SultaDIC тот Dyeing and Printing from Dioxytartaric (Carboxytartronic) Acid
Year: 1885

page_text: SultaDIC тот Dyeing and Printing from
Dioxytartaric (Carboxytartronic) Acid.
I, JOHN HENRY JOHNSON of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman do hereby declare the nature of said invention for " IMPROVEMENTS
IN THE MANUFACTURE OF YELLOW AND ORANGE COLORING MATTERS SUITABLE FOR
DYEING AND PRINTING FROM DIOXYTARTARIC (CARBOXYTARTRONIC) ACID" which
Invention has been communicated to me from abroad by The Badische Anilin
and Soda Fabrik at Ludwigshafen on the Rhine, Germany, Chemists, to be as
follows:-
--
This Invention relates to improvements in the manufacture of a new series of
yellow and orange coloring matters suitable for dyeing and printing from Dioxy-
tartaric acid.
The said acid the production of which from Tartaric acid has been described by
Kekulé (Annalen der Chemie vol. 221 p. 245 sequ) has formerly been known
under the name of Carboxytartronic acid, and has never before this present
Invention, so far as can be ascertained, received any industrial application.
In order to apply Dioxytartaric acid to the production of yellow and orange
colouring matters, suitable for dyeing and printing, my foreign Correspondents
avail themselves of a peculiar and novel reaction, which may be observed to take
place, whenever solutions of the said acid are mixed with Phenylhydrazine, or with
its sulphonated derivatives or with a great number of other primary Hydrazine-
compounds (such as may be prepared from their corresponding Diazo compounds
by the employment of suitable reducing agents and according to methods now well
known to Chemists).
By adding gradually any of the before named primary Hydrazine-compounds to
a solution of Dioxytartaric acid it will soon be observed, that a yellow or orange
coloured precipitate is forming, the colour of which gradually increases in intensity,
and it will also be noticed that this reaction proceeds in two consecutive stages.
In the first of the said stages equal molecules of Dioxytartaric and of the
Hydrazine-compound react upon one another under formation of a condensation
product possessing few, if any, colouring properties.
In the second stage of the reaction the desired yellow or orange colouring
matters, suitable for dyeing and printing, are produced by the subsequent con-
densation of the before named condensation product with another molecule of the
Hydrazine compound. It is self-evident that in the described two stages of the
reaction either two molecules of the same or of two different Hydrazine compounds
may be employed.

page_text: From the foregoing remarks and the following examples the nature of this
Invention will be clearly understood.
First example About ten parts by weight of the nearly insoluble sodium salt of
Dioxytartaric acid are well mixed with about thirty parts of cold water and
gradually about thirty five parts by weight of hydrochloric acid of about 1·16
specific gravity are added. The clear solution of Dioxytartaric acid thus produced
is then mixed with about thirteen parts by weight of Hydrochlorate of Phenyl-
The above
hydrazine previously dissolved in about one hundred parts of water.
described reaction quickly sets in and may be assisted by a gentle application of
heat. The mixture is then. allowed to stand for a time (say about 12 hours) and
the abundant yellow precipitate of the colouring matter thus produced may then
be filtered, pressed and dried.
-$2
The result of the operation is a yellow colouring matter, sparingly soluble in
water but easily soluble in alkaline solutions and in alcohol.
Second example About ten parts by weight of the before named Dioxytartrate
of sodium are mixed with about sixteen parts of cold water, the resulting mixture
'is then heated to about forty degrees Centigrade. and about thirteen parts by
weight of Hydrochloric acid of about 1.16 specific gravity (or as much of the said
acid as will be found sufficient to produce a clear solution) are added. The solution
of Dioxytartaric acid thus obtained is then mixed with about twenty parts by
weight of Phenylhydrazine-para-sulphonic acid (such as may be derived from
Sulphaurlic acid) previously dissolved in a mixture of about sixty parts of water
with about ten parts by weight of Caustic soda liquor (containing about thirty
per cent of dry caustic soda).
The resulting mixture is afterwards kept at a temperature of about eighty
degrees Centigrade during about one hour or until the reaction appears to be
finished, and after about twelve hours standing at the ordinary temperature, the
yellow precipitate of the colouring matter may then be collected upon a filter,
pressed and dried.
The colouring matter thus obtained is readily soluble in water, insoluble in
alcohol, and suitable for dyeing and printing a fast golden yellow colour upon
animal fibre with the aid of acids or of acid mordaunts.
Third example The following is an example of the manner in which, as before
stated, two different Hydrazine-compounds may be employed in the before
described consecutive stages of the reaction.
About ten parts by weight of Dioxytartrate of Sodium are mixed with water
and then rendered soluble by the addition of hydrochloric acid substantially in the
manner described in the second example. The solution of Dioxytartaric acid thus
obtained is then mixed with an alkaline solution prepared as above described of
about ten parts by weight of Phenylhydrazine-para-sulphonic acid and afterwards
about six and one half parts by weight of Hydrochlorate of Phenylhydrazine
previously dissolved in about fifty parts of water, are added. It will be observed
that the pale yellow-colored crystalline precipitate produced in the first stage of
the reaction will gradually assume an intense yellow colour upon being digested
with the Phenylhydrazine solution owing to the production of a yellow colouring
matter soluble both in alcohol and in water. In an analogous manner yellow
colouring matters suitable for dyeing and printing are obtained by the employment
of the higher homologues of Phenylhydrazine and their sulpho acids whilst
Alphanaphthylhydrazine and its sulpho acids are capable of producing orange
colouring matters by the before described action of Dioxytartaric acid.

page_text: Colouring Matters Suitable for Dyeing and Printing from
Dioxytartaric (Carboxytartronic) Acid.
I JOHN HENRY 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
Ludwigshafen on the Rhine 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 improvements in the manufacture of a new series of
yellow and orange colouring matters, suitable for Dyeing and Printing, from
Dioxytartaric acid.
The said acid, the production of which from Tartaric acid has been described by
Kekulé (Annalen der Chemie vol 221 p 245 sequ) has formerly been known' under
the name of Carboxytartronic acid and has never before this present Invention so
far as can be ascertained been applied to any industrial purpose.
In order to apply Dioxytartaric acid to the production of yellow and orange
colouring matters, suitable for Dyeing and Printing, my foreign correspondents
avail themselves of a peculiar and novel reaction which may be observed to take
place, whenever solutions of the said acid are mixed with Phenylhydrazine, or
with its sulphonated derivatives or with a great number of other primary
Hydrazine-compounds, (such as may be prepared from their corresponding Diazo-
compounds by the employment of suitable reducing agents, and according to
methods now well known to Chemists).
By adding gradually any of the before named primary Hydrazine-compounds to
an acid solution of Dioxytartaric acid it will soon be observed that a yellow or
orange colour is forming which gradually increases in intensity, and it will also be
noticed, that this reaction proceeds in two consecutive stages. In the first of the
said stages equal molecules of Dioxytartaric acid and of the Hydrazine-compound
react upon one another under formation of a condensation-product possessing few;
if any, colouring properties. In the second stage of the reaction the desired yellow
or orange colouring matters, suitable for Dyeing and printing, are produced by the
subsequent condensation of the before-named condensation-product with another
molecule of the Hydrazine-compound. It is self-evident that in the described
two stages of the reaction either two molecules of the same or of two different
Hydrazine-compounds may be employed.
Generally the colouring matters thus produced are precipitated during the
progress of the reaction, and require only to be separated by filtration. In the
event of their remaining partly or wholly in solution, the latter may be rendered
alkaline by means of carbonate of soda and be then precipitated with common salt.
From the foregoing remarks and the following examples the nature of this
Invention and the manner in which it may be performed will be clearly
understood.

page_text: First Example. About ten parts by weight of the nearly insoluble sodium salt
of Dioxytartaric acid are well mixed with about thirty parts of cold water, and
gradually about thirty-five parts by weight of hydrochloric acid, of about
1-16 specific gravity are added. The clear solution of Dioxytartaric acid thus
produced is then mixed with about thirteen parts by weight of Hydrochlorate of
Phenylhydrazine, previously dissolved in about one hundred parts of water. The
above described reaction quickly sets in and may be assisted by a gentle application
of heat. The mixture is then allowed to stand for a time (say about 12 hours)
and the abundant yellow precipitate of the colouring matter thus produced may
then be filtered pressed and dried.
The result of the operation is a yellow colouring matter, sparingly soluble in
water but easily soluble in alkaline solutions and in alcohol.
In an analogous manner yellow colouring matters, possessing similar properties,
are obtained by the employment of equivalent proportions of the higher homologues
of Phenyl-hydrazine, whilst Alphanaphthylhydrazine is capable of producing an
orange colouring matter by the before described action of Dioxytartaric acid. The
said colouring matters are however not. sufficiently soluble in water to enter, for
dyeing purposes, into competition with their corresponding 'sulpho acids the pre-
paration of which I shall now proceed to describe.
Second example. About ten parts by weight of the before named Dioxytartrate
of sodium are mixed with about sixteen parts of cold water, the resulting mixture
is then heated to about forty degrees Centigrade, and about thirteen parts by
weight of hydrochloric acid of about 1.16 specific gravity (or as much of the said
acid as will be found sufficient to produce a clear solution) are added. The solution
of Dioxytartaric acid thus obtained is then mixed with about twenty parts by
weight of Phenylhydrazine-para-sulphonic acid (such as may be derived from
sulphanilic acid) previously dissolved in a mixture of about sixty parts of water
with about ten parts by weight of caustic soda liquor (containing about thirty
per cent of dry caustic soda).
The resulting mixture is afterwards kept at a temperature of about eighty
degrees Centigrade during about one hour or until the reaction appears to be
finished, and after about twelve hours standing at the ordinary temperature, the
yellow precipitate of the colouring matter may then be collected upon a filter,
pressed and submitted to a final purification by dissolving the same in water of
about sixty degrees Centigrade with the addition of as much carbonate of soda, as
will be required to render the solution slightly alkaline. The solution thus
obtained is then filtered and precipitated with common salt. The resulting
precipitate of the purified coloring matter is afterwards filtered, pressed and dried.
The colouring matter thus obtained (to which the Inventor gives the name of
"Tartrazine") is readily soluble in water and almost insoluble in strong alcohol.
It can be used for dyeing and printing a fast golden yellow colour upon animal
fibre with the acid of acids or of acid mordants.
I
Yellow colouring matters possessing the general character of the before
described "Tartrazine" are obtained in a similar manner by the condensation of
one molecule of Dioxytartaric acid with two molecules of analogous primary
Hydrazine-sulpho-acids. Good results have thus been obtained with the employ-
ment of Phenylhydrazine-metasulphonic acid, or with the Hydrazines prepared
from the known sulpho acids of either Ortho- or Paratoluidine or of Metaxylidine.
The Hydrazine derived from Naphthionic or Alphanaphthylamine sulphonic acid
has been found capable of yielding an orange colouring matter.
Third example:-The following is an example of the manner in which, as before
stated, two different Hydrazine compounds may be employed in the before described
consecutive stages of the reaction.
About ten parts by weight of Dioxytartrate of sodium are mixed with water,
and then rendered soluble by the addition of hydrochloric acid, substantially in
the manner described in the second example. The solution of Dioxytartaric acid
thus obtained is then mixed with an alkaline solution (prepared as above described).

page_text: of about ten parts by weight of Phenylhydrazine-para-sulphonic acid, and
afterwards about six and one half parts by weight of the Hydrochlorate of
Phenylhydrazine, previously dissolved in about fifty parts of water, are added.
It will be observed, that the pale yellow-coloured crystalline precipitate produced
in the first stage of the reaction will gradually assume an intense yellow colour
upon being digested with the Phenylhydrazine solution, owing to the production of
a yellow colouring matter, soluble both in alcohol and in water.
The same result will be obtained by reversing the order, in which the different
Hydrazine-compounds are made to react upon Dioxytartaric acid, or by simply
employing mixtures of the component Hydrazines. In an analogous manner
colouring matters, soluble in water and suitable for Dyeing and Printing various
shades from a pure yellow to an orange yellow, are obtained by employing in lieu
of the above named Phenylhydrazine the Hydrazine-derivatives of Ortho-Toluidine
Paratoluidine, Metaxylidine, Alphanaphthylamine and Betanaphthylamine, or the
Hydrazine sulpho acids named in the above description of the second example.
The said Hydrazine sulpho acids may likewise be substituted for the beforenamed
Phenylhydrazine para sulphonic acid.
Although a useful series of colouring matters may be obtained in all the
before described manners the Inventor considers that the hereinbefore described
"Tartrazine" is the most useful derivative of Dioxytartaric acid.
Having now particularly described and ascertained the nature of this Inven-
tion and in what manner the same is to be performed I declare that what
I claim is:
First: The preparation of a new colouring matter suitable for Dyeing and
Printing which has been hereinbefore referred to as "Tartrazine" by the con-
densation of one molecule of Dioxytartaric (Carboxy-tartronic) acid with two
molecules of Phenylhydrazine-para sulphonic acid (Hydrazine-derivative of sul-
phanilic acid) substantially as herein before described.
Second The preparation of yellow and orange yellow colouring matters
possessing the general character of the before named Tartrazine by replacing either
one or two molecules of the Phenylhydrazine-para sulphonic acid (employed in
the above-defined process of the first claim) by any of the following Hydrazine
compounds or mixtures thereof viz:-Phenyl hydrazine-meta-sulphonic acid, or
the Hydrazines prepared (by the application of known methods) from the known
monosulpho acids of ortho-toluidine, paratoluidine, metaxylidine, alpha- and beta-
naphthylamine, substantially as hereinbefore described.
Third: The preparation of yellow and orange yellow colouring matters by
replacing one molecule of the Hydrazine sulpho acids employed in the before
defined processes of the first and second claims by one molecule of the Hydrazines
prepared from Aniline, Orthotoluidine, Paratoluidine, Metaxylidine, Alpha- and
betanaphthylamine, substantially as herein before described.
Dated this 10th day of May 1886