The Manufacture or Production of New Colouring Matters.
Year: 1892

page_text: Date of Application, 31st Oct., 1892
Complete Specification Left, 31st July, 1893-Accepted, 9th Sept., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
It is known that certain azo dye stuffs derived from resorcinol can be converted
into nitroso coloring matters. These azo dye stuffs, which are described in the
Specification of German Patent No. 46479, and result from the action of nitrous
acid, or nitrites, on the azo products obtained from the diazo derivatives of certain
amines or amidosulpho acids and resorcinol, have been technically valueless, as they
possess only in a moderate degree the property mentioned in the above named
Patent, viz., the capability of nitroso dye stuffs to dye mordanted material.
My foreign correspondents have now found that the nitroso derivatives of the
azo products resulting from the combination of diazotised aromatic amido carbonic
acids with resorcinol, unlike the products described in the above German Patent,
are of technical value, as they possess in an eminent degree the capability of
yielding fast and stable lakes, if metallic mordants be employed.
Here also, as in the case of the products mentioned in English Patents No. 8299
of 18 May 1889, and No. 1828 of 3 February 1890, for instance, the influence of
the carboxylic group makes itself observable, as it imparts before all to the said
azo dye stuffs, the property of dyeing on mordanted material, which property is still
further increased by the nitroso group.
Amongst aromatic amido carbonic acids, the following can be employed, for
example, viz., orthoamidobenzoic acid, meta amidobenzoic acid, paraamidobenzoic
acid, ortho- and para-amido salicylic acid, amido cresolcarbonic acid, amido para-
hydroxy benzoic acid, amido phthalic acid, amido anisic acid. Other amido carbonic
acids, and the substitution products of all these amido carbonic acids, especially the
sulpho derivatives thereof, likewise can be used.
The combination of the diazo compounds of the said amidocarbonic acids and
their substitution products with resorcinol (in equi-molecular proportions) is effected
in the well known manner, most practically in an alkaline solution.
In order to couvert these resorcinol azo carbonic acids into the corresponding
nitroso derivatives, one molecular proportion of the azo products derived from
resorcinol in the manner hereinbefore specified, is dissolved in alkali lye, and after
adding one molecular proportion of sodium nitrite, and cooling by means of ice to
about 0 degrees centigrade, the alkaline solution is acidulated by means of any
mineral acid.
After some hours' standing, the nitroso dye stuff thus produced is filtered off,
washed out, and can then be employed for dyeing and printing.
In order to illustrate more in detail the manufacture of these new nitroso dye
stuffs, the following example is given :
COLORING MATTER OBTAINED FROM PARA AMIDOSALICYLIC ACID AZO
RESORCINOL.
2.75 parts (the parts are by weight) of the dye stuff resulting from diazotised
para amido salicylic acid and resorcinol, in equal molecular proportions, are
dissolved in the necessary quantity of water, with the addition of 0.4 parts of
sodium hydroxide. After adding a watery solution prepared by dissolving 0.7 parts

page_text: of sodium nitrite in 3-5 parts of water, the mixture is cooled by means of ice to
0 degrees centigrade, and then acidulated (with continual stirring) by adding
hydrochloric acid. The resulting mixture is then allowed to stand for twelve
hours, and the nitroso dye-stuff (soluble with difficulty) is filtered off and purified by
washing out.
In an analogous manner as described in the above example, the other dye stuffs
are obtained by employing, in place of the azo coloring matter from diazotised para-
amidosalicylic acid and resorcinol, the isomeric product derived from diazotised
ortho amido salicylic acid, or, in general, the corresponding quantities of the dye
stuffs resulting by the combination of the diazo compounds of aromatic amido
carbonic acids, or substitution products thereof, especially sulpho derivatives thereof,
with resorcinol.
My foreign correspondents have described in the above example one method for
converting resorcinol azo carbonic acids into their nitroso products, which are dye
stuffs of a greater technical value, but they do not limit themselves to the
proportions above given, as the latter can be varied. Of course, in place of sodium
nitrite, other soluble nitrites can be employed; the hydrochloric acid used for
acidulating may be replaced by other mineral acids, and the like.
The same coloring matters also are obtained when nitrous acid is introduced into
the solutions of the resorcinol azo carbonic acids hereinbefore specified.
Of course, all methods known in chemistry for the production of nitroso compounds
can also be employed, and it is evident that the process described in the above
example can be varied. The nature of this invention, however, is not altered by
these modifications, as the present invention relates to the conversion of resorcinol
azo carbonic acids derived from diazotised amidocarbonic acids, or substitution
products thereof, and resorcinol, into new, technically more valuable dye stuffs,
by treatment with nitrites, nitrous acid, or analogous reagents producing the
Rame effect.
The resulting new nitroso coloring matters can be employed for different.
purposes, as they are azo dye stuffs and nitroso dye stuffs. They dyo unmordanted
wool, and likewise wool mordanted with metallic mordants (such as iron or chromium
salts), and they are also suitable for dyeing cotton mordanted in any manner.,
They possess a particular value for printing purposes, as they yield, when fixed on
the fibre by means of the known methods, very fast and clear shades. The latter
are, if chromium mordants be employed, in general from yellow to reddish brown,.
whilst in the employment of printing pastes containing iron salts, much darker
shades, viz., from dark olive colored to black, are produced.
Dated this 31st day of October 1892.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Colouring Matters.
I, HENRY EDWARD NEWTON, of The Office for Patents, 6, Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, 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 :-
It is known that certain azo dye-stuffs derived from resorcinol can be converted
into nitroso colouring matters.
The azo dye-stuffs which are described in the Specification of the German
Patent, No. 46479, and which are produced by the action of nitrous acid on the
azo compounds obtained from the diazo derivatives of certain amines or amido
sulpho acids and resorcinol, have proved to be technically valueless, however, as
they only in a moderate degree possess the property ascribed to them in the
said Patent, of dyeing mordanted materials..

page_text: My foreign correspondents have now found that the nitroso derivatives of the
azo products formed by the combination of diazotised aromatic amidocarboxylic
acids with resorcinol, unlike the products described in the above mentioned
German Patent, are of technical importance, as they are eminently capable of
yielding fast and stable lakes, when employed in dyeing or printing, together with
metallic mordants.
As in the case of the products mentioned in the English Patents No. 8299, of
18th May 1839, and No. 1828, of 3rd February 1890, the carboxylic group exerts
an influence by imparting the property of dyeing unmordanted material, and this.
property is enhanced by the presence of the nitroso group.
The following aromatic amidocarboxylic acids can be employed, viz.-orthamido-
benzoic acid, metamidobenzoic acid, paramidobenzoic acid, orth- and paramido-
salicylic acid, amidocresolcarboxylic acid, amido para hydroxy benzoic acid,
amidophthalic acid and amidoanisic acid; but other amidocarboxylic acids, and
the substitution products of all the above mentioned amidocarboxylic acids,
especially the sulpho derivatives thereof, can also be used.
The combination of the diazo compounds of the said amidocarboxylic acids and
their substitution products with resorcinol (in equimolecular proportions) is effected
in the well known manner, most profitably in an alkaline solution.
In order to convert these resorcinol-azo-carboxylic acids into the corresponding
nitroso derivatives, one molecular proportion of the azo products derived from
resorcinol in the manner hereinbefore specified, is dissolved in alkali-lye, and one
molecular proportion of sodium nitrite having been added, and the liquid having
been cooled by means of ice to about 0 degrees centigrade, the alkaline solution is
acidulated with a mineral acid.
After several hours, the nitroso dye-stuff thus produced is filtered off and washed,
and can then be employed for dyeing and printing.
In order to illustrate the manufacture of these new nitroso dye-stuffs more in
detail, the following example is given, the parts being by weight.
EXAMPLE.
COLOURING MATTER OBTAINED FROM PARAMIDO SALICYLIC ACID-AZO -
RESORCINOL,
2.75 parts of the dye-stuff formed by the combination of equal molecular
proportions of resorcinol and diazotised paramidosalicylic acid, are dissolved in
the necessary quantity of water, and 0-4 parts of sodium hydroxide are added.
A solution prepared by dissolving 0-7 parts of sodium nitrite in 3-5 parts of
water having been added, the mixture is cooled by means of ice to about 0 degrees
centigrade, and acidulated with muriatic acid, stirring the while. The resulting
mixture is allowed to stand during twelve hours, and the difficultly soluble nitroso
dye-stuff is then filtered off and purified by washing.
The colouring-matter thus obtained is a brown paste, and produces reddish-brown
shades on wool mordanted with chromium salts.
The other dye-stuffs are obtained in a manner analogous to that described in the
above example, viz., by employing in place of the azo colouring-matter from
diazotised paramidosalicylic acid and resorcinol, the isomeric product derived from
diazotised orthamidosalicylic acid, or, in general, the corresponding quantities of
the dye-stuff's resulting from the combination of the diazo compounds of aromatic
amidocarboxylic acids or substitution products thereof, especially sulpho derivatives
thereof, with resorcinol.
The dye-stuff acids are almost insoluble in water, while the alkaline salts thereof
dissolve in water, producing from red to brown coloured solutions.
My foreign correspondents have described in the above example, one method of
converting resorcinol-azo-carboxylic acids into their nitroso products, which are
technically valuable dye-stuffs, but they do not limit themselves to the directions

page_text: above given, as the latter can be varied. For instance, in place of sodium nitrite
other soluble nitrites can be employed; the muriatic acid used for acidulating may
be replaced by other mineral acids, and the like.
The same colouring-matters are obtained when "nitrous acid" is directly
introduced into the solutions of the resorcinol-azo-carboxylic acids hereinbefore
specified.
In fact, all methods known to chemists, and in use for the production of nitroso
compounds, can he employed, and it is therefore obvious that the process described, in
the above example can be varied. The nature of this invention, however, is not
altered by such or similar modifications, the object being to convert the resorcinol-
azo-carboxylic acids obtainable from resorcinol and diazotised amidocarboxylic
acids, or substitution products thereof, into new technically valuable dye-stuffs, by
treatment with nitrous acid or analogous agents producing the same effect.
7
The resulting new nitroso colouring-matters can be employed for a variety of
purposes, as they are both azo dye-stuffs and nitroso dye-stuffs. They dye both
unmordanted wool, and wool mordanted with metallic mordants (such as iron or
chromium salts), and they are also suitable for dyeing cotton which has been
mordanted in any suitable manner. They are of special value for printing purposes,
as they yield very fast and clear shades, when fixed on fibres by known methods.
The shades produced are in general from yellowish-brown or brownish-yellow to
reddish-brown or brownish-red, if chromium mordants be employed, while, by using
printing pastes containing iron salts, much darker shades, varying, in general, from
olive coloured to yellowish-olive or olive-brown, are produced.
The following table is given in order to illustrate more in detail the variety
of shades obtainable by means of the colouring-matters hereinbefore defined,
the shades indicated in the second and third columns being those produced by
the dye-stuffs referred to in the first column, on wool mordanted either with
chromium or with iron salts respectively :-
:-
NITROSO DERIVATIVE OF THE COLOURING-MATTER FROM :-
orthamidobenzoic acid
metamidobenzoic acid
yellowish-brown | dark olive
yellowish-brown dark olive
brownish-yellow dark olive yellowish-
paramidobenzoic acid-
orthamidosalicylic acid
paramidosalicylic acid.
amido-para-hydroxybenzoic
acid
amidophthalic acid
resorcinol
brown
brownish-red
reddish-brown
dark olive brown
dark olive brown
brownish-red
dark olive brown
dark yellowish olive
dark olive brown
-17>>>
yellowish-brown dark olive
brownish-red
dark olive brown
amido-ortho-cresotinic acid-
amido-meta-cresotinic acid
amido-para-cresotinic acid
amidophenolether-para-car-
boxylic acid
-
yellowish-brown
reddish-brown
brownish-yellow dark yellowish-olive.
The shades produced by means of the dye-stuffs hereinbefore referred to, with
and fulling and exposure to light.
Having now particularly described and ascertained the nature of the said inven
on and in what manner the same is to be performed, as communicated to me
om abroad, I declare that what I claim is :-
-
1. The production of nitroso- azo dye-stuffs by converting resorcinol - azo
rboxylic acids, or salts thereof, into nitroso compounds.
2. The process for producing nitroso-azo-dye-stuffs by means of the azo colouring-
atters obtainable by the action of one molecular proportion of resorcinol on one

page_text: molecular proportion of the diazo derivatives of aromatic amidocarboxylic acids,
amidohydroxycarboxylic acids, amidoalkylhydroxycarboxylic acids, or of sulpho or
other substitution products thereof, which process consists in treating the said azo
colouring-matters with nitrous acid, or other agents capable of producing the same
result.
3. As new products of manufacture, the new nitroso-azo colouring-matters
prepared by the processes hereinbefore defined, or by any other means producing
the same result.
NEWTON & SON,
Agents for the Applicant.