Improvements in and connected with Azo Colouring Matters.
Year: 1896

page_text: Date of Application, 26th June, 1896
Complete Specification Left, 22nd Mar., 1897-Accepted, 1st May, 1897
Improvements in and connected with Azo Colouring Matters.
We, IVAN LEVINSTEIN and LEVINSTEIN LIMITED, both of Minshull Street
Manchester in the County of Lancaster, Chemical Manufacturers, do hereby
declare the nature of this invention to be as follows:-
The Specification of Letters Patent No. 22641A, dated the 28th December 1891,
describes the use of the three Clève's naphthylamine sulpho-acids, (as ẞ, as ẞs, a₁ B),
in the production of azo and tetrazo colours, for so called middle components, as
substitutes for a naphthylamine. The specification also emphasises that the
a naphthylamine-a, mono-sulpho acid, which is also known as Schöllkopf's acid,
cannot be used for this purpose.
Further, in the Specification of Letters Patent No. 2789 dated the 12th
February 1892, it is stated that "amongst all isomeric naphthylamine sulpho acids
only the two acids which Clève has obtained by nitration and reduction from
naphthalene-6-sulpho-acid and which he has designated by the letters ẞ and 8 are
fit for the said purpose."
We can confirm the statements above referred to as far as they relate to
tetrazodiphenyl, tetrazoditolyl, tetrazodianisidine, and the like compounds. But,
we have found that if, instead of benzidine and its homologues specified in the cases
hereinbefore referred to, paraphenylenediamine is combined with one molecule of
a naphthylamine-a; mone-sulpho acid, the para-amidobenzene-azo-a, naphthyl-
amine-a-mono-sulpho acid thus obtained may be easily tetrazotised, and
combined with two molecules of naphthol-sulpho acids, dioxynaphthalene-sulpho
acids, or amidonaphthol mono- or di- sulpho acids, produce very valuable colouring
matters.
It is well known that, in order to produce tetrazo colours from paraphenylene-
diamine, two indirect methods may be employed.
Firstly. Diazoparanitrobenzene may be combined with one of the well known
colour components and the nitro group in the resulting nitro-azo colour reduced by
means of alkaline sulphides to the amido group, which may now be easily diazotised
and combined again.
Secondly. Acetylparaphenylenediamine may be diazotised and combined with a
colour component, the acetyl group split off, and the resulting amido-azo colouring
matter diazotised and combined again.
Therefore, to carry out our present invention, we may proceed as follows:-

page_text: was blue-violet, is changed into an orange-red and when it also becomes soluble in
dilute hydrochloric acid.
The reduced azo colour crystallises in bronze, leaf-shaped crystals which may be
entirely separated by salting out. It is then tetrazotised in the usual manner with
14.4 kilos. of nitrite of sodium and 40 kilos. of hydrochloric acid 20° Be.
The tetrazo compound, which is a difficultly soluble brown powder, is added to an
alkaline solution containing 48.0 kilos. of y amidonaphthol-mono-sulpho acid, and
this combination is well stirred for about 12 hours. It is then heated to about:
60 deg. C., salted out, filtered and dried.
EXAMPLE II.
150 kilos. of monoacetyl-paraphenylenediamine are dissolved in 200 litres of
water and 45 kilos. of hydrochloric acid 20° Be., and after cooling by means of ice,
the solution is diazotised with a concentrated solution containing 7.2 kilos. of nitrite
of sodium. When the formation of the diazo compound is completed, the solution
is allowed to run, whilst stirring, into a neutral solution of 24.5 kilos. of the sodium
salt of a naphthylamine-a mono-sulpho acid, the combination being completed
within a few hours, when the azo colour is filtered and pressed. The pressed
product is mixed with about 1000 litres of water and 240 kilos. of soda lye
of about 35° Be., and is boiled until the acetyl group is split off. The amidoazo
dye-stuff so obtained is identical with that obtained by the reduction of the nitroazo
dye-stuff of the preceding example, and when this dye-stuff is tetrazotised in the
usual manner, as set forth under Example 1, and combined with two molecules of
y amidonaphtholmono-sulpho acid, a colour is obtained identical with that obtained
according to that example.
The colouring matters obtained by following either method of procedure, dye
cotton without a mordant, a deep indigo blue, whilst wool is coloured thereby a
deep black when dyed in a bath acidulated with acetic acid. These colours there-
fore are not only valuable for dyeing cotton or wool, but may also be use with great
advantage for dyeing mixed fibres in a single bath, such for example as a mixture
of cotton and wool.
The above colouring matter, produced as hereinbefore described, having the
formula:
may also be further diazotised on the fibre in the well known manner, aud the
colour thus diazotised and fixed on the fibre may be combined with phenols, amines,
or diamines. The shades produced by diazotising the colouring matter on the
fibre in the manner described, are deeper and darker than the original colouring
matter and are also faster to soaping.
Dated this 24th day of June 1896
W. E. HEYS & SON,
Agents for the Applicants.

page_text: Improvements in and connected with Azo Colouring Matters.
We, IVAN LEVINSTEIN and LEVINSTEIN LIMITED, both of Minshull Street
Manchester in the County of Lancaster, Chemical Manufacturers, 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 Specification of Letters Patent No. 22,641A, dated the 28th day of
December A.D. 1891, describes the use of the three Cléve's naphthylamine sulpho
acids (alpha, beta, alpha, beta,, alpha, beta,), for so called middle components in
the production of azo and tetrazo colours, as substitutes for alpha-naphthylamine.
That specification also especially emphasises that the alpha,-naphthylamine alpha-
mono-sulphonic acid, which is also known as "Schöllkopf's acid," cannot be used
for this purpose.
Further, in the Specification of Letters Patent No. 2789 dated the 12th day of
February A.D. 1892, it is stated that "amongst all isomeric naphthylamine sulpho
acids, only the two acids which Cléve has obtained by nitration and reduction from
naphthalene beta-sulpho acid and which he has designated by the letters 'beta
and 'delta' are fit for the said purpose."
We can confirm the statements above referred to so far as they relate to tetrazo-
diphenyl, tetrazoditolyl, tetrazodianisidine, and the like compounds. But, we have
found that if, instead of benzidine and its homologues specified in the cases herein-
before referred to, paraplienylenediamine is combined with one molecule of alpha,-
naphthylamine alpha-mono-sulphonic acid, the para-amidobenzene-azo-alpha-
naphthylamine alpha,-mono-sulphonic acid thus obtained may be tetrazotised and,
combined with two molecules of naphthol sulpho acids, dioxynaphthalene sulpho
acids, or amidonaphthol mono- or di- sulpho acids, produce very valuable colouring
matters.
It is well known that in order to produce tetrazo colours from paraphenylene-
diamine, two indirect methods may be employed.
Firstly. Diazoparanitrobenzene may be combined with one of the well known
colour components and the nitro group in the resulting nitroazo colour reduced by
means of alkaline sulphides to the amido group, which may now be easily
diazotised and combined again.
Secondly. Acetylparaphenylenediamine may be diazotised and combined with a
colour component, the acetyl group split off, and the resulting amidoazo colouring
matter diazotised and combined again.
Therefore, to carry out our present invention, we may proceed as follows:-
13-8 kilos. of paranitraniline are diazotised in the usual manner, and the resulting
diazo compound is allowed to flow whilst stirring, into a neutral solution containing
24-5 kilos. of the sodium salt of alpha,-naphthylamine alpha,-mono-sulpho acid.
The combination begins at once and is complete within a few hours. The nitroazo
dye-stuff thus produced is entirely precipitated as blueish red needle shaped
crystals which may be filtered off and pressed.
The pressed cake is dissolved in about 300 litres of hot water with the addition
of soda or other suitable alkali. To this solution, whilst stirring, sodium sulphide
is gradually added. The reduction is completed when the colour, which was at
first blue violet, is changed into an orange-red, and when it also becomes soluble
in dilute hydrochloric acid.

page_text: The reduced azo colour crystallises in bronze, leaf-shaped crystals which may
be entirely separated by salting out. It is then tetrazotised in the usual manner
with 144 kilos. of sodium nitrite and 10 kilos. of hydrochloric acid 20° Bé.
The tetrazo compound which is a difficultly soluble brown powder, is added to
an alkaline solution containing 48.0 kilos. of gamma-amidonaphthol mono-sulphonic
acid, and this combination is well stirred for about 12 hours. It is then heated
to about 60° C., salted out, filtered and dried.
EXAMPLE 1I.
15.0 kilos. of mono-acetyl-paraphenylenediamine are dissolved in 200 litres of
water and 45 kilos. of hydrochloric acid 20° Bé., and after cooling by means of
ice, the solution is diazotised with a concentrated solution containing 7.2 kilos.
of sodium nitrite. When the formation of the diazo compound is completed, the
solution is allowed to run whilst stirring, into a neutral solution containing
24-5 kilos. of the sodium salt of alpha,-naphthylamine alpha-monosulpho acid, the
combination being completed within a few hours when the azo colour is filtered
and pressed. The pressed product is mixed with about 1000 litres of water and
240 kilos. of soda lye of about 35° Bé., and is boiled until the acetyl group is split
off. The amidoazo dye-stuff so obtained is identical with that obtained by the
reduction of the nitroazo dye-stuff of the preceding example, and when it is
tetrazotised in the usual manner, as set forth under Example I, and combined with
two molecules of gamma-amidonaphthol mono-sulphonic acid, a colour is obtained
identical with that obtained according to that example.
The colouring matters obtained by following either method of procedure, dye
cotton without a mordant, a deep indigo blue, whilst wool is coloured thereby a
deep black when dyed in a bath containing, acetic acid. These colours therefore
are not only valuable for dyeing cotton or wool, but may also be used with great
advantage for dyeing mixed fibres in a single bath, such for example as a mixture
of cotton and wool.
The colouring matter produced as hereinbefore described and which has the
formula:-
may also be further diazotised on the fibre in the well known manner, and the
colour thus diazotised and fixed on the fibre may be combined with phenols, amines
or diamines. The shades produced by diazotising the colouring matter on the fibre
in the manner described are deeper and darker than those produced by the original
colouring matter and are also faster to soaping.
Having now particularly described and ascertained the nature of our said inven-
tion and in what manner the same is to be performed, we declare that what we
claim is :-
1. Aga new substance

page_text: of paraphenylenediamine with one molecule of alpha-naphthylamine alpha-mono-
sulphonic acid, tetrazotising and further combining the intermediate product with
two molecules of naphthol sulphonic acids, dioxynaphthalene sulphonic acids,.
or amidonaphthol mono- or di- sulphonic acids, substantially as hereinbefore
described.
2. The hereinbefore described process for the production of an azo colour,.
which consists in combining diazoparanitrobenzene with alpha,-naphthylamine
alpha-sulphonic acid, reducing the nitro group to the amido group by alkaline
sulphides, diazotising, and recombining; substantially as set forth under Example I.
3. The hereinbefore described process for the production of an azo colour,.
which consists in diazotising acetyl paraphenylenediamine, combining it with
alpha, naphthylamine alpha-sulphonic acid, splitting off the acetyl group, and
diazotising and recombining the resulting amido-azo colouring matter; substantially
as set forth under Example II.
Duted this 19th day of March A D 1897
W. E. HEYS & SON,
Agents for the Applicants..