Year: 1899

page_text: amido trichlorbenzene and their homologues with the alpha, amido alpha, naphthol
beta, beta, disulphonic acid H.
If these monoazo colouring-matters be combined in an alkaline solution with one
molecule of a tetrazotised paradiamine such as benzidine, tolidine, dianisidine,
ethoxybenzidine and the like, and the intermediate products thus obtained be then
further coupled under well known suitable conditions with any suitable colour-
producing agent as for instance amines, diamines, phenols, amidophenols, oxyphenols
their sulpho- and carboxylic acids both of the benzene and naphthalene series; blue,
green to black direct colouring-matters result possessing the above mentioned valuable
properties.
However it may be stated that in some cases it may be preferable to reverse the
course of these operations, that is to say it may be preferable first to combine the
tetrazotised paradiamine with one molecule of a suitable colour producing agent to a
n
027

page_text: 80 called intermediate-product and coupling it then in an alkaline solution with one
molecule of the above mentioned monoazocolouring matters.
1 L
don of Amil 1900
HASELTINE, LAKE, & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.
Improvements in the Manufacture of Azo Colouring-matters.
I, HENRY HARRIS LAKE, of the Firm of Haseltine, Lake and Co., Patent Agents,
45, Southampton Buildings, in the County of Middlesex, 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 monoazodyes prepared by coupling in an acid solution in molecular proportions
the diazocompound of an aromatic amine having in its nucleus at least two chlorine
groups with the alpha, amido alpha, naphthol beta, beta, disulphonic acid H, are
as such without any particular value for dyeing and printing.
But we have found that they may be used as initial material for the production of
new and very valuable colouring matters, dyeing vegetable fibres without a mordant
blue, green to black shades which are distinguished by their brilliancy and great
fastness to alkalies.
By an aromatic amine having in its nucleus at least two chlorine groups those
derivatives of aniline, toluidine their analogues and homologues are to be understood
in which two or more hydrogen atoms of the nucleus are replaced by chlorine.
The best results have up to now been obtained with the monoazocolouring matters
resulting from the combination in acid solution of one molecule of amidodichlor-
benzene
or amidodichlorbenzene
[NH, CI, CI
1, 2, 4],
[NH, Cl, Cl
===
1, 2, 5],
or amidodichlorbenzene
[NH₂, CI, Cl
=
1, 3, 4],
or amidotrichlorbenzene and their homologues with the alpha, amido alpha
naphthol beta, beta, disulphonic acid H.
If these monoazocolouring matters be combined in an alkaline solution with one
molecule of a tetrazotised paradiamine such as benzidine, tolidine, dianisidine,
ethoxybenzidine and the like, and the intermediate products thus obtained be then
further coupled under well known suitable conditions with any suitable colour-
producing agent as for instance, amines, diamines, phenols, amidophenols, oxyphenols
their sulpho-and carboxylic acids both of the benzene and naphthalene series; blue,
green to black direct colouring matters result possessing the above mentioned
valuable properties.
However it may be stated that in some cases it may be preferable to reverse the
course of these operations, that is to say it may be preferable first to combine the
tetrazotised paradiamine with one molecule of a suitable colour producing agent to a
so called intermediate product and coupling it then in an alkaline solution with one
inolecule of the above mentioned monoazocolouring matters.
The following examples may illustrate the carrying out of our invention.

page_text: 34.1 kilos. of the acid sodium salt of 1.8 amidonaphtol 3.6 disulphonic acid (H)
100% are dissolved in 400 liters of water by addition of 5 kilos. of sodium carbonate
and then precipitated with 30 kilos. of muriatic acid of 21° Bé. The finely divided
paste thus obtained is combined whilst stiring well with the diazɔcompound prepare 1
by diazotizing an ice cold solution of 16.25 kilos. of dichloraniline
(NH, : C1: C11:2:5)
in 300 liters of diluted muriatic acid of 7.3% with 6.9 kilos. of sodium nitrite. The
reaction is finished within about twelve hours. The monoazodye thus formed
represents a brown-red paste, easily soluble in alkalies with a violet-red color.
The acid paste of this monoazodye is then mixed with the tetrazo diphenyl
solution obtained in the well known inanner from 18.4 kilos. of benzidine and the
resulting mixture thoroughly stirred up, is afterwards poured slowly into an ice cold
solution of 40 kilos. of sodium carbonate in 400 liters of water.
After having been stirred for an hour the black precipitation of the intermediate
product is then combined with a solution of 20 kilos. of phenol in 10 kilos. of ammonia
of 16% and 50 liters of water. The mixture is allowed to stand for about 20 hours,
care being taken to stir from time to time. The combination is then completed and
the fine dark green precipitate is filtered, dried and pulverized.
The
The dyestuff thus obtained represents a dark powder with a bronzelike lustre,
soluble with
a green color in
water, nethylic alcohol, and spirit.
solution in strong sulphuric acid is of dark violet coloration. Reducing agents as
for instance, zincdust in presence of soda lye destroy the green color and by boiling
the colorless solution thus obtained the characteristic strong smell of the dichloraniline
distilling with steam will be observed.
The new trisazocolor dyes unmordanted cotton in a neutral or alkaline bath and
also wool and silk in an acid or neutral bath in presence of glaubersalt or common-
salt, green shades fast to light and alkali carbonate.
EXAMPLE II.
The acid paste of the monoazodye formed according to the foregoing example
from 16.25 kilos. of 1.2.4 dichloraniline and 34.1 kilos. of 1.8 amidonaphtol 3.6
disulphonic acid (H), is made alkaline by addition of 35 kilos. of caustic soda
dissolved in 100 liters of water. The violet-red solution thus obtained is allowed to
pour into the finely divided yellow paste of the intermediate product prepared in the
usual manner from the tetrazo compound of 18.5 kilos. of benzidine, 14 kilos. of
salicylic acid, 4 kilos. of caustic soda, and 15 kilos. of sodium carbonate. The
mixture diluted to 10000 liters is stirred up from time to time during a week. As
soon as the precipitate has turned entirely into dark green flakes, it is boiled up and
the dyestuff is precipitated by addition of 300 kilos. of cominonsalt, filtered dried and
pulverized.
It dyes unmordanted cotton nearly the same green shade as the trisazocolor of the
example I.
Similar green dyestuffs can be prepared by using in the foregoing examples the
tetrazo compounds of tolidine, dianisidine, ethoxybenzidine and the like in place of
benzidine and by substituting the phenol by o-or m-cresol or resocinol and the
salicylic acid by o-cresotinic acid. It may also be stated, that in all these cases the
diazodiclilorbenzene 1.2.4 or 1.2.5 can be replaced by the other isomeric diazodichlor-
benzenes and their homologues, diazotrichlorbenzenes and their homologues.
EXAMPLE III.

page_text: carbonate and are then precipitated in a finely divided state by the addition of
30 kilos. of muriatic acid of 21° Bé. The finely divided paste thus obtained is then
combined with the diazo compound prepared by diazotizing with 6.9 kilos. of sodium
nitrite an ice cold solution of 16.25 kilos. of dichloraniline
(NH2: Cl: Cl=1:2:5)
in 300 liters of diluted muriatic acid of 7.3%. The combination is finished within
about twelve hours, when by the well known tests neither free diazocompound nor
uncombined amidonaphtolsulphonic acid can any more be detected.
The redbrown acid paste of this monoazodye is then mixed with the tetrazo-
diphenyl solution obtained in the well known manner from 18.4 kilos, of benzidine and
the resulting mixture thoroughly stirred up, is afterwards poured slowly into an ice
cold solution of 80 kilos. of sodium carbonate in 800 liters of water. The combination
begins at once and after stirring for about one hour the black precipitate of the
intermediate product thus obtained is then combined with the solution of 34.1 kilos.
of 1.8 amidonaphtol 3.6 disulphonic acid H (100% acid sodiumsalt) in 400 liters of
water and 4 kilos. of caustic soda. By stirring from time to time the combination is
completed within about 20 hours. The darkblue rather gelatinous mass is then
heated up to boiling and the colouring matter salted out in the heat by addition
of 20 kilos, of common salt filtered and dried.
The new trisazocolour thus obtained yields on unmordanted cotton in a neutral or
slightly alkaline bath and also on wool and silk in a neutral or acid bath in presence
of glaubersalt or commonsalt blue shades.
Similar colouring matters result by substituting the benzidine of this example by
other suitable paradiamines, such as tolidine, dianisidine, ethoxybenzidine and the
like, and by substituting the diazodichlorbenzene 1.2.5 by other isomeric diazodi-
chlorbenzenes or their homologues or diazotrichlorbenzenes or their homologues.
By combining the intermediate products obtained as described in Example I
and III and having the general formula
(wherein P indicates the radical of a paradiamine and X the radical of an aromatic
amine having in its nucleus at least two chlorine groups (with metaphenylendiamine
metatoluylendiamine metaoxydiphenylamine naphtylamines or naphtylaminesulphonic
acids colouring matters are produced dyeing shades varying from grey to black, and
by combining those intermediate products with naphtols, naphtolsulphonic acids,
dioxynaphtalenes, dioxynaphtalenesulphonic acids, amidonaphtols, amidonaphtol-
sulphonic acids such as 1.8.4 or 1.8.5 or 2.8.6 amidonaphtolmonosulphonic acid or
1.8.2.4 or 1.8.3.5 or 1.8.4.6 amidonaphtoldisulphonic acid blueish black to greenish
blue colouring matters result.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, as communicated to me by
my foreign correspondents, I declare that what I claim is :-

page_text: alkaline solution one molecule, of a tetrazotized paradiamine such as benzidine,
tolidine, dianisidine, ethoxybenzidine and the like with one molecule of the monoazo-
dye formed in a mineral acid solution from a diazodichlorbenzene, diazotrichlor-
benzene or their homologues with 1.8 amidonaphtol 3.6 disulphonic acid and coupling
the intermediate product thus obtained with one molecule of an amine, diamine,
phenol, amidophenol oxyphenol their sulpho- and carboxylic acids both of the
benzene and naphtalene series, substantially as set forth.
2. The process for the production of new green trisazo-dyestuffs which consists
in combining one molecule of a tetrazodized paradiamine, such as benzidine, tolidine,
dianisidine, ethoxybenzidine and the like with one molecule of an orthooxycarbonic
acid of the benzene series in an alkaline solution to a so called intermediate product
and coupling the intermediate product thus obtained in an alkaline solution with one
molecule of the monoazodye resulting from the combination of one molecule of a
diazodichlorbenzene or one molecule of a diazotrichlorbenzene or their homologues
with one molecule of 1.8 amidonaphtol 3.6 disulphonic acid in an acid solution,
substantially as set forth.
3. As new articles of manufacture the new trisazo-colouring matters herein before
described.
HASELTINE, LAKE & Co.,
45, Southampton Buildings, London, W.C., Agents for the Applicant.