The Manufacture or Production of Dye Stuffs.
Year: 1894

page_text: Date of Application, 17th Jan., 1894
Complete Specification Left, 16th Oct., 1894-Accepted, 17th Nov., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Dye Stuffs.
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:-
My foreign correspondents have described in the Specification of Application for
Letters Patent No. 4756, dated 4th March 1893, that those naphthol monosulpho
acids and naphthol polysulpho acids which contain the hydroxylic group to a
sulpho group in the position 1:3, yield (when combined with certain diazo
compounds) azo dye stuffs distinguished by a great fastness against alkalies, whereas
other naphthol sulpho acids have not this property.
As described in the Specification of the said Application, my foreign corre-
spondents have succeeded in producing new dye-stuffs possessing great fastness
against the action of alkalies and light, by combining the diazo derivatives of
dehydrothiotoluidine, or analogues thereof, or of sulpho acids of these thio com-
pounds, with a-naphthol-3,-mono sulpho acid, or salts thereof.
My foreign correspondents have now found that also amidonaphtholsulpho
acids containing the hydroxylic group and a sulpho group in the position 1 : 3,
can be combined with certain diazo compounds, to form azo colouring matters,
distinguished by their fastness against the action of alkalies and light. "Of amido
naphthol sulpho acids containing the sulpho and hydroxylic group in the said
position, the following for instance, can be used, viz. ẞ-amido-a,-naphthol-3-mono
sulpho acid and B, amido-a,-naphthol-a, B-disulpho acid.
The former of these two acids is obtained by melting 3-amido-a, B-disulpho
acid with alkalies, whilst the latter can be prepared by sulphonating -naphthyl-
amine-a-mono sulpho acid (B-uaphthylamine-y-mono sulpho acid), or 3-naphthyl-
amine--monosulpho acid (B-naphthylamine mono sulpho acid F.), and melting
with alkalies the Bi-naphthylamine-a, a, B-trisulpho acid thus obtained.
My foreign correspondents have prepared beautiful dye stuffs yielding from red
to bluish-red shades distinguished by their intensity, brilliancy, and fastness
against the action of alkalies, viz., by combining the diazo derivatives of "dehydro
thio toluidine, its analogues, or the sulpho acids thereof." with the above defined
amido naphthol sulpho acids, or salts thereof. The researches of my foreign
correspondents have also shown that the colouring matters thus obtained possess
the valuable property of being further diazotisable (when fixed on the fibre), aud
of then combining with phenols, amines, diamines, amidophenols, amidophenolethers
of the benzene or naphthalene series, the sulpho or carboxylic acids thereof, new
very fast and beautiful shades being thus produced.
By the above expression "dehydrothiotoluidine, its analogues, or the sulpho
acids thereof," my foreign correspondents mean those thio bases which can be
obtained on heating paratoluidine, meta-xylidine, or pseudocumidine, with sulphur,
and the sulpho acids derived therefrom, that is to say, dehydrothio-para-toluidine,
dehydrothio-meta-xylidine, dehydro-thio-pseudo-cumidine, primuline base, or the
like, and the sulpho acids of these or similar thio bases. However, other
analogous products, for instance, those known in commerce as chromine, poly-
chromine, thio chromogen, or the like, can likewise be used.
The production of these azo colouring matters derived from the above named
B-amido-a-naphthol-3-monosulpho acid, or ẞ-amido-a-naphthol-a 3-disulpho

page_text: acid, or the like, is effected in the manner well known, and in use for the
manufacture of analogous azo dye stuffs.
One of the methods is illustrated by the following example. The parts are by
weight.
EXAMPLE.
DYE-STUFF OBTAINED BY COMBINING ONE MOLECULAR PROPORTION OF
DIAZOTISED DEHYDRO THIO-META XYLIDINE WITH ONE MOLECULAR
PROPORTION OF ß₁AMIDO ¤, NAPHTHOL-a₁ ß-disulpho acid.
26-8 parts of dehydrothio meta-xylidine are, in the well known manner,
converted into the diazo compound. The diazo product is then allowed to flow
slowly into a cold solution prepared by dissolving 36-3 parts of the disodium salt of
B₁ amido a, naphthol a B. disulpho acid, and rendered alkaline by means of
sodium carbonate. The formation of the dye begins immediately. In order to
complete the process, the liquid mixture, after standing for about 12 hours, is
heated during some time at about 90 degrees centigrade. After cooling, the
dye-stuff, which is soluble with difficulty, is filtered off, pressed, and dried. The
colouring matter thus obtained possesses the following formula :-
It possesses a great affinity for cotton fibre, and yields (when dyed on unmordanted
cotton) bluish-red shades which are but little altered by the action of alkalies.
Other dye-stuffs result in an analogous manner, if either the diazotised dehydro
thio-meta-xylidine is replaced by the corresponding quantity of the diazo derivatives
of its analogues, which result on heating para-toluidine, meta-xylidine, or pseudo
cumidine, with a greater or less quantity of sulphur, or of the sulpho acids of such
thio bases containing one or several atoms of sulphur, or if the B₁-amido-a,-a-B
disulpho acid is replaced by B₁-amido-a,-naphthol-B-mono sulpho acid, or another
ainido naphthol sulpho acid containing the hydroxylic group and a sulpho group
in the position 1:3, and if these acids, or salts thereof, are combined with the
diazo derivatives of the above defined thio bases, or sulpho acids thereof.
In order to produce these dye stuffs, my foreign correspondents do not limit
themselves to the directions given in the above example, as the method of producing
them can be varied, without departing thereby from the nature of this invention.
Dated this 17th day of January 1894.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye Stuffs.
I HENRY EDWARD NEWTON of The Office for l'atents, 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 4
particularly described and ascertained in and by the following statement :-
My foreign correspondents have pointed out in the Specification of Letters
Patent No. 4756, dated 4th March 1893, that 1:3 alpha, naphthol-beta, mono-
÷

page_text: sulphonic acid (OH: SO,H=1:3) and alpha naphthol epsilon disulphonic acid
(OH: SO,H: SO,H=1:3:8), which both contain the hydroxyl and a sulphonic
group relatively in the meta position (1:3), when combined with certain diazo-
compounds, yield azo dye stuffs which are distinguished by great fastness in
presence of alkalies, whereas analogous azo coloring matters obtained from alpha
naphtholmono or alphanaphtholdisulphonic acids containing hydroxyl and a
sulphonic group otherwise than in meta positions, exhibit but a slight degree of
fastness towards alkalies, owing (my correspondents believe) to the absence of such
meta relationship.
As described in the Specification of the said Letters Patent, my foreign
correspondents have succeeded in producing new dye-stuffs of great fastness in
presence of alkalies and in light, by combining the diazo derivatives of dehydro-
thiotoluidine, or analogues thereof, or of sulphonic acids of these thio compounds,
with alpha, naphthol beta, monosulphonic acid or salts thereof.
acids
My foreign correspondents have now found, that amidonaphtholsulphonic
containing hydroxyl and a sulphonic group in the meta position, can be combined
with certain diazo compounds to form azo coloring matters, also distinguished by
fastness in presence of alkalies and in light. Of the amidonaphtholsulphonic acids
containing the sulphonic group and hydroxyl relatively in the meta position, the
following can be used, viz., beta, amido alpha, naphthol beta, monosulphonic acid,
and beta, amido alpha, naphthol alpha, beta, disulphonic acid.
The former of these is obtained by fusing beta, amido alpha, beta, disulphonic
acid with alkalies, whilst the latter can be prepared by sulphonating beta,
naphthylamine alpha, monosulphonic acid (beta naphthylamine gamma mono-
sulphonic acid), or beta, naphthylamine beta4 monosulphonic acid (beta naphthyl-
amine monosulphonic acid F), and fusing the beta, naphthylamine alpha, alpha,
beta, trisulphonic acid thus obtained with alkalies.
My foreign correspondents have prepared beautiful dye-stuffs yielding from red
to bluish-red shades, distinguished by their intensity, brilliancy, and fastness in
presence of alkalies and acids, viz. by combining the diazo derivatives of "dehydro-
thiotoluidine, its analogues, or the sulphonic acids thereof," with the above defined
amidonaphtholsulphonic acids or salts thereof.
The researches of my foreign correspondents have also shown, that the coloring
matters thus obtained possess the valuable property of being further diazotisable
(when fixed on the fibre), and of then combining with phenols, amines, diamines,
amidophenols amidophenolethers of the benzene or naphthalene series, the
sulphonic or carboxylic acids thereof, new, very fast, beautiful shades being thus
produced.
By the above expression, "dehydrothiotoluidine, its analogues, or the sulphonic
acids thereof," my foreign correspondents mean the thio bases containing one or
several atoms of sulphur which can be obtained on heating paratoluidine, meta-
xylidine, or pseudo cumidine, with sulphur, and the sulphonic acids derived
therefrom, that is to say, the following compounds: dehydrothioparatoluidine,
dehydrothiometaxylidine, dehydrothio pseuducumidine, primuline base, and the like,
and the sulphonic acids of these and similar thio amido compounds. Other
analogous thio amido compounds, for instance, these known in commerce as
chromine, polychromine, thiochromogen, and the like, can also be used.
The production of these azo coloring matters derived from the above named
beta, amido alpha, naphthol beta monosulphonic acid, or beta, amido alphas
naphthol alpha, beta, disulphonic acid, is effected in the manner well known and in
use for the manufacture of analogous azo dye stuffs.
The researches of my foreign correspondents have shown that the combination
of the aforesaid amidonaphtholsulphonic acids with the diazo derivatives of the
thio amido compounds herein before defined, can be effected in either alkaline or
acidulated solutions.
One of the methods is illustrated by the following example. The parts are by
weight.

page_text: DYE-STUFF OBTAINED BY
EXAMPLE.
COMBINING ONE MOLECULAR PROPORTION OF
DIAZOTISED DEHYDROTHIOMETAXYIIDINE WITH ONE MOLECULAR PRO-
PORTION OF BETA, AMIDO ALPHA, NAPHTHOL ALPHA₁ BETA. DISULPHONIC
ACID.
26-8 parts of dehydrothiometaxylidine are diazotised in the well-known manner,
and the diazo compound is allowed to flow slowly into a cold solution prepared by
dissolving 36-3 parts of the disodium salt of beta, amido alpha, naphthol alpha,
beta, disulphonic acid, rendered alkaline by sodium carbonate. The formation of
the dye begins immediately. In order to complete the process, the liquid mixture
is allowed to stand during about 12 hours, and is then heated during some time at
about 90 degrees centigrade. It is then cooled, and the dye-stuff, which is
difficultly soluble, is filtered off, pressed, and dried. The coloring matter thus
obtained is represented by the following formula:—
4
It possesses a great affinity for cotton fibre, and yields (when dyed on
unmordanted cotton) bluish-red shades which are but little altered by alkalies.
The same coloring matter is formed if the combination of the beta, amido alpha,
naphthol alpha, beta, disulphonic acid with the diazo derivative of dehydrothio-
metaxylidine is effected in acid solution, for instance, in a solution acidulated with
acetic or muriatic acid.
Analogous dye-stuffs are formed if either instead of diazotised dehydrothio-
metaxylidine, the corresponding quantity of the diazo derivatives of the analogous
thio amido compounds, or sulphonic acids of such thio amido bases containing one
or several atoms of sulphur be used, or if the beta, amido alpha, alpha beta
disulphonic acid is replaced by beta, amido alpha, naphthol beta, monosulphonic
acid, and if this latter acid or salts thereof are combined either in alkaline or
acid solution with the diazo derivatives of the above defined thio amido compounds
or sulphonic acids thereof.
The shades produced on unmordanted cotton by the coloring matters hereinbefore
defined, are in general bluish-red or red.
In order to produce these dye-stuffs, my foreign correspondents do not limit
themselves to the directions given in the above example, as the method of
producing them can be varied, and, in general, all methods can be used which are
known or in use for producing analogous or similar dye-stuffs.
Having now particularly described and ascertained the nature of the said inven-
tion, and in what manner the same is to be performed, as communicated to me from
abroad, I declare that what I claim is :-
1. The process for producing azo dye-stuffs by combining one molecular pro-
portion of beta, amido alpha, naphthol beta monosulphonic acid, or beta, amido
alpha, naphthol alpha, beta, disulphonic acid, or an alkaline salt thereof, with one
molecular proportion of the diazo derivatives of dehydrothio para toluidine,
dehydrothiometaxylidine, dehydro thio pseudo cumidine, primuline base, dehydro-
thioparatoluidine sulphonic acid, debydrothiometaxylidine sulphonic acid, dehydro-
thiopseudocumidine sulphonic acid, primuline, or analogous thio amido compounds.

page_text: 2. As new products of manufacture, the new coloring matters produced by the
process hereinbefore defined, or by any other process affording the same result.
Dated this 28th day of September 1894.
NEWTON & SON,
Agents for the Applicant.