The Production of a Yellow Colouring Matter from Carbazol.
Year: 1888

page_text: Date of Application, 9th Oct., 1888
Complete Specification Left, 9th July, 1889-Accepted, 10th Aug.. 1839
PROVISIONAL SPECIFICATION.
The Production of a Yellow Colouring Matter from Carbazol.
N
I, JAMES YATE JOHNSON, of 47 Lincoln's 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 and Soda Fabrik of Ludwig-
shafen-on-the-Rhine in the Empire of Germany, to be as follows. :-
This Invention relates to the production of a new yellow colouring matter from
carbazol, a hitherto waste byc product in the manufacture of pure or refined
anthracene. The said colouring matter belongs to the class of the so-called diazo
compounds and results from the combination of one molecule of tetrazocarbazol
with two molecules of salicylic acid.
In carrying out this Invention carbazol is first converted into dinitrocarbazol by
allowing, for instance, about thirteen parts by weight of nitric acid of about 1.38
specific gravity gradually to run into a well agitated mixture of about ten parts
by weight of carbazol with about fifty parts by weight of glacial acetic acid
at a temperature of about eighty degrees Centigrade. After the addition of
nitric acid the temperature of the mixture is raised to about one hundred
degrees Centigrade and maintained thereat for about half an hour. On cooling
dinitrocarbazol will separate out in the form of a yellow crystalline powder,
which is to be filtered and washed. The diuitrocarbazol is then submitted to the
action of reducing agents in order to convert the same into its corresponding diamido
derivative. For this purpose any suitable reducing process may be employed, such
as for instance treatment with stannous chloride or with a mixture of tin and hydro-
chloric acid at about one hundred degrees Centigrade, but by preference the action
of zinc dust in the presence of caustic alkalies is made use of in the following manner.
About sixty five parts by weight of dinitrocarbazol are intimately mixed with
about three hundred parts by weight of water and about one hundred parts by weight
of zinc dust. The mixture thus prepared is then heated up to about fifty degrees
Centigrade and about two hundred and fifty parts by weight of caustic soda liquor
of about 138 specific gravity are gradually added to the well agitated mixture.
After the addition of caustic soda the temperature is raised to about ninety degrees
Centigrade and maintained thereat for about eight hours or until the conversion of
dinitrocarbazol into diamido carbazol has been completed or nearly so. In order to
separate the said diamido compound from the alkaline mixture, about one thousand
parts by weight of water are then added, the undissolved residue (principally
consisting of diamidocarbazol and unchanged zinc dust or oxide of zinc) is filtered,
washed and treated with about five hundred parts by weight of hydrochloric acid of
about 1-16 specific gravity, whereby a crystalline mixture of hydrochlorate of
diamido-carbazol and of its chloride of zinc compound will be obtained, which is then
to be filtered and pressed. A further purification may afterwards be effected by
dissolving the said saline compounds of diamidocarbazol in about fifteen hundred
parts by weight of water and precipitating the filtered solution (which may be
previously decolorized by means of animal charcoal) by the addition of about one
hundred parts of crystallized sulphate of soda, when sulphate of dianiidocarbazo! thus
produced will separate out in a pure and well crystallized condition. The said saline
compound is almost insoluble in pure water but dissolves readily in water acidulated
by a mineral acid. From its aqueous solution pure diamidocarbazol may be obtained
npon the addition of an alkali as a crystalline precipitate consisting of silverish white
lamina, hardly soluble in water and not entering into fusion at about two hundred and
fifty degrees Centigrade.

page_text: The final step in the process consists in the conversion of diamidocarbazol (or
of its above named saline compounds) into tetrazocarbazol by the action of nitrous
acid, immediately followed by the combination of the latter.compound with salicylic
acid, as above mentioned.
The following is an example of the manner in which the said operations may be
carried out.
About fifty parts by weight of the before named sulphate of diamidocarbazol are
intimately mixed with about sixty parts by weight of hydrochloric acid of about 1:16
specific gravity and with about one thousand parts by weight of water and about one
thousand parts by weight of ice. The mixture thus produced is then diazotized by.
the addition of a solution of about fifty parts by weight of nitrite of soda in about one
hundred and fifty paris by weight of water and the solution of tetrazocarbazol thus
obtained is then immediately allowed to run into a well agitated solution of about
forty-seven and a half parts by weight of salicylic acid in about two thousand parts
by weight of water and about one hundred and fifty parts by weight of caustic soda
liquor of about 1-38 specific gravity. The mixture immediately assumes an intense
red colour, which within about twenty four hours turns into a yellowish-brown. This
point being arrived at the mixture is heated to ebullition and common salt is added in
order to precipitate the yellow colouring matter, which upon cooling, separates out
as a brown crystalline precipitate and may then be filtered, washed, pressed and
used for dyeing and printing either in the state of a paste or of a dry powder.
The yellow colouring matter, prepared as above described, is the sodium salt of an
acid azo compound, which itself is insoluble in water and may by the addition of a
stronger acid, say hydrochloric acid, be precipitated from the yellowish-brown aqueous
solutions of its alkaline salts in the form of a dark blueish-green precipitate, soluble
in concentrated sulphuric acid with a bright blueish purple colour. The colouring
matter possesses the property of imparting in. its alkaline solution a bright and
intense yellow colour to cotton without the aid of mordants. Wool and other animal
fibre may be dyed a bright and fast yellow either in a neutral or acidified bath of the
dyestuff.
COMPLETE SPECIFICATION.
The Production of a Yellow Colouring Matter from Carbazol.
JAMES YATE JOHNSON of 47 Lincoln's 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 Ludwig-
shafen-on-the-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 relates to the production of a new yellow colouring matter from
carbazol a. hitherto waste bye-product in the manufacture of pure or refined
anthracene. The said colouring matter belongs to the class of the so-called Disazo-
compounds and results from the combination of one molecule of Tetrazocarbazol with
two molecules of salicylic acid:
"In carrying out this Invention carbazol is first converted into Dinitrocarbazol by
allowing, for instance, about thirteen parts by weight of nitric acid of about 1-38
specific gravity gradually to run into a well agitated: mixture of about ten parts by
weight of carbazol with about fifty parts by weight of glacial acetic acid at a temperature
of about eighty degrees Centigrade. After the addition of nitric acid the temperature
of the mixture is raised to about one hundred degrees Centigrade and maintained
thereat for about half an hour. On cooling dinitrocarbazol will separate out in the
form of a yellow crystalline powder, which is to be filtered and washed.

page_text: The dinitrocarbazol is then submitted to the action of reducing agents in order to
convert the same into its corresponding diamido-derivative. For this purpose any
suitable reducing process may be employed, such as for instance treatment with
stannous chloride or with a mixture of tin and hydrochloric acid at about one hundred
degrees Centigrade, but by preference the action of zinc dust in the presence of
caustic alkalies is made use of in the following manner :-
About sixty five parts by weight of Dinitrocarbazol are intimately mixed with.
about three hundred parts by weight of water and about one hundred parts by weight
of zinc dust. The mixture thus prepared is then heated to about fifty degrees
Centigrade and about two hundred and fifty parts. by weight of caustic soda liquor
of about 1-38 specific gravity are gradually added to the well agitated mixture. After
the addition of caustic soda the temperature is raised to about ninety degrees
Centigrade and maintained thereat for about eight hours, or until the conversion of
dinitrocarbazol into diamidocarbazol has been completed or nearly so. In order to
separate the said diamido-compound from the alkaline mixture, about one thousand
parts by weight of water are then added, the undissolved residue (principally
consisting of diamido-carbazol and unchanged zinc dust or oxide of zine)-is filtered,
washed and treated with about five hundred parts by weight of hydrochloric acid of
about 1-16 specific. gravity, whereby a crystalline mixture of hydrochlorate of
diamidocarbazol and of its chloride of zinc compound is obtained, which is then filtered
and pressed.
A further purification may afterwards be effected by dissolving the said saline
compounds of diamidocarbazol in about fifteen hundred parts by weight of water and
precipitating the filtered solution (which may he previously decolorized by means of
animal charcoal) by the addition of about one hundred parts of crystallised sulphate
of soda, when sulphate of diamidocarbazol thus produced will separate out in a pure
and well crystallised condition. The said saline compound is almost insoluble in pure
water but dissolves readily in water acidulated by a mineral acid. From its aqueous
solution pure diamidocarbazol may be obtained upon the addition of an alkali as a
crystalline precipitate consisting of silverish-white lamina, hardly soluble in water and
not entering into fusion at about two hundred and fifty degrees Centigrade.
The final step in the process consists in the conversion of diamidocarbazol (or
of its above named saline compounds) into Tetrazocarbazol by the action of nitrous
acid, immediately followed by the combination of the latter compound with salicylic
acid, as above mentioned.
The following is an example of the manner in which the said operations may be
carried out.
About fifty parts by weight of the before named sulphate of diamidocarbazol are
intimately mixed with about sixty parts by weight of hydrochloric acid of about 1.16
specific gravity and with about one thousand parts by weight of water and about one
thousand parts by weight of ice. The mixture thus produced is then diazotised by
the addition of a solution of about fifty parts by weight of nitrite of soda in about
one hundred and fifty parts by weight of water and the solution of tetrazocarbazol
thus obtained is then immediately allowed to run into a well agitated solution of
about forty seven and a half parts by weight of salicylic acid in about two thousand
parts by weight of water and about one hundred and fifty parts by weight of caustic
soda liquor of about 1.38 specific gravity. The mixture immediately assumes an
intense red colour which within about twenty four hours turns into a yellowish-brown.
This point being arrived at, the mixture is heated to ebullition and common salt is
added in order to precipitate the yellow colouring matter, which upon cooling
separates out as a brown crystalline precipitate and may then be filtered, washed,
pressed and used for Dyeing and Printing either in the state of a paste or of a dry
powder.
The yellow colouring matter, prepared as above described, is the sodium salt of an
acid azocompound, which itself is. insoluble in water and may by the addition of a
stronger acid, say hydrochloric acid be precipitated from the yellowish-brown solutions
of its alkaline salts in the form of a dark blueish-green precipitate, soluble in

page_text: concentrated sulphuric acid with a bright blueish-purple colour. The colouring
matter possesses the property of imparting in its alkaline solution a bright and intense
yellow colour to cotton without the aid of mordants. Wool and other animal fibre.
may be dyed a bright and fast yellow either in a neutral or in an acidified bath of the
dyestuff, with or without the aid of suitable mordants.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed I declare that what
I claim is :-
The manufacture of the hereinbefore described yellow colouring matter from
carbazol, by converting carbazol into diamidocarbazol, and subsequently transforming
this diamidoderivative into the corresponding tetrazocarbazol by the action of nitrous
acid and finally combining one molecule of the said tetrazocompound with two
molecules of salicylic acid, all substantially in the manner hereinbefore described.
Dated this 9th day of July 18×0
J. H. JOHNSON & Co.,
Agents.