The Manufacture or Production of Dye-stuffs.
Year: 1895

page_text: Date of Application, 19th Mar., 1895
.1°
..Complete. Specification Left, 19th Dec., 1895-Accepted, 29th Feb., 1.896
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
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:-
O. N. Witt, in the Berichte der Deutschen Chemischen Gesellschaft (volume 18,
page 1119, and volume 19, page 441), has stated that amidoazo paratoluene melting
at 118.5 degrees Centigrade can be easily condensed with alphanaphthylamine, to
form so-called eurhodines.
My foreign correspondents have now found, that in place of alphanaphthyl-
amine, alphanaphthylamine sulphonic acids, and particularly alkylalphanaphthyl-
amine sulphonic acids (such as phenylalphanaphthylamine sulphonic acids,
tolylalphanaphthylamine sulphonic acids, or the like, obtainable, for instance, by
means of the processes described. in the Specification of Letters Patent No. 7337A,
dated 16th April 1892), can be condensed with amidoazoparatoluene, dye-stuffs
being thus obtained which differ from the analogous dye-stuffs described in the
Specification of Letters Patent No. 10138c, dated 27th May 1892, in that the
former coloring matters contain sulphonie groups in place of hydrogen atoms of
the naphthalene nucleus. The said dyestuffs described in the Specification of the
last-named Letters Patent, are sulphonic acids, and result by sulphonating the
eurhodine, which has the formula-
They contain the sulphonic groups in the nuclei 5 and 3, for it is stated in
the Specification of the German Patent which corresponds with the last mentioned
English Letters Patent, that sulphonic groups cannot be substituted for hydrogen
in the nuclei 1 and 2, on sulphonating the said eurhodine.
My foreign correspondents have further tried to alkylate the nitrogen of the
azine group contained in the said eurhodine sulphonic acids obtainable by con-
densing alphanaphthylamine sulphonic acids, or alkylalphanaphthylamine sulphonic
acids, with amidoazoparatoluene, and these researches have shown that the greater
part of the said dye-stuffs (or eurhodine sulphonic acids) is not acted on by
methyliodide in the manner desired, but that the alkylation readily takes place on
using those eurhodine sulphonic acids which are derived from alpha, naphthyl-
aminealpha, sulphonic acid.
The production of these dye-stuffs, which chemically are sulphonic acids, or
salts of sulphonic acids, of phenyl- or tolyleurhodines, alkylated on the one
nitrogen atom of the azine nucleus, is in general effected by allowing amido-
E
7

page_text: azoparatoluene to act on phenyl or tolyl alpha, naphthylamine alpha, sulphonic
acid in the presence of a suitable solvent or diluent (such as phenol, alcohol, glacial
acetic acid, glycerinol, paratoluidine, or the like), converting the so-formed mono-
sulphonic acids into readily soluble disulphonic acids by treatment with suitable
sulphonating agents, and finally alkylating these disulphonic acids, for instance,
by heating their alkaline solutions with methyliodide at from about 120 to
150 degrees Centigrade.
According to the researches of my foreign correspondents, the same or analogous
coloring matters can also be obtained by condensing monoalkylamidoazopara-
toluene, or "analogues of monoalkylamidoazoparatoluene," with phenyl- or
tolyl-alpha, naphthylamine alpha, sulphonic acid, and subsequently sulphonating
the so formed phenyl- or tolyleurhodine monosulphonic acid alkylated on the one
nitrogen atom of the azine group. My foreign correspondents mean by the above
expression "analogues of monoalkylamidoazoparatoluene," such compounds as
result from the combination of any diazo compounds with monoalkyl- or dialkyl-
paratoluidine. It is to be noted that one of the two alkyl groups contained in
the dialkylamido group of the dialkylated amido azo products. is split off on con-
densing these dialkylated amido azo_products with phenyl- or tolyl-alpha,
naphthylamine alpha, sulphonic acid. For instance, those amido azo compounds
can be used which are formed by allowing diazo benzene chloride to act on
monomethylparatoluidine, and transforming the first formed diazo-amido com-
pound, or by acting with diazotised sulphanilic acid on dimethylparatoluidine or
the like.
In order to illustrate the production of the dye-stuff's hereinbefore defined, the
COLORING MATTER OBTAINED BY CONDENSING PARATOLYLALPHA₁
THYLAMINE ALPHA SULPHONIC ACID WITH
NAPH-
AMIDOAZOPARATOLUENE,
AND SUBSEQUENTLY SULPHONATING AND ALKYLATING.
313 parts of paratolylalpha, naphthylamine alpha, sulphonic acid are stirred
into from 50 to 60 parts of phenol, heated by means of a water bath. 33 parts of
amido azoparatoluene are then added to the liquid, while stirring. A green liquid
results, which, after some time, turns into yellow, and finally into red. Heating by
means of a water bath is continued until a sample taken out dissolves in concentrated
sulphuric acid, yielding no longer a yellow-colored, but a pure green-colored
solution. At this stage, the resulting mass is treated with an excess of dilute soda
lye, in order to remove the phenol used in excess. The sodium salt of the mono-
sulphonic acid thus formed, which dissolves with difficulty in the excess of soda lye,
remains after removing the alkaline solution of phenol. The said residue is
dissolved in a large quantity of hot water, and after cooling, this liquid is filtered,
in order to remove a small quantity of insoluble resinous by-products. On adding
muriatic acid to the yellow filtrate thus obtained, the paratolyl eurhodine mono-
sulphonic acid which is insoluble even in hot water, is separated. It forms a violet
precipitate. This precipitate, when pressed and dried, is treated with boiling
alcohol, which dissolves a slight quantity of coloring matters formed as by-
products, whereas the pure monosulphonic acid is scarcely dissolved. The mono-
sulphonic acid thus purified is carefully dried, and then stirred into about 6 parts
of sulphuric acid (at 66 degrees Baumé), and this sulphuric acid liquid is heated
by means of a water bath, until a test portion taken out, when dissolved in dilute
ammonia liquor, no longer yields a precipitate of monosulphonic acid unaffected
by acidulation with acetic acid. If this stage is arrived at, the sulphuric acid
liquid is poured into ice water and the disulphonic acid, which is insoluble in an
excess of sulphuric acid, and therefore is separated, is filtered off and pressed. In
order to purify it, this disulphonic acid is dissolved in the calculated quantity of
soda-lye and a small quantity of water. The resulting yellow solution is then

page_text: filtered, and the filtrate thus formed is allowed to flow into a saturated solution of
common salt, rendered strongly alkaline by means of soda lye. The sodium
salt of the paratolyleurhodine disulphonic acid thus formed then separates as a
light yellow crystalline mass, which is filtered off, pressed, and dried. In order
to alkylate this disulphonic acid, 55;5 parts of the aforesaid scdium salt of
paratolyleurhodine disulphonic acid, and 14 parts of sodium acetate, are dissolved
in 150 parts of water and 150 parts of methylalcohol. After adding about 18 parts
of methyliodide the resulting liquid is heated, during about 3 hours, at from 120 to
130 degrees Centigrade, in a closed vessel capable of withstanding pressure. The
original yellow solution of the disulphonic acid thus turns into red. When the
reaction is complete, the alcohol is distilled off, and the remaining watery solution
is mixed with an excess of soda lye. The dye-stuff thus formed, which is the
sodium salt of the phenyl methyleurhodine disulphonic acid, then separates, and is
purified by repeatedly dissolving and salting out, with the aid of common salt and
soda-lye. It produces, on wool, bluish-red shades which are distinguished by
reason of their evenness and their fastness against the action of light. It possesses
the following formula :—
The corresponding phenyl dye, which results from phenyl alpha, naphthylamine-
alpha-sulphonic acid and amido azo paratoluene, according to the directions given
in the above example, yields, on wool, shades which are somewhat more yellowish
than those produced by the aforesaid paratolyl dye.
In place of sulphonating the phenyl- or tolyleurhodine monosulphonic acid, and
subsequently alkylating the so-formed disulphonic acids, the process can also be
carried out in such a manner that the said monosulphonic acids are first alkylated
and subsequently sulphonated. According to the researches of my foreign corre-
spondents, the carrying out of the process in this inverse manner is, however, less
advantageous.
As above mentioned, the same or analogous colouring matters can also be
obtained by condensing mono alkyl amido azo paratoluene, or "analogues of mono
alkyl amido azo-para-toluene," with phenyl- or tolyl-alpha, naphthylamine alpha
sulphonic acid, and subsequently sulphonating the so-formed sulphonic acids of
phenyl- or tolyleurhodine, alkylated on the one nitrogen atom of the azine nucleus.
The production of the dye-stuffs according to the last named process, is analogous
to that described in the preceding example; of course, the further alkylation is
omitted in this case.
In the production of the dye-stuffs hereinbefore defined, my foreign corre-
spondents do not limit themselves to the directions hereinbefore given, as, in general,
for condensing, alkylating, and sulphonating the products hereinbefore mentioned,
all methods known and in use for analogous or similar purposes can be employed.
Such modifications in practically producing the dyestuffs hereinbefore defined,
do not alter the nature of the present invention, which in general relates to the
production of dye-stuffs, that is to say, sulphonic acids of phenyl- or tolyleurhodines
alkylated on the one nitrogen atom of the azine nucleus, or salts of these sulphonic
acids, from phenyl or tolyl-alpha-naphthylamine alpha, sulphonic acid, and either
amido azo para toluene or mono alkylamido azo-para-toluene, or "analogues of
mono alkyl amido azo-para-toluene."
Dated this 19th day of March 1895.
NEWTON & SON,
Agents for the Applicant.

page_text: GUMI LEIE ECIFICATION.
The Manufacture or Production of Dye-stuffs.
1 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 has been stated by O. N. Witt, in the Berichte der Deutschen Chemischen
Gesellschaft (volume 18, page 1119, and volume 19, page 441), that amidoazo
paratoluene, melting at 118.5 degrees Centigrade, can be easily condensed with
alpha naphthylamine, to form so-called eurhodine.
My foreign correspondents have now found, that in place of alpha-naphthyl-
amine, alpha naphthylamine sulphonic acids, and particularly alkylalphanaphthyl-
amine sulphonic acids (such as the phenyl alpha naphthylamine sulphonic acids,
tolylalphanaphthylamine sulphonic acids, or the like, which are obtainable, for
instance, by means of the processes described in the Specification of Letters
Patent No. 7337A, dated 16th April 1892), can be condensed with amidoazo-para-
toluene, dye-stuffs being thus obtained which differ from the analogous dye-stuffs
described in the Specification of Letters Patent No. 10138c, dated 27th May 1892,
in that the former contain sulphonic groups in the naphthalene nucleus. The said
dye-stuffs described in the Specification of the last-named Letters Patent, on the
other hand, are sulphonic acids formed by sulphonating the eurhodine of the
formula:-
They contain the sulphonic groups in the nuclei 5 and 3, and not in the
naphthalene nucleus, it being stated in the Specification of the German Patent
No. 75017, dated 21st June 1892, which corresponds with the last mentioned
English Letters Patent, that sulphonic groups cannot be substituted for hydrogen
in the nuclei 1 and 2, by sulphonating the said eurhodine.
Furthermore, my foreign correspondents have tried to alkylate the nitrogen of
the azine group in the said eurhodine sulphonic acids obtainable by condensing
alpha naphthylamine sulphonic acids, or alkylalphanaphthylamine sulphonic acids,
with amido azo para-toluene, they find that the greater number of the said dye-
stuffs (or eurhodine sulphonic acids) are not acted on by methyliodide in the
desired manner, but that the alkylation readily takes place, in the case of
eurhodine sulphonic acids derived from alpha, naphthylamine-alpha sulphonic
acid.
The production of such dye-stuffs, being sulphonic acids, or salts of sulphonic
acids, of phenyl- or tolyleurhodines containing an alkylated azine nucleus, speaking
generally, is effected by allowing amido azo-para-toluene to act on phenyl- or tolyl-
alpha, naphthylamine-alpha, sulphonic acid, in the presence of a suitable solvent
or diluent (such as phenol, alcohol, glacial acetic acid, glycerol, paratoluidine, or
the like), converting the monosulphonic acids thus formed into readily soluble
disulphonic acids by means of suitable sulphonating agents, and finally alkylating
these disulphonic acids, for instance, by heating their alkaline solutions with
methyliodide at from about 120 to 150 degrees Centigrade.

page_text: COLOURING-MATTER OBTAINED
BY CONDENSING
PARATOLYL-ALPHAI
NAPHTHYLAMINE-ALPHA SULPHONIC ACID WITH AMIDOAZO-PARA-
TOLUENE AND BY SUBSEQUENT SULPHONATION AND ALKYLATION.
313 parts of paratolyl-alpha, naphthylamine alpha, sulphonic acid are mixed with
from 50 to 60 parts of phenol, heated in a water bath, and 33 parts of amido-azo-para-
toluene are then stirred into the liquid mixture. A green liquid is obtained which,
after some time, becomes yellow, and finally red. The heating is continued until, on
dissolving a test portion in concentrated sulphuric acid, it no longer affords a yellow,
but a pure green coloured solution. At this stage, the mixture is mixed with an
excess of dilute soda-lye, in order to remove the phenol. The sodium salt of the mono-
sulphonic acid thus formed is but slightly soluble in the excess of soda-lye. After
filtering off the alkaline solution of phenol, the residue is dissolved in a large
quantity of hot water, and the solution is then cooled and filtered, in order to remove
a small quantity of insoluble resinous bye-products. On adding muriatic acid to the
yellow filtrate, the paratolyleurhodine mono-sulphonic acid at once separates, being
insoluble even in hot water. It forms a violet precipitate. This precipitate, having
been collected and dried, is boiled with alcohol, which extracts a small quantity of
colouring matter formed as by-product, the pure mono-sulphonic acid being:
scarcely dissolved. The monosulphonic acid thus purified is carefully dried, and
one part thereof is then stirred into about 6 parts of sulphuric acid (at 66 degrees
Baumé), and the mixture is heated by means of a water-bath, until a test portion
dissolved in dilute ammonia-liquor no longer yields a precipitate of unaltered
mono-sulphonic acid, on acidulation with acetic acid. When this stage is arrived
at, the acid liquid is poured into ice-water. Being almost insoluble in an excess
of sulphuric acid, the disulphonic acid at once separates. It is filtered off and
pressed, and, in order to purify it, is dissolved in the calculated quantity of soda-
lye and a small quantity of water. The yellow solution is then filtered, and the
filtrate is run into a saturated solution of common salt, rendered strongly alkaline
with soda-lye. The sodium salt of the paratolyleurhodine disulphonic acid thus
formed separates as a light-yellow crystalline mass, which is filtered off, pressed,
and dried. In order to alkylate this disulphonic acid, 55-5 parts of the aforesaid
sodium salt of paratolyleurhodine disulphonic acid, and 14 parts of sodium acetate,
are dissolved in 150 parts of water, and 150 parts of methylalcohol. After adding
about 18 parts of methyl iodide, the liquid is heated during about 3 hours, at from.
120 to 130 degrees Centigrade, in an autoclave. The originally yellow solution
of the disulphonic acid becomes red. When the action is complete, the alcohol is.
distilled off, and the solution is then mixed with an excess of soda-lye. The
dye-stuff thus formed, being the sodium salt of para tolylmethyleurhodine
disulphonic acid, which separates, is purified by repeatedly dissolving it and salting
out with common salt and soda-lye. It produces, on wool, bluish-red shades which
are distinguished in their evenness and their fastness on exposure to light. It is
represented by the following formula :-
-

page_text: alpha, sulphonic acid and amido azo-paratoluene, in accordance with the directions
given in the above example, produces shades on wool which are somewhat more
yellow than those produced by the aforesaid paratolyl dye.
In preparing the dye-stuffs herein before defined, my foreign correspondents do not
limit themselves to the directions herein before given, as, in condensing, alkylating,
and sulphonating the products herein before mentioned, speaking generally, all
known methods in use for analogous or similar purposes can be adopted.
Such modifications in the process of producing the dye-stuffs herein before
defined do not alter the nature of the present invention, which, in general terms,
relates to the production of dye-stuffs which are sulphonic acids of phenyl-or
tolyleurhodines containing an alkylated azine nucleus, or salts of these sulphonic
acids, from phenyl or tolyl alpha, naphthylamine alpha, sulphonic acid and
amido-azo-para-toluene.
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 phenyl and paratolylmethyleurhodine disulphonic
acids or salts thereof, from phenyl and paratolylalpha, naphthylamine alpha4
sulphonic acid, which process consists in condensing amido azo paratoluene with
phenyl- or paratelyl alpha-naphthylamine alpha, sulphonic acid, or salts thereof,
in the presence of suitable solvents or diluents, converting the so-formed phenyl
and paratolyleurhodine mono-sulphonic acids into the corresponding disulphonic
acids, by n means of sulphonating agents, methylating these disulphonic acids, or
salts thereof, by heating with methyliodide, and finally isolating the so-formed
phenyl and paratolylmethyl eurhodine disulphonic acids, either in the free state,
or in the form of their alkaline salts, which are the finished colouring matters.
2. As new products of manufacture, the phenyl and paratolylmethyleurhodine
disulphonic acids represented by the formulæ :-