate product is completed, there is addedau alkaline
solution of 1138 parts of the amidoazo compound obtained by combining diazotised
gamma-amidonaphtholsulphonic acid with this acid itself in alkaline solution. The
mixture is stirred for some time and then gradually heated up to 50° and 80° C.
The colouring matter produced dyes cotton from grey to reddish black-blue. The
constitution of this colour may be expressed by the following formula:

page_text: amidoazo compound may be substituted by other similar bodies, for instance, by the
combination of diazotised gamma-amido-naphtholsulphonic acid with
(a) other amidonaphthols, or their sulpho acids, such as amidonaphtholdisulphonic
acid H.,
(b) naphthols or their sulpho acids, such as 1.4 naphthol sulpho acids,
(c) naphtylamines, and their sulpho acids such as 1.4 naphtylaminsulphonic acid.
Tetrazoditolyl is combined with 1 mol. of gamina amidonaphtholsulphonic aoid in
acid solution, and the intermediate product allowed to act upon the ortho-amidoazo-
compound & 2, mentioned in the foregoing examples in alkaline solution. The
resulting colour dyes cotton violet, and can, although not easily, be combined with
2 mol. of a diazo compound.

page_text: invention, and in what manner the same has to be carried out, we declare that
what we claim is:
1. Tho production of colouring matters of the general formula:
D
N₁ -
N, G.2 N
-
N₂
D
N,-X X-N,
by combining 2 mol. of a tetrazotised paradinmine with one mol. of the ortho-amidoazo 5
compound obtained by combining diazotised gamma-amnido-naphtholsulphonic acid
with amidonaphtholdisulphonic acid H. in acid solution, and coupling the inter-
mediate product obtained in alkaline or acid solution with 2 mol. of an amine,
diamine, phenol, resorcinol, naphthol, amidonaphthol, or sulpho or carboxy acid
thereof, or a chrysoidine, or by an equivalent method substantially as described.
2. The production of colouring matters of the general formula:
1
by combining two mol. of a tetrazotised paradianine with 1 mol. of the ortho-
amidonzo compound, obtained by combining diazotised gamma-amidonaphthol-
sulphonic acid with amidonaphtholdisulphonic acid H. in acid solution, and coupling
the intermediate product obtained with 2 mol. of an azo compound obtained by
coupling diazotised gamma-amidonaphtholsulphonic acid with an amine, phenol,
naphthol, amido-naphthol, or sulpho or carboxy acid thereof, or by an equivalent
method substantially, as described.
3 The production of colouring matters of the general formula
(in which D. represents a paradiamine, N. atoms of nitrogen, G.2 the ortho-
amidoazo compound, X. gamina-amidonaphtholdisulphonic acid or alpha-naphthyl-
amine or 1:6 or 1:7 naphthylaminesulphonic acid, and Y. a phenol, like resorcinol,
or a diamine, such a m-phenylenediamine, or amidophenol), by combining two mols.
of a tetrazotised paradiamine with two mol. of alpha-naphthylamine or 1:6 or
1:7 naphthylaminsulphonic acid, and coupling the intermediate products obtained
with mol. of the ortho aunidoazo compound G-2, mentioned in the foregoing

page_text: claims, tetrazotising the colour produced, and combining it in substance or on the
fibre with 2 mol. of an amino, phonol, or amidophenol.
4. The production of colouring matters of the general formula:
by combining 2 mols. of a tetrazotised pamdiamine with one mol. of the ortho
amidoazo compound obtained by combining diazotised gamma-amidonaphtholsulphonie
acid with amidonaphtholdisulphonic acid H. in acid solution, and coupling the
intermediato product obtained with a second molecule of the ortho-amidonzo
compound mentioned above.
5. The colouring matters described.