The Manufacture or Production of Dye Stuffs.
Year: 1895

page_text: Date of Application, 7th Mar., 1895
Complete Specification Left; 9th Dec., 1895-Accepted, 11th Jan.. 1896
[Communicated from abroad by IHE
ARDEN
PRIREN
BAYER & Co., of Elberfeld, 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:-
Azine dye-stuffs capable of dyeing with the aid of mordants have not yet been
produced, though theoretically it might have been assumed that such colouring
inatters would be more valuable than the other induline dyes, owing to their
superior dyeing properties.
My foreign correspondents have now found that the "symmetrical" and "mixed "
dialkyl-alpha, beta, naphthylene diamines, and sulphonic derivatives thereof, which
can be obtained by means of the processes described in the Specifications of Letters
Patent No. 8898, 16780", and 19623, can be converted, as such, or in the form
of suitable derivatives thereof, into azine dye-stuffs, capable of dyeing with the
aid of mordants.
"
This process, for instance, consists in heating the said "symmetrical" or "mixed
dialkyl-alpha, beta, naphthylene diamines, or sulphonic acids thereof, with such
nitroso products or azo compounds of the benzene or naphthalene series, which
contain, in a suitable position, groups capable of forming so-called lakes, and in
subsequently sulphonating the so-formed azine products, in oase they are found to
be insoluble, or soluble with difficulty.
According to the researches of my foreign correspondents, polysulphonic acids
distinguished by reason of their valuable dyeing properties are especially obtained
on using fuming sulphuric acid as sulphonating agent.
The new azine dye-stuffs, my foreign correspondents have further found, can
also be produced, if, in place of heating the nitroso products or azo compounds
hereinbefore defined, with the "symmetrical" or "mixed" dialkyl-alpha, beta
naphthylene diamiues, or sulphonic acids thereof, any other known process for
preparing azine dye-stuffs is employed. The azine products, however obtained, are
subsequently treated with sulphonating agents, to render them soluble.
•
Of nitroso products and azo compounds my foreign correspondents use, for
instance, those derived from ortho-hydroxy-carbonic acids (such as salicylic acid,
hydroxy-naphthoic acid, or the like), ortho- or peri-dihydroxy compounds of the
benzene or naphthalene series, or the like.
In order to illustrate one method of producing the new dyo-stuffs, the following
examples are given, which, however, are merely typical. The parts are by weight.

page_text: benzene azo salicylic acid (obtained from the combination of diazotised aniline with
salicylic acid), are then added, and the resulting mixture is heated during from
4 to 5 hours at from 110 to 130 degrees Centigrade. The condensation begins at
once, and after cooling, the resulting mass forms a crystalline mass, consisting of
greenish lustrous small needles, which are filtered off and treated with sodium
carbonate or ammonia, in order to obtain the finished dye-stuff, that is to say, a
soluble salt of the dye-stuff acid first produced.
The colouring matter thus prepared dissolves in hot water, affording a beautiful
blaish red coloured solution, and yields beautiful bluish-red shades on wool
mordanted with chromium salts. It is soluble with difficulty in strongly acidulated
water.
This dye-stuff is advantageously converted into a colouring matter which easily
dissolves even in acidulated water, viz., by sulphonation, which process can be
carried out as described in the following example.
'
CONVERSION OF THE COLOURING MATTER OBTAINED AS DESORIBED IN THE
POREGOING FIRST EXAMPLE, INTO A DYE-STUFF SOLUBLE WITH GREATER
READINE88.
1 part of the dye-stuff obtained as described in the preceding first example is
dissolved in four times its weight of sulphuric acid (at 66 degrees Baumé), and the
resulting liquid is heated at from 70 to 90 degrees Centigrade, until a sample taken
out is found to be soluble with ease in hot water.
The sulphonated dye is isolated in a suitable manner. It yields red shades on
ordinary wool, and produces beautiful bluish-red and fast shades on wool mordanted
with chromium salts. It is also distinguished by reason of its capability of yielding
eveu shades, when dyed together with other suitable colouring matters.
resulting shades are fast against the action of acids and alkalies.
The
In the production of the azine dye-stuffs herein before defined, and their sulpho-
nated derivatives, my foreign correspondents do not limit themselves to the
particulars given in the above examples. All other methods known and in use for
producing analogous or similar aziue dye-stuffs, and sulphonating such or the like
products, can be used. For instance, phenol or the like can be employed us a
suitable solvent or diluent for the azo products obtained from the combination of
diazo derivatives with the hydroxy carbonic acids, or the like materiale, containing
groups capable of forming so-called lakes.
The process proceeds in an analogous manner, if the corresponding nitroso
compounds are used in place of the azo products above referred to. In this case,
alcohol acetic acid, glacial acetic acid, glycerinol, or the like, can be employed as
Folvents or diluents.
"
Analogous products result, if the "symmetrical" or mixed" dialkyl-alpha,
beta, naphthylene diamines, or other sulphonic acids thereof, are substituted for the
ditolyl alpha, beta, naphthylene diamine alpha, sulphonic acid, or if the azo dye-
stuff from diazo benzene and salicylic acid is replaced by corresponding quantities
of other dye-stuffs resulting from the combination of other diazo compounds and
salicylic acid, or by the azo products resulting from the combination of diazo
bodies with cresolcarboxylic acid, alpha, alpha, diliydroxynaphthalene, pyrogaliol,
or other components containing groups capable of forming lakes.
As hereinbefore mentioned, the corresponding nitroso compounds can be employed
with the sanie result.
These azine colouring matters, capable of dyeing with the aid of mordants, can
also be produced by means of other processes known and in use for preparing
azine dye-stuffs. Thus, for instance, the same azine colouring matters can be
obtained on using the amido compounds which result from the reduction of the azo
compounds or nitroso products hereinbefore defined, or otherwise produced. In
this case, the process is carried out by subjecting the "symmetrical" or "mixed "5

page_text: dialkyl-alpha beta, naphthylene diamines. or sulphonic acids thereof, to a joint
oxidation, together with the last defined amido compounds.
Such or similar modifications do not alter the nature of this invention, which,
in general, relates to the production of new azine dye-stuffs capable of dyeing,
with the aid of mordants from such components as contain groups capable of
forming lakes, and to the further sulphonation of the so formed products, in case
they are found to be insoluble, or soluble with difficulty.
Dated this 7th day of March 1895.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
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 and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
Azine dye-stuffs, capable of dyeing with the aid of mordants, have not yet been
produced, though theoretically it might have been assumed that such coloring
matters would have superior dyeing properties, and be more valuable than the
other induline dyes.
My foreign correspondents have now found that the "symmetrical" and "mixed"
dialkyl alpha, beta, naphthalene diamines, and sulphonio derivatives thereof, which
can be obtained by means of the processes described in the Specifications of Letters
Patent No. 8898, 16780", and 19623", can be converted into uzine dye-stuffs
capablo of dyeing with the aid of mordants.
or
This process, for instance, consists in henting the said " symmetrical "
"mixed" dialkyl alpha, beta, naphthalene diamines, or sulphonic acids thereof,
with nitroso products, or azo compounds of the benzene or naphthalene series,
containing, in a suitable position, groups capable of forming lakes, and in sub-
sequently sulphonating such azine products, in case they are found to be
insoluble, or to dissolve with difficulty. According to the researches of my
foreign correspondents, polysulphonio acids, distinguished on account of their
valuable dyeing properties, are obtained especially on using fuming sulphuric
acid as sulphonating agent.
My foreign correspondents have further found, that the new azine dye-stuffs can
also be produced, if, instead of heating the nitroso products or azo compounds
hereinbefore defined with the "symmetrical" or "mixed" dialkyl alpha, beta,
naphthylene diamines, or sulphonic acids thereof, any other known process for
preparing azine dye-stuffs is employed. The azine products, however, obtained, are
subsequently sulphonated, in case they are insoluble, or dissolve with difficulty.
The nitroso products and azo compounds used by my foreign correspondents are,
for instance, those derived from ortho-hydroxy-carboxylic acids (such as salicylio
acid, hydroxy naphthoic acid, or the like), and ortho or peri dihydroxy-compounda
of the benzene or naphthalene series, or the like.
In order to illustrate one method of producing the new dye-stulfs, the following
typical examples are given. The parts are by weight.

page_text: dissolved in a mixture of 2-6 parts of sodium acetate and 50 parts of acetic acid
(containing 60 per cent. of pure acid). 7.3 parts of the dye-stuff benzene azo
salicylic acid (obtained by combining diazotised aniline with salicylic acid)
are then added, and the mixture is heated during from 4 to 5 hours, at from
110 to 130 degrees Centigrade. The comlensation begins at once. When cool,
the product forms a crystalline mass of small, lustrous greenish needles, which
are filtered off and neutralized with sodium carbonate, or ammonia, in order to
obtain the finished dye-stuff, that is to say, a soluble salt of the dye-stuff acid first
produced.
The coloring matter thus prepared dissolves in hot water, affording a beautiful
bluish-red colored solution, and yields beautiful bluish red shades on wool
mordanted with chromium salts. It dissolves with difficulty in strongly
acidulated water.
This dye-stuff is advantageously converted into a coloring matter which is
easily soluble, even in acidulated water, by sulphonation, which process can be
carried out as described in the following example.
DYE-STUFF FROM DIPHENYL ALPHA BETA, NAPHTHYLENE DIAMINE ALPHA
BULPRONIO ACID AND BENZENE AZO ALPHA ALPHA DIHYDROXY-
NAPHTHALENE.
7.8 parts of diphenyl alpha, beta,-naphthylene diamine alpha, sulphonic acid aro
mixed with 8 parts of benzene azo alpha, alpha, dihydroxy naphthalene, and
2-7 parts of sodium acetate, and 20 parts of glacial acetic acid. The mixture is
moderately boiled, say, during six hours, until the whole has dissolved, and the
solution exhibits a blue color. When cool, the whole is poured into alcohol. The
dye-stuff separates in a crystalline state. It is isolated by filtration, and purified
by washing with alcohol, in order to remove adherent mother liquor. The
coloring matter thus formed is a monosulphonic acid, which is with advantage
converted into a polysulphonic acid by a subsequent sulphonation, for instance, by
meaus of fuming sulphuric acid (containing 25 per cent. of sulphuric anhydride),
at 50 degrees Centigrade. The polysulphonic acid separates out, on pouring the
sulphonated mixture into water. It is filtered off, and converted into sodium salt.
This sodium salt, constituting the finished dye-stuff, readily dissolves in hot water.
It produces on wool mordanted with chromium salte, blue shades which withstand
the action of alkalies and acids.
In producing the azine dye-stuffs hereiubefore defined and their sulphonated
derivatives, my foreign correspondents do not limit themselves to the particulars
given in the above examples. All other known methods in use for producing
analogous or similar azine dye-stuffs, and sulphonating such or the like products,
can be adopted. For instance, phenol or the like can be used as a suitable solvent
:or diluent for the azo products obtained by combining diazo derivatives with the

page_text: hydroxy carboxylic acids, or the like materials containing groups capable of
forming lakes.
The process proceeds in an analogous manner, if the corresponding nitroso.
In this
compounds are used in place of the azo products above referred to.
case, alcohol, acetic acid, glacial acetic acid, glycerol, or the like, can be used as.
solvents or diluents.
"
"mixed "
Analogous products are formed, if the "symmetrical or
dialkyl
alpha, beta, naphthylene diamines, or other sulphonic acids thereof, are substituted
for the ditolyl alpha, beta, naphthylene diamine alpha-sulphonic acid, and diphenyl
alpha, beta, naphthylene diamine alpha, sulphonic acid, prescribed in the preceding
Examples A, B, and C; or if, instead of the azo dye-stuff from diazo benzene and.
salicylic acid, and the azo product benzene azo alpha, alpha, dihydroxynaphthalene
used in the said examples, corresponding quantities of other dye-stuffs are used,
Buch as are formed by combining other diazo compounds with salicylic acid, or
alpha, alpha, dihydroxynaphthalene, or the azo products formed from diazo com-
pounds and cresol-carboxylic acid, pyro-gallol, or other components containing
groups capable of forming lakes.
As hereinbefore mentioned, the corresponding nitroso compounds can be used.
with the same result.
Azine coloring matters, capable of dyeing with the aid of mordants, can also be-
produced by means of the other known processes in use for preparing azine
dye-stuffs. Thus, for instance, the same azine coloring matters can be obtained
on using the amido compounds formed by reducing the azo compounds, or nitroso-
products hereinbefore defined. In this case, the process is carried out by subjecting.
the "symmetrical" or "mixed" dialkyl alpha, beta, naphthylene diamines, or.
sulphonic acids thereof, to oxidation, conjointly with the last defined amido.
compounds.
Such or similar modifications do not alter the nature of this invention, which,
speaking generally, relates to the production of new azine dye-stuffs capable of
dyeing, with the aid of mordants, from the "symmetrical" and "mixed "dialkyl
alpha, beta, naphthylene diamines, or sulphonic acids thereof, and from such com-
ponents as contain groups capable of formning lakes, and to the further sulphonation
of the products, in case they are found to be insoluble, or to dissolve with.
difficulty.
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 production of azine coloring matters capable of dyeing wool with the
aid of mordants, from "symmetrical" or "mixed" dialkyl alpha, beta, naphthy-.
lene diamines, or sulphonic acids thereof, which process consists either in allowing
"symmetrical" or "mixed" dialkyl alpha, beta, naphthylene diamines, or sulphonic
acids thereof, to act on nitroso compounds, or azo products containing suitable
groups adapted for the formation of lakes, or in subjecting "symmetrical" or
"mixed" dialkyl-alpha, heta, naphthylene diamines, or sulphonic acids thereof, to
oxidation, conjointly with the amines which can be obtained by reducing the
aforesaid nitroso compounds, or azo products, and which also contain suitable.
groups adapted for the formation of lakes, and in subsequently sulphonating the
products, in case they are found to be insoluble, or to dissolve with difficulty.
2. As new products of manufacture, the new azine dye-stuff's produced in the.
manner hereinbefore defined, or in any other manner affording the same result.
Dated this 7th day of December 1895.
NEWTON & SON,
Agents for the Applicant.