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

page_text: Date of Application, 10th Aug., 1892
Complete Specification Left, 10th May, 1893-Accepted, 17th June, 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:-
In the Specifications of Letters Patents granted to Benjamin Willcox, riz.,
No. 3397, dated 4th March 1890; No. 13443, dated 26th August 1890; and
No. 5984, dated 7th April 1891, for inventions communicated to the said Benjamin
Willcox by my present correspondents, valuable monoazo and tetrazo colouring-
matters are described, which result by combining the so-called 1:8-dihydroxy-
naphthalene-a-monosulpho acid, 1:8-dihydroxynaphthalene-a-disulpho acid, and
1:8-dihydroxynaphthalene-ß-disulpho acid, either with the diazo derivatives of
amines, amidophenols, amidophenol-ethers of the benzene and naphthalene series,
sulpho and carboxylic acids of the said amido compounds, or with the salts of the
following tetrazo compounds, namely: tetrazodiphenyle, tetrazophenyle ortho
tolyle, tetrazo ortho ditolyle, tetrazostilbene, tetrazofluorene, tetrazonaphthalene,
tetrazodiphenolether, tetrazoalkylhydroxydiphenyle, tetrazoalkylhydroxyphenyle
ortho tolyle, the analogues thereof, and suplo or carboxylic acids thereof.
My foreign correspondents have now found that dye stuffs, analogous, and like-
wise technically valuable, can be obtained by the combination of the aforesaid
diazo- or tetrazo-compounds with 1:8 dihydroxynaphthalene, and by further treating
the dyes thus formed with sulphurising or suphonating agents.
The colouring matters, to start from in this process, are produced in the well
known manner by coupling the above mentioned diazo or tetrazo compounds with
the 1:8 dihydroxynaphthalene first described in Liebig's Annalen, voluine 247,
page 356.
In subjecting to this process tetrazo dye-stuffs derived from 1:8-dihydroxy-
naphthalene, both the so-called symmetrical products, obtained from one molecular
proportions of the said dihydroxynaphthalene, and the so called mixed dye-stuffs
resulting from the combination of equi-molecular proportions of a tetrazo salt,
1:8 dihydroxynaphthalene, and an other dye-stuff component, can be employed.
The investigations of my foreign correspondents have proved that the dye-stuffs
obtained by this sulphurising process are in chemical composition not identical with
the corresponding products formed by combining the same diazo or tetrazo salt
with 1:8 dihydroxynaphthalene-alpha-monosulpho acid, 1:8-dihydroxynaphthalene-
alpha-disulpho acid or 1:8 dihydroxynaphthalene-beta-disulpho acid. It is, however,
noticeable, that these new colouring matters likewise produce beautiful and fast
shades, and in general possess the same technical value as the dye-stuffs formed
from 1:8 dihydroxynapthalene sulpho acids.
My foreign correspondents have found that in heating, for a short time, the
intermediate products derived from 1:8 dihydroxynaphthalene with monohydratic
sulphuric acid or the like, sulpho acids are formed which change in colour into
yellow when alkalies are added, and in heating with monohydratic sulphuric acid,
or the like, those dyes soluble in alcohol for a longer period, colouring matters
result which are "fast" to the action of alkalies. If heating be continued for too
long a time, the "fastness" to alkalies again ceases, products being formed the
shades of which are changed into blue by the addition of alkalies.

page_text: DYE-STUFF OBTAINED BY
FURTHER SULPHURISING THE INTERMEDIATE
PRODUCT FROM EQUIMOLECULAR PROPORTIONS OF DIAZOTISED ANILINE
AND 1:8 DIHYDROXYNAPHTHALENE.
The solution of diazobenzolchloride produced from 13 parts of aniline
hydrochlorate by means of 7 parts of sodium nitrite, is allowed to flow with
stirring into a mixture prepared from about 30 parts of sodium acetate and
16 parts of 1: 8-dihydroxynaphthalene, with the addition of a large quantity of
water and some acetic acid. After several hours standing, the combination is
complete. The dye-stuff which separates perfectly is filtered off, washed out with
water, pressed, and dried. The so-formed dry product, after having been finely
sifted, is introduced into from five to ten times its weight of monohydratic. sulphuric
acid, and this mixture is heated at from about 40 to 50 degrees centigrade, until a
sample taken out readily dissolves in water, with a magenta red colour, which is no
longer alterable into yellow by the addition of alkalies. If this stage be arrived
at, the mixture, after cooling, is poured into water. The product not sulphurised,
and which does not readily dissolve, is filtered off, and the new dye stuff,
sulphurised, is isolated in usual manner by salting ont, filtering off, pressing, and
drying.
This dye stuff dyes wool not mordanted, in an acid bath, a magenta-red, whilst
the shades produced on wool mordanted with chromium salts, are violet-black.
DYE-STUFF FORMED BY FURTHER TREATING WITH SULPHURISING AGENTS
THE PRODUCT OBTAINED FROM THE COMBINATION OF ONE MOLECULAR
PROPORTION OF TETRAZODIPHENYLE CHLORIDE AND TWO MOLECULAR
PROPORTIONS OF 1:8-DIHYDROXYNAPHTHALENE.
18.4 parts of benzidine, or the equivalent quantity of a salt of this diamine, are
converted in a hydrochloric acid solution, by means of 14 parts of sodium nitrite, into
tetrazodiphenyle chloride. The resulting solution is allowed to flow into an
alkaline solution of 32 parts of 1:8 dihydroxynaphthalene, moderately acidulated
by means of acetic acid, and mixed with about 60 parts of sodium acetate. After
several hours' standing, the combination is completed. Soda-lye is added, and the
dye-stuff is isolated by salting out, filtering off, pressing, and drying.
In order to sulphurise or sulphonate this intermediate product, the latter, after
carefully drying is introduced into from ten to twenty times its weight of mono-
hydratic acid, and the mixture thus obtained is heated at about 50 degrees centigrade,
until a portion of the dyestuff isolated in usual manner, dissolves with facility in
sodium carbonate or sodium acetate. If this stage be arrived at, the mixture is
poured into water, the precipitate separated is filtered off, and treated with a
solution of sodium carbonate. The dye stuff is precipitated by adding common salt
to the alkaline solution, which is previously filtered in order to remove the product
not sulphurised. The precipitate is filtered off, pressed, and dried.
This new colouring matter dyes unmordanted cotton, in alkaline soap baths, a
blue, whilst the shades produced by the intermediate product not sulphurised, are
bluish-violet.
Of course, this invention is not restricted to the production of the two dye-stuffs
obtainable as described in the foregoing examples. My foreign correspondents
have illustrated in these examples merely a method of producing two dye-stuffs
amongst the great number of products obtainable by means of this process. The
methods described in the said two examples can likewise be modified. Thus, the

page_text: monohydratic acid can be replaced by the equivalent quantity of fuming sulphuric
acid or other sulphurising agents acting in the same or a similar manner, and the
complete dye-stuff likewise can be isolated in any other way, etc.
In order to produce the other analogous so-called monoazo dyes, the diazo
compound of the preceding first example, is to be replaced by the equivalent
quantities of diazo salts of other amines, or substitution products thereof.
As amines and their substitution products, my foreign correspondents understand
all the amines capable of being employed as dye stuff components, likewise amines
substituted in the nucleus by halogen atoms, nitroamines, amidophenols, nitroamido-
phenols, amidophenolethers, nitroamidophenolethers of the benzene and naphthalene
series, the sulpho, carbonic, and sulphocarbonic acids of the amido products last
mentioned, also amidoazobenzene, amidoazotoluene, amidoazoxylene, and their
sulpho acids, phenylene diamines, and toluylene diamines, and naphthalene diamines,
which are substituted in either of the amido groups by fatty or aromatic acid
radicles or alkyl groups (including the benzyl groups), and the sulpho derivatives
of these diamines substituted.
In a similar manner as the sulphonation of the intermediate product from one
molecular proportion of tetrazodiphenyle chloride, and two molecular proportions
of 1:8 dihydroxynaphthaline is effected as described in the foregoing second
example, this process can be carried out in employing the other symmetrical
products obtained from one molecular proportion of the salts of analogous tetrazo
compounds or their sulpho and carboxylic derivatives, with two molecular pro-
portions of 18 dihydroxynaphthalene. New valuable dye stuffs are obtained in
this manner, as my foreign correspondents have found.
By subjecting the so-called mixed products resulting from the combination of
equimolecular proportions of a tetrazo salt, 1:8 dihydroxynaphthalene, and
another dye stuff component, such as an amine, a phenol, an amidophenol, amido-
phenolether of the benzene or naphthol series, or a supho or carboxylic acid
thereof, to a further treatment with sulphurising agents, likewise products of high
technical value have been obtained by my foreign correspondents in analogous
manner to that described in the preceding second example.
The dye stuffs produced in the ways substantially as hereinbefore described,
possess the property of dyeing when combined together with other dyes, and
yield shades excellent for their fastness," when submitted to the action of alkalies.
Dated this 10th day of August 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:-
In the Specifications of Letters Patent granted to Benjamin Willcox, viz.,
No. 3397, dated 4th March 1890, No. 13443, dated 26th August 1890; and
No. 5984, dated 7th April 1891, for inventions communicated to the said Benjamin
Willcox by my present correspondents, valuable mono-azo colouring matters are
described, which result on combining the so called 1:8-dihydroxynaphthalene
alpha-monosulpho acid, 1:8-dihydroxynaphthalene-alpha-disulpo acid, or 1:8 diby-
droxynaphthalene-beta-disulpho acid, with the diazo derivatives of amines,
amidophenols, amidophemolethers of the benzene and naphthalene series, sulpho
or carboxylic acids of the said amido compounds.
My foreign correspondents have now found, that analogous, and also technically

page_text: valuable, dye stuffs, can be obtained by the combination of diazo derivatives with
1:8 dihydroxynaphthalene, and by further treating the dyes thus formed with
sulphurising or sulphonating agents.
The colouring matters which form the starting point in this process, are produced
in the well known manner, riz., by coupling diazo compounds with the 1:8 dihy-
droxynaphthalene first described in Liebig's Annalen, volume 247, page 356.
The investigations of my foreign correspondents have proved that the dye stuffs
obtained by this sulphurising process are not identical in chemical composition with
the corresponding products formed by combining the same diazo salts with
1:8 dihydroxynaphthalene-alpha monosulpho acid, 1:8-dihydroxynaphthalene alpha
disulpho acid, or 1:8 dihydroxynaphthalene-beta disulpho acid. It is, however,
noticeable that these new colouring matters likewise produce beautiful and fast
shades, and in general possess the same technical value as the dye-stuffs formed
from 1:8 dihydroxynaphthalene sulpho acids.
My foreign correspondents have found that on heating the intermediate products
obtained from diazo compounds and 1:8 dihydroxynaphthalene, for a short time,
with monohydratic sulphuric acid (or the like agents), sulpho acids are formed
which change in colour to yellow, when alkalies are added, and, on heating those
dyes for a longer period with monohydratic sulphuric acid (or the like agents),
colouring matters result which are "fast" to the action of alkalies. If the heating
be continued for too long a time, the "fastness" to alkalies is destroyed, products
being formed the shades of which are changed into blue by the addition of
alkalies.
The process or method is extremely simple, and can be illustrated by the
following example, the parts being by weight.
DYE STUFF OBTAINED BY
FURTHER SULPHURISING THE INTERMEDIATE
PRODUCT FROM EQUIMOLECULAR PROPORTIONS OF DIAZOTISED ANILINE
AND 1:8 DIHYDROXYNAPHTHALENE.
The solution of diazobenzenechloride produced from 13 parts of aniline hydro-
chlorate by means of 7 parts of sodium nitrite, is allowed to flow, during agitation,
into a mixture prepared from about 30 parts of sodium acetate, and 16 parts
of 1:8 dihydroxynaphthalene, with the addition of a large quantity of water, and
some acetic acid: After several hours standing, the combination is complete. The
dye stuff, which separates perfectly, is filtered off, washed out with water, pressed,
and dried. The so-formed dry product, after having been finely sifted, is introduced
into from five to ten times its weight of monohydratic sulphuric acid, and this
mixture is heated at from about 40 to 50 degrees centigrade, until a sample taken
out readily dissolves in water with a magenta red colour, which will not be changed
to yellow on the addition of alkalies. When this stage is arrived at, the mixture
is poured into water. The product, not sulphurised, and which does not readily
dissolve, is filtered off, and the new dye-stuff, sulphurised, is isolated in usual manner
by salting out, filtering off, pressing, and drying.
This dye stuff dyes unmordanted wool in an acid bath a magenta red, whilst the
shades produced on wool mordanted with chromium salts are violet-black.
Of course, this invention is not restricted to the production of the dye-stuff
obtainable as described in the foregoing example. My foreign correspondents have
illustrated, in this example, merely a method of producing one dye-stuff amongst
the great number of products obtainable by means of this process. The method
described in the said example can likewise be modified. Thus, the monohydratic
acid can be replaced by the equivalent quantity of fuming sulphuric acid, or other
sulphurising agents acting in the same or a similar manner, and the complete
dye-stuff can be isolated in any other way.
My foreign correspondents has ascertained that amongst the dye-stuffs obtainable

page_text: by means of the process illustrated by the above example, those products are of
special technical value, which result from diazobenzene, diazotised meta-amido
benzene sulpho acid, or diazotised para amidobenzene sulpho acid.
The colouring matter obtained from diazotised meta amido benzene sulpho acid,
yields, on unmordanted wool magenta red shades shewing a yellowish-hue, whilst
the dye-stuff from diazotised para-amido benzene sulpho acid produces, on
unmordanted wool, magenta red shades shewing a bluish huc. The shades
produced by these colouring matters on wool mordanted with chromium salts, are
violet-black, and similar to the shades which are obtained in dyeing chromated
wool with the dye stuff from diazobenzene, as described in the foregoing example.
In producing the last named colouring matters from diazotised meta- or para
amido benzene sulpho acid, the sulphonation process proceeds in such a manner that
sulphonated products result at, first, which are not fast to the action of alkalies,
whilst after further treatment, sulpho dye stuffs are formed which possess the
desired fastness to alkalies, but the latter products, if treated for too long a time
with the sulphonating agents, lose their fastness, and accordingly the time for
stopping the sulphonation can be readily be ascertained by the change in colour
which is effected by adding alkalies to the sulphonated products isolated from
samples of the re-action mixture during the process.
The dye stuffs produced substantially as hereinbefore described, possess the
property of dyeing equally when combined with other dyes, and yield shades
excellent for their fastness, when submitted to the action of alkalies.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be perforined, I declare that what I
claim is:-
1. The process of producing azo colouring-matters fast against the action of
alkalies, which process consists in first combining diazotised aniline, meta or para
amido benzene sulpho acid, with 1:8 dihydroxynaphthalene (in equimolecular
proportions), and then treating the resulting products with sulphonating agents,
until the sulpho products thus formed are found to be perfectly fast against the
action of alkalies.
2. As new products of manufacture, the new colouring matters resulting in the
manner hereinbefore described, or by any other process producing the same result.
Dated this 9th day of May 1893.
NEWTON & SON,
Agents for the Applicant.