Year: 1895

page_text: Date of Application, 9th Dec., 1895
Complete Specification Left, 9th Sept., 1896--Accepted, 5th Dec., 1896
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:-
A great disadvantage, which prevents the more extensive use of some of the
direct dyeing red and brown azo colours, is that they are not fast to daylight.
The object of our present invention is the production of such colours which will
surpass, in fastness to light, most of the azo colours hitherto known.
For this purpose, we have found that the mixed tetrazo colours resulting from
the combination of one molecule of the tetrazo compounds of paradiamines with one
molecule of salicylic acid or homologues thereof and one molecule of aniline or
homologues thereof, when further diazotised and combined with naphthylamine
sulpho acids, naphthol sulpho acids, amidonaphthol sulpho acids, or dioxynaphtha-
lene sulpho acids, produce colours giving the desired result.
The following examples are given as illustrating the methods we may employ in
carrying out our invention.
18.4 kilos. of benzidine are converted in the usual manner into tetrazodiphenyl
chloride, which is then combined with 14 kilos. of salicylic acid. The formation of
the intermediate product begins at once and the reaction is completed in a
comparatively short time.
The intermediate product is allowed to run into a solution in water of 26 kilos.
of aniline hydrochloride.
The resulting mixture is stirred for about 12 hours and is afterwards heated to
about from 40 to 50 degrees C., and kept at this temperature for about six hours.
The mixture is then made alkaline, and the auiline which has not entered into
combination is removed in the usual well known manner. As soon as the super-
Huous aniline has been removed, the mixture, which contains a yellow colouring
matter having the following formula :-
O is then acidulated by means of hydrochloric or other suitable acid, and is then
diazotised with 7.2 kilos. of nitrite of sodium and stirred for a few hours.
After subsequently standing for about 12 hours, the formed, insoluble, brown
diazo compound is poured into an alkaline solution containing 24 kilos. of
y amidonaphthol sulpho acid, whilst stirring.

page_text: The formation of the dye-stuff is completed after a short time, whereupon it is
salted out, filtered, pressed and dried. It forms a brownish black powder and dyes
unmordanted cotton a deep brown.
EXAMPLE II.
A colouring matter similar to that produced according to Example I, is the
result, if monodiazotised benzidine, (Täuber, Ber. 1894, p. 2627), is combined with
one molecule of aniline and if the so obtained amido-azo base :-
is tetrazotised and combined, first, with one molecule of salicylic acid, and
afterwards with one molecule of y amido-naphthol sulpho-acid.
We may adopt the following mode of procedure:
:-
28.8 kilos. of the above named amido-azo base are converted, in the well known
manner, into the tetrazo compound with 144 kilos. of nitrite of sodium. The
solution of the tetrazo compound is allowed to run into a solution containing
14 kilos. of salicylic acid rendered alkaline, preferably by means of sodium
carbonate. The formation of the intermediate product begins at once and is
completed in a short time.
24 kilos. of y amidonaphthol sulpho-acid in an alkaline solution are now added
and the resulting dye-stuff may be salted out, filtered, pressed and dried.
If, instead of y amidonaphthol sulpho-acid, y phenylamidonaphthol sulpho-acid
is employed, a dye-stuff is obtained which dyes much darker shades.
Red dye-stuffs result if, instead of y amidonaphthol sulpho-acid, naphthol
sulpho-acids, such for instance as a' naphthol-a2 sulpho-acid, are substituted.
A series of very valuable dye-stuffs, from red to deep brown, result if, instead of
benzidine, other paradiamines are employed as for example, tolidine, dianisidine,
ethoxy-benzidine, diamidostilbene-disulpho-acid, and if, instead of aniline, its
homologues such as orthotoluidine, or paraxylidine are used.
The colouring matters produced according to this invention are suitable not only
for cotton, but also for wool, silk, jute, and other textile fibres, leather, paper and
similar materials.
Dated this 6th day of December A.D. 1895.
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 :-
A great disadvantage, which prevents the more extensive use of some of the
direct dyeing red and brown azo colours, is that they are not fast to daylight.

page_text: The object of our present invention is the production of such colours which will
surpass, in fastness to light, most of the azo colours hitherto known.
For this purpose we have found that the mixed tetrazo colours resulting from
the combination of one molecule of the tetrazo compounds of paradiamines with
one molecule of salicylic acid or homologues thereof, and one molecule of aniline or
homologues thereof, when further diazotised and combined with amines, phenols,
anidophenols, dioxy-compounds both of the benzene and naphthalene series, as
well as their known carboxyl- and sulpho-acids, produce colours giving the desired
result.
The following examples are given as illustrating the methods which we may
employ in carrying out our invention.
18.4 kilos. of benzidine are converted, in the usual manner into tetrazodiphenyl
chloride, which is then combined with 14 kilos. of salicylic acid. The formation of
the intermediate product begins at ouce, and the reaction is completed in a
comparatively short time.
The intermediate product is allowed to run into a solution in water of 26 kilos. of
aniline hydrochloride.
The resulting mixture is stirred for about 12 hours, and is afterwards heated to
about from 40° to 50° C., and is kept at this temperature for about 6 hours. The
mixture is then made alkaline, and the aniline which has not yet entered into
combination, is removed in the usual known manner. As soon as the superfluous
aniline has been removed, the mixture, which contains a yellow colouring matter
having the following formula :--
is acidulated by means of hydrochloric acid or other suitable acid, and is then
diazotised with 7.2 kilos. of sodium nitrite, and stirred for a few hours.
After subsequently standing for about 12 hours, the formed browu diazo com-
pound is poured into an alkaline solution containing 24 kilos. of amidonaphthol
sulpho-acid y, whilst stirring.
.
The formation of the dyestuff is completed after a short time, whereupon it is
salted out, filtered, pressed, and dried. It forms a brownish-black powder and
dyes unmordanted cotton a deep brown.

page_text: with about 20 parts of water to a thin paste, cooled by means of ice, and acidulated
with 70.0 kilos. of hydrochloric acid 18° Bé.
This mixture is then diazotised with a solution of 7.2 kilos. of sodium nitrite.
After being stirred for about 12 hours, the reaction is completed. The insoluble
brown diazo compound thus formed is allowed to run into an alkaline solution of
31-5 kilos. of phenylamidonaphthol sulpho-acid y. The formation of the dye stuff
is completed after a short time. It is then salted out, filtered, pressed and dried.
It dyes unmordanted cotton a deep black-brown.
Red dye-stuffs result if, instead of amidonaphthol sulpho-acid y, naphthol
sulpho-acids, such for instance as naphthol sulpho-acid N.W., are substituted in
the examples above given, and yellow dye-stuffs result if salicylic acid be
substitutively employed.
A series of very valuable dye-stuffs, from red to deep brown, result if, instead of
benzidine, other paradiamines are employed, as for example, tolidine, dianisidine,
ethoxybenzidine, diamidostilbene disulpho-acid; and if, instead of aniline, its
homologues such as orthotoluidine or paraxylidine are used.
The colouring matters produced according to this invention are suitable, not
only for cotton, but also for wool, silk, jute, and other textile fibres.
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. The hereinbefore described process for the production or manufacture of
direct dyeing trisazo colours, which consists in diazotising mixed tetrazo colours
which result from the combination of one molecule of a paradiamine with oue
molecule of an ortho-oxycarbonic acid (of the benzene series), and with one
molecule of a primary aromatic monamine of the benzene series and combining the
so obtained diazo compounds with amines, phenols, amidophenols, and dioxy-bodies
both of the benzene and naphthalene series as well as the known carboxyl- and
sulpho-acids of these, substantially as set forth.
2. As new articles of manufacture, the colouring matters or dye-stuffs which
result from the process set forth in the preceding claiming clause and more
particularly herein before described.
Dated this 29th day of August A.D. 1896.
W. E. HEYS & SON,
Agents for the Applicants.