The Manufacture or Production of Colouring Matters.
Year: 1894

page_text: Date of Application, 10th Mar., 1894
Complete Specification Left, 10th Dec., 1894-Accepted, 12th Jan., 1895
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of 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:
My foreign correspondents have discovered some time since, that blue oxazine
dye stuffs, capable of dyeing with the aid of mordants, are obtained on acting with
nitroso derivatives of alkylated metamido phenols, metamido cresols, or the like,
on ai i naphthahydroquinone, ẞ-amido-a-naphthol, or a amido-ẞ₁-naphthol, or
sulphonic or carboxylic, or hydroxy derivatives thereof.
The researches of my foreign correspondents have now shewn, that in the
production of the dye stuffs hereinbefore defined, the nitroso compounds can be
replaced by the corresponding amido products, which result, for instance, on
reducing the said nitroso derivatives, or are obtained by other convenient methods.
Naturally, oxidising agents must be used, in order to effect the formation of dyes in
this case. According to the researches of my foreign correspondents, the oxygen
of the air can be profitably used in the presence of alkalies for effecting the
oxidation. Other oxidising agents, however, can also be used.
In order to illustrate one of the methods of producing the said dye stuffs, the
following example is given. The parts are by weight.
COLOURING-MATTER FROM PARAMIDO META-HYDROXYDIETHYLANILINE AND
a1 NAPHTHAHYDROQUINONE-ẞSULPHONATE OF POTASSIUM.
2.
18 parts of paramido-meta-hydroxydiethylaniline are dissolved in water. After
adding a small quantity of a sulphurous acid solution, in order to prevent the
oxidation of the very unstable base, 28 parts of a B-naphthahydroquinone
B, sulphonate of potassium are added. The resulting solution is then heated at from
about 50 to 80 degrees Centigrade, and 100 parts of soda-lye (containing 25 cent.
per
of pure sodium hydroxide) are introduced, whilst a current of atmospheric air is
allowed to pass continually through the heated liquid. The mixture assumes, after
some time, a deep green colour, which turns into an intense blue colour on adding
acetic acid. The re-action is complete when the intensity of the colour does not
increase. When this stage is arrived at, the greater part of the alkali contained
in the liquid mixture is, neutralised with the aid of a mineral acid, and after
acidulating by means of a etic acid, the separated dye-stuff is filtered off. According
to the researches of my foreign correspondents, the colouring matter thus produced.
י מ'

page_text: It
is identical with that resulting from the condensation of nitroso meta hydroxy.
diethylaniline with a ₁ naphthahydroquinone-ẞ,-sulphonate of potassium.
probably possesses the following formula:
OH
C,H,
\C₂H,
Other colouring matters result in an analogous manner, if, on the one hand, the
paramido-meta-hydroxydiethylaniline used in the foregoing example, is replaced
by the corresponding quantities of other amido derivatives of alkylated amido
phenols, or amido cresols, or the like (for instance, peramido-meta-hydroxydi-
methylaniline, paramido meta hydroxymono methylaniline, paramido-meta-hydroxy-
mono ethylaniline, amido meta hydroxydimethyl-ortho toluidine, amido-meta-
hydroxydiethyl-ortho-toluidine, and so on), or if, on the other hand, the
a B₁ naphthahydro-quinone ẞ, sulphonate of potassium is replaced by the equivalent
quantities of other a, B₁-naphthahydro quinone sulphonic salts, or, in general,
of a, naphthahydro quinone, a, ẞ, naphthaquinone, a₁-amido-ß,-naphthol, 6, amido-
a-naphthol, or sulphonic acids, carboxylic acids, or hydroxy compounds thereof, or
other substituted derivatives thereof.
My foreign correspondents do not limit themselves, in the production of the
dye-stuffs hereinbefore defined, to the directions given in the above example, as
these can be varied without departing from the nature of this invention; for
instance, the oxidation may be effected by means of other oxidising agents in place
of the atmospheric air; and it is also to be understood that the resulting products,
in case they are insoluble, or soluble with difficulty, can be transformed into more
valuable dye-stuffs by a subsequent treatment with sulphonating agents in the well
known manner.
Dated this 10th day of March 1894.
NEWTON & SON,
Agents for the Applicant.
:
COMPLETE SPECIFICATION.
The Manufacture or Production of 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 :--
My foreign correspondents have described in the application of Letters Patent
No. 8093, dated 21st April 1893, a process for producing blue oxazine dye-stuffs
capable of dyeing with the aid of mordants, which process consists in acting with
nitroso derivatives of alkylated metamidophenols, metamido cresols, or the like, on
alpha beta, naphthahydroquinone, betai amido-alpha, naphthol, or alpha, amido
beta, naphthol, or certain sulphonic, or carboxylic, or hydroxy derivatives thereof,
and in subsequently sulphonating the condensation products so formed, in case they
are found to be insoluble, or difficulty soluble in water.

page_text: The researches of my foreign correspondents have now shewn, that such dye-stuffs
can also be produced from the amido compounds, formed for instance, on reducing
the said nitroso derivatives, or obtained by other convenient methods. Naturally,
oxidising agents must be used, in order to effect the formation of dyes in this case,
but according to the researches of my foreign correspondents, the oxygen of the
air can be profitably used in the presence of alkalies, for effecting the oxidation.
In order to illustrate one of the methods of producing the said dye-stuffs, the
following example is given. The parts are by weight.
COLOURING MATTER FROM
PARAMIDO META-HYDROXYDIETHYLANILINE
BETA-SULPHONATE
AND ALPHA1 BETA-NAPHTHAHYDROQUINONE
POTASSIUM.
OF
23-1 parts of nitroso metahydroxydiethylaniline hydrochloride are dissolved in
500 parts of water, and reduced, in the usual manner, by means of zinc dust and
muriatic acid. The solution, containing 18 parts of paramidometahydroxydiethyl-
aniline, is filtered, and after adding to it a small quantity of an aqueous solution
of sulphurous acid, in order to prevent the oxidation of the very unstable base, is
mixed with 28 parts of alpha, beta, naphthahydroquinone-beta, sulphonate of
potassium. The solution is then heated at from about 50 to 80 degrees Centigrade,
and 200 parts of soda lye (containing 25 per cent. of pure sodium hydroxide) are
introduced, whilst a current of atmospheric air is allowed to pass continually
through the heated liquid. The mixture assumes a deep greenish-blue colour,
and after some time, the dye-stuff separates, in the form of its disodium salt, in
dark coloured crystals, being soluble with difficulty in the excess of soda-lye.
The action is complete, when a further separation of these crystals no longer takes
place. When this stage is arrived at, the precipitate is filtered off from the hot
liquid and re-dissolved in hot water. After again filtering, in order to remove an
insoluble residue, the filtrate is acidulated with acetic acid. On adding common
salt, the dye-stuff separates in the form of greenish lustrous crystals.
According to the researches of my foreign correspondents, the colouring matter
thus produced is identical with that formed by the condensation of nitroso-meta-
hydroxydiethylaniline with alpha, beta, naphthahydroquinone-beta,-sulphonate of
potassium. It is probably represented by the following formula :-
Other colouring matters are formed in an analogous manner, if, on the one hand,
instead of the paramido-meta-hydroxydiethylaniline used in the foregoing example,
the corresponding quantities of other amido derivatives of alkylated metamido-
phenols, or metamido cresols, or the like (for instance, paramido-meta-hydroxydi-
methylaniline, amido-meta-hydroxydimethyl-ortho-toluidine, and so on) be taken,
or if, on the other hand, equivalent quantities of other alpha, beta, naphthahydro-
quinone sulphonic salts, or of alpha, beta, naphthahydroquinone, or carboxylic, or
of hydroxy derivatives, or other derivatives of alpha, beta-naphtha hydroquinone,

page_text: are used in place of the alpha, beta, naphthahydroquinone-beta; sulphonate of
potassium used in the preceding example.
My foreign correspondents use only such sulphonic, carboxylic, hydroxy- or other
derivatives of alpha, beta, naphthahydroquinone as correspond to the orthonitroso-
naphthol derivatives used in the process described in the Specification of Letters
Patent No. 6035A of 1893.
In producing the dyestuffs hereinbefore defined, my foreign correspondents do
not limit themselves to the directions given in the above example, as these can be
varied without departing from the nature of this invention.
As a matter of course, those products which are insoluble, or soluble with
difficulty, are profitably transformed into more valuable dyestuffs, by a subsequent
treatment with sulphonating agents, in the well known manner.
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 :-
The production of oxazine dyestuffs capable of dyeing with the aid of mordants,
from alpha beta, naphthahydroquinone, or such sulphonic or carboxylic or hydroxy
derivatives thereof, as correspond to the orthonitrosonaphthol derivatives used in
the process described in the Specification of Letters Patent No. 6035A³, which
process consists in subjecting to a joint oxidation, by means of the oxygen of the air,
in the presence of alkalies, alpha, beta, naphthahydroquinone, or the above named
derivatives thereof, together with those amido products (such as parainido meta-
hydroxydiethylaniline, amido-metahydroxydimethylorthotoluidine, or the like),
which are formed on reducing the nitroso derivatives of alkylated amido-phenols,
amido cresols, or the like, or are obtained by other suitable methods, and sub-
sequently sulphonating the oxidation products so formed, in case they are found to
be insoluble, or difficultly soluble, in water.
Dated this 10th day of December 1894.
NEWTON & SON,
Agents for the Applicant.