Improvements in and relating to the Manufacture of Colouring Matters suitable for Dyeing and Printing.
Year: 1889

page_text: Date of Application, 23rd Dec., 1889
Complete Specification Left, 16th Sept., 1890-Accepted, 18th Oct., 1890
PROVISIONAL SPECIFICATION.
Improvements in and relating to the Manufacture of Colouring
Matters suitable for Dyeing and Printing.
I, JAMES YATE JOHNSON, of 47 Lincolns Inn Fields, in the County of Middlesex,
Gentleman, do hereby declare the nature of this invention (which has been com-
municated to me from abroad by The Badische Anilin & Soda Fabrik, of
Ludwigshafen-on-Rhine, in the Empire of Germany,) to be as follows:-
This invention is based upon the discovery of a new derivative of diamidodipheny-
lene-ketone, which by appropriate treatment is made to yield a series of dyestuffs
possessing the valuable property of fixing themselves on cotton in the presence of
alkalies without the aid of a mordant, thus yielding various shades of orange, red,
brown, purple or blue.
It is
This new derivative is in chemical language a ketoxime and results from the action
of hydroxyl-amine or its sulpho acids on the above mentioned diamido body. It is an
orange to yellowish brown substance very slightly soluble in water, soluble in
alcohol and ether, in dilute mineral acids and in strong acetic acid. The chlorhydrate
can be precipitated from its aqueous solution by means of hydrochloric acid.
also soluble in solutions of the fixed alkalies. On treatment with nitrous acid it is
converted into its tetrazo-compound which yields the above mentioned series of dye-stuffs
by its combination with phenols, amines, their sulpho and carboxylic acids, such as
for instance resorcinol, metaphenylenediamine, alpha naphtol-alpha sulpho acid
(Meville and Winthers acid), naphthionic acid, beta-naphthylamine-beta-sulpho acid,
salicylic acid, beta-naphthylamine-delta-sulpho acid and analogous bodies. These
combinations may be symmetrical, that is to say, combinations of one molecule of the
tetrazo-compound with two molecules of the same phenolic or amido derivative or
assymetrical, that is to say, combinations of one molecule of the tetrazo-compound with
one molecule of one phenolic or amido-derivative and one molecule of a different
one.
In carrying out this invention the above named diamidodiphenylene ketone, a
body already known to chemists, may be conveniently prepared by mixing one part
of dinitrodiphenylene ketone (Annalen der Chemie Vol. 203 page 104) with about ten
parts of alcohol and then reducing with about 10 parts of sodium sulphide-the parts
being by weight. The reduction is effected at the boiling point of the mixture and
the alcohol is subsequently distilled off and the residue extracted with dilute hydro-
chloric acid whereby a solution of the chlorhydrate is obtained, a residue of sulphur
remaining. From the hot solution the free base is precipitated by adding the
requisite quantity of calcined soda and on cooling the base is obtained as orange or
brown-yellow needles which are filtered, washed with cold water pressed and dried.
In order to illustrate and explain the subsequent stages of the process according to
this invention, I give by way of an example, the following directions.
Take, say about, twenty one parts by weight of diamidodiphenylene ketone and
dissolve in a hot mixture of about thirty-five parts by weight of hydrochloric
acid of about 111 specific gravity and about sixteen hundred parts by weight of water.
To this solution add a concentrated aqueous solution of ten parts by weight of hydro-
xylamine chlorhydrate and allow the whole to cool down to the ordinary temperature.
Any precipitate consisting of the hydrochlorate of the base which may separate out
should be kept suspended in the liquor. Now add gradually (in small quantities at a
time) about sixty three and a half parts by weight of caustic soda lye of about 1.38
specific gravity and during this addition gradually raise the temperature to about

page_text: from 60 to 70° Centigrade. The addition of the first portions of caustic soda will
cause a precipitation of the ketonic base, but this will begin to redissolve as the
solution becomes more alkaline. After all the caustic soda has been added bring the
mixture to the boil and keep it gently boiling until the base is redissolved or nearly
80. Filter if necessary, and in any case add carefully to the clear yellowish brown
solution, thus obtained, sufficient hydrochloric acid of 1.11 specific gravity to precipi-
tate the ketoxime base (generally about forty four to forty eight parts by weight
will be necessary.
An excess of the acid is to be carefully avoided as it will re-dissolve the base.
Filter wash and press. If the product be dried, the operation must be carefully
conducted at a low temperature, as it is otherwise liable to undergo changes which
cause a deterioration in quality, it is therefore advisable to keep and use the ketoxime
in the condition of a pulp or paste.
In the above process the hydroxylamine hydrochlorate may be replaced by an
equivalent quantity of its sulpho-acids (Annalin der Chemie Fol. 241 pp. 187 & seq.)
which acting similarly give the same final product.
The above mentioned dyestuffs may be obtained from the ketoxime as follows:-
Take say about forty five parts by weight of diamidodiphenylene ketoxime, and dis-
solve in a mixture of about ninety six parts by weight of hydrochloric acid of about 1:175
specific gravity and sixteen hundred parts by weight of water. Keep cold with ice
and add gradually a concentrated aqueous solution of twenty eight parts by
weight of sodium nitrite. In this way a solution of the tetrazo-compound of
diphenylene ketoxime is obtained, which is to be at once combined with the above
named phenolic or amido-derivatives in the manner illustrated by the following
examples:-
First. In order to obtain a symmetrical combination with two molecules of
naphthionic acid, run the solution of the tetrazo-compound obtained as described, from
forty-five parts by weight of the ketoxime base into a solution of about one hundred
and thirty parts by weight of sodium naphthionate and about eighty parts by weight
of crystallized sodium acetate in about six thousand parts by weight of water. Stir
for about 36 hours, add soda till alkaline, boil and salt out the dyestuff formed. If
necessary purify by redissolving and reprecipitating. This dye stuff dyes cotton in an
alkaline bath a blueish red.
In a similar manner analogous dye stuffs containing two molecules of beta
naphthylamine-beta sulpho acid and beta naphthylamine delta sulpho-acid may be
obtained.
Second. An orange yellow dye may be obtained by a similar symmetrical com-
bination with salicylic acid in the following manner.
Run the cold solution of the tetrazo compound from forty five parts by weight of
diamido-diphenylene ketoxime into a solution of about sixty parts by weight of
salicylic acid and about two hundred and seventy six parts by weight of caustic soda
liquor of about 1.38 specific gravity in four thousand parts by weight of water. After
standing for eighteen hours neutralize the excess of alkali with acetic acid, boil and
filter after cooling. Wash with cold water press and dry.
Third. A violet brown dye results from the assymetrical combination of one mole-
cule of the tetrazo-compound, with one molecule of alpha naphthol-alpha mono-sulpho-
acid (Neville & Winthers acid) and one molecule of metaphenylene diamine. This
combination is thus effected.
Run the solution of the tetrazo-compound from forty five parts by weight of the
ketoxime base into a solution of fifty one parts by weight of the sodium salt of the
above named alpha naphthol-alpha-monosulpho acid and eighty parts by weight of
crystallized sodium acetate in four thousand parts by weight of water. Stir for three
hours and pour the product into a solution of forty four parts by weight of chlor-
hydrate of metaphenylene diamine and sixty parts by weight of sodium acetate in one
thousand parts by weight of water, stir again for eighteen hours, and then add soda
till alkaline, boil and when cold filter, press and dry.

page_text: In an analogous manner the other herein before mentioned combinations may be
effected.
בד
11
02
1
1
CD 1000
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in and relating to the Manufacture of Colouring
Matters suitable for Dyeing and Printing.
I JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of this invention (which has been communi- .
cated to me from abroad by The Badische Anilin and Soda Fabrik of Ludwigshafen on:
Rhine in the Empire of Germany) and in what manner the same is to be performed
to be particularly described and ascertained in and by the following statement:-
This invention is based upon the discovery of a new derivative of amido dipheny
lene ketone which by appropriate treatment is made to yield a series of dyestuffs
possessing the valuable property of fixing themselves on cotton in the presence of
alkalies, without the aid of a mordant thus yielding various shades of orange, red,
brown, purple, or blue.
This new derivative is in chemical language a ketoxime and may be called "diamido-
diphenylene ketoxime" and it results from the action of hydroxylamine or its sulpho
acids on the above mentioned diamido body. It is an orange to yellowish brown
substance, very slightly soluble in water, soluble in alcohol and ether, in dilute
mineral acids and in strong acetic acid. The chlorhydrate can be precipitated from its
aqueous solution by means of hydrochloric acid. It is also soluble in solutions of the
fixed alkalies. On treatment with nitrous acid it is converted into its tetrazo-
compound which yields the above mentioned series of dyestuffs by its combination
with many phenols, amines, their sulpho and carboxylic acids, such as for instance
metaphenylene diamine, alpha-naphthol-alpha-sulpho acid (Nevile & Winther's acid),
Schoellkopf's alpha-naphthol-disulpho acid (see British Patent 17785) naphthionic
acid, beta-naphthylamine-beta-sulpho ac'd, beta-naphthylamine-delta sulpho acid and
salicylic acid. These combinations may be symmetrical, that is to say, combinations
of one molecular proportion of the tetrazo-compound with two molecular proportions
of the same phenolic or amido derivative, or asymmetrical, that is to say, combina-
tions of one molecular, proportion of the tetrazo compound with one molecular
proportion of one phenolic or amido-derivative and one molecular proportion of a
different one.
2
In carrying out this invention the above named diamidodiphenyleneketone, a body
already known to chemists, may be conveniently prepared by mixing one part of
dinitrodiphenylene ketone (Annalen der Chemie Vol. 203 p. 104) with about ten parts
of alcohol and then reducing with, about 10 parts of sodium sulphide (Na, S + 9 H, O)
the parts being by weight. The reduction is effected at the boiling point of the
mixture and the alcohol is subsequently distilled off and the residue extracted w.th
dilute hydrochloric acid, whereby a solution of the chlorhydrate is obtained, a residue
of sulphur remaining. From the hot solution the free base is precipitated by adding
the requisite quantity of calcined soda and on cooling the base is obtained as dark
brown needles, which are filtered, washed with cold water pressed and dried.
In order to illustrate and explain the invention and the manner in which it can best
be carried into effect I give as examples the following directions: the parts being
by weight.
EXAMPLE 1. PRODUCTION OF THE NEW KETOXIME BASE.
Take say about twenty one parts of diamidodiphenylene ketone and dissolve in a
1.11

page_text: aqueous solution of ten parts of hydroxylamine chlorhydrate and allow the whole
to cool down to the ordinary temperature of the atmosphere. Any precipitate
consisting of the hydrochlorate of the base which may separate out should be kept
suspended in the liquor. Now add gradually in small portions at a time about sixty
three and a half parts of caustic soda lye of about 138 specific gravity and during
this addition gradually raise the temperature to about sixty to seventy degrees
Centigrade. The addition of the first portions of caustic soda will cause a precipita-
tion of the ketonic base, but this will begin to redissolve as the solution becomes more
alkaline. After all the caustic soda has been added bring the mixture slowly to the
boil and keep it gently boiling until the base is redissolved or nearly so.
necessary and in any case add carefully to the clear yellowish brown solution thus
obtained sufficient hydrochloric acid of 1.11 specific gravity to precipitate the
ketoxime base (generally about forty four to forty eight parts will be necessary). An
excess of the acid is to be carefully avoided as it will re-dissolve the base. Filter,
wash and press. If the product be dried, the operation must be carefully conducted
at a low temperature, as it is otherwise liable to underge changes which cause a
deterioration in quality; it is therefore advisable to keep and use the ketoxime in
the condition of a pulp or paste.
Filter if
In the above process the hydroxylamine hydrochlorate may sometimes be advan-
tageously replaced by rather more than an equivalent quantity of its sulpho acids
(see Annalen der Chemie Vol. 241 pp. 181 & seq. and British Patent No. 3028 of
1887) which acting similarly give the same final product.
The above mentioned dyestuffs may be obtained from the ketoxime as follows:-
EXAMPLE 2. PRODUCTION OF THE NEW TETRAZO COMPOUND FROM THE KETOXIME
BASE.
Take say about forty five parts of diamidodiphenylene ketoxime, and dissolve in a
mixture of about ninety six parts of hydrochloric acid of about 1.175 specific gravity
and sixteen hundred parts of water. Keep cold with ice and add a concentrated
aqueous solution of twenty eight parts of sodium nitrite. In this way a solution of
the tetrazo compound of diphenylene ketoxime is obtained which is to be at once
combined with the above named phenolic or amido derivatives in the manner
described in the succeeding examples.
EXAMPLE 3. PRODUCTION OF A RED SUBSTANTIVE DYESTUFF.
In order to obtain a symmetrical combination with two molecular proportions
of naphthionic acid, run the solution of the tetrazo compound obtained as described
from forty five parts by weight of the ketoxime base into a solution of about one hundred
and thirty parts of crystallized sodium naphthionate and about eighty parts of
crystallized sodium acetate in about six thousand parts of water. Stir for about
36 hours, add soda till alkaline, boil and salt out the dyestuff formed. If necessary
purify by redissolving and reprécipitating. This dyestuff dyes cotton in an alkaline
bath a red colour.
In a similar manner other red dyestuffs containing two molecular proportions
of beta-naphthylamine beta-sulpho acid and beta-naphthylamine-delta-sulpho acid
may be obtained.
EXAMPLE 4. PRODUCTION OF AN ORANGE-YELLOW SUBSTANTIVE DYestuff.
An orange-yellow dye may be obtained by a similar symmetrical combination
with salicylic acid in the following manner.
Run the cold solution of the tetrazo compound from forty five parts of diamidodi-
phenylene ketoxime into a solution of about sixty parts of salicylic acid and about two
hundred and seventy six parts of caustic soda liquor of about 1.38 specific gravity in
four thousand parts of water. After standing for eighteen hours, neutralize the
excess of alkali with acetic acid, boil and filter after cooling. Wash with cold water
press and dry.

page_text: EXAMPLE 5.
PRODUCTION OF A VIOLET-BROWN SUBSTANTIVE DYESTUFF.
A violet-brown dye results from the symmetrical combination of one molecular
proportion of the tetrazo compound with one molecular proportion of alpha-naphthol-
alpha-monosulpho acid (Nevile & Winthers acid) and one molecular proportion of
metaphenylene diamine. This combination may be thus effected.
Run the solution of the tetrazo compound from forty five parts of the ketoxime
base into a solution of fifty one parts of the sodium salt of the above named alpha-
naphthol-alpha monosulpho acid and eighty parts of crystallized sodium acetate in
four thousand parts of water. Stir for three hours and pour the product into a
solution of forty four parts of chlorhydrate of metaphenylene diamine and sixty
parts of sodium acetate in one thousand parts of water, stir again for eighteen
hours and then add soda till alkaline, boil and, when cold, filter, press and dry.
In an analogous manner the other herein before mentioned combinations may be
effected, and a blue dyestuff can be obtained by the combination of two molecular
proportions of Schöllkopf's naphthol disulpho acid with one molecular proportion
of the tetrazo compound and a violet one from two molecular proportions of
Nevile & Winther's acid and one molecular proportion of the tetrazo compound.
Although I have named only a few amido and phenolic derivatives, as yielding
dyestuffs with the tetrazo-compound of the new base, still, as will be readily under-
stood by chemists, this tetrazo-compound can be combined with all the amido and
phenolic derivatives in ordinary use for combination with diazo- or tetrazo-compounds
in the manufacture of azo dyes, yielding dyestuffs of the colours herein before
mentioned. The dyestuffs of which the preparation is described in the last three
examples have not been chosen so much on account of their importance but as
being good typical cases.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. As a new product, the hereinbefore described ketoxime-base, or
diphenylene-ketoxime."
"diamido-
2. The process of producing the new ketoxime base (diamido-diphenylene-
ketoxime) by the treatment of diamido-diphenylene ketone with hydroxylamine or
hydroxylamine sulpho acids, substantially as herein before described.
3. As a new product the tetrazo compound of the new ketoxime base (diamido-
diphenylene-ketoxime) produced in solution by the action of sodium nitrite in acid
solution on the said base.
4. The process of producing the tetrazo-compound of the new ketoxime base
(diamido-diphenylene-ketoxime) by the action of a nitrite in acid solution on the said
base, substantially as described."
5. The process of producing dyestuffs by the combination of the new tetrazo-
compound (symmetrically or asymmetrically) with the hereinbefore named amido or
phenolic bodies (including sulpho and carboxylic acids of those bodies) substantially as
hereinbefore described.
6. As a new product the red substantive dyestuff hereinbefore described which may
be produced by the combination of one molecular proportion of the tetrazo-compound
of the new ketoxime base with two molecular proportions of naphthionic acid.
7. As a new product, the orange-yellow dyestuff herein before described which may
be produced by the combination of one molecular proportion of the tetrazo-compound
of the new ketoxime base with two molecular proportions of salicylic acid.
8. As a new product, the violet-brown dyestuff hereinbefore described, which may
be produced by the combination of one molecular proportion of the tetrazo con pound
of the new ketoxime base with one molecular proportion of alpha-naphthol alpha-sulpho-
acid (Nevile and Winther's acid) and one molecular proportion of meta-phenylene-
diamine.

page_text: 9. The application of the new ketoxime base (diamido-diphenylene-ketoxime) to the
manufacture of dyestuffs by the conversion of the said base into its tetrazo-compound
and combining this compound with phenols, amines, or their sulpho or carboxylic acids
such as those herein before mentioned or others equivalent thereto as hereinbefore
explained.