The Manufacture or Production of Dye-stuffs.
Year: 1893

page_text: Date of Application, 21st Apr., 1893
Complete Specification Left, 21st Feb., 1894-Accepted, 24th Mar., 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 Breams 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 stated in the Specification of application for
5 Letters Patent No. 4757, dated 4th March 1893, that the condensation products
obtainable by the action of thiosulphuric salts on nitroso-derivatives of secondary
or tertiary amines, and having probably the general formula :-
are capable of reacting with beta naphthoquinone sulpho acids, beta naphthohydro-
quinone sulpho acids, betanaphthoquinone thiosulpho acids, or analogous sulpho
acids, or thiosulpho acids, derived from naphthoquinones, naphthohydroquinones, or
substitution products thereof, in or without the presence of thiosulphuric salts (thio
sulphates), blue dyestuffs being thus formed which are suitable for dyeing and
printing with the aid of mordants.
In the Specification of application for Letters Patent No. 6035, dated 21st March
1893, it is further stated, that in producing the dye stuffs suitable for dyeing and
printing with the aid of mordants, and obtainable by means of the processes
described in the Specifications of applications for Letters Patent No. 825
dated 13th January 1893, and No. 4757, dated 4th March 1893, it is not necessary
to employ the complete naphthoquinone sulpho acids, or naphthohydroquinone
sulpho acids, but that in place thereof, nitroso naphthols, or nitroso naphtholsulpho
acids, or the corresponding amido naphthols or amidonaphtholsulpho acids, can be
used; and that in the same or a similar manner as nitroso naphthols, nitroso
naphtholsulpho acids, amidonaphthols, or amidonaphtholsulpho acids, also other
nitroso or amido compounds of the naphthalene or benzene series, or the corre
sponding quinones or quinone-like products, are capable of reacting (in or without
the presence of thio sulphates) with nitroso derivatives of secondary or tertiary
amines, or with the condensation products resulting by the action of thio sulphates
on nitroso derivatives of secondary or tertiary amines, coloring matters being thus
produced which can be employed either directly, or after previously treating them
with sulphonating agents (in order to render them soluble).
My foreign correspondents have now found, that in the processes described in
the Specifications of applications for Letters Patent No. 4757 of 1893 and

page_text: No. 6035 of 1893, the condensation products employed therein, and resulting from
the action of thiosulphates on nitroso-derivatives of tertiary or secondary amines,
can be replaced by the so-called sulphuretted compounds of dimethylaniline,
diethylaniline, methylethylaniline (which products are first described in the
Specification of Letters Patent No. 10314, dated 16th July 1888, and which now
are termed usually paraamido-dimethyl aniline thio sulpho acid, paraamido-diethyl
aniline thio sulpho acid, paraamido-methyl ethyl aniline thio sulpho acid), or by
analogous or homologous amido thiosulpho acids, or substitution derivatives of the
above thio sulpho acids, the same or similar dye stuffs being thus formed.
In order to illustrate this new method, the following example is given. The
parts are by weight.
COLORING
MATTER FROM PARAAMIDO DIMETHYL ANILINE THIO SULPHO
ACID AND a₁ NITROSO ẞ₁ NAPHTHOL ẞ, SULPHO ACID.
A solution of paraamidodimethylaniline thio sulpho acid (dimethylparaphenylene-
diamine thio sulpho acid) obtained from 18.6 parts of nitroso dimethylaniline hydro-
chlorate, by means of the method described in the said Patent 103148, is mixed
with 27 parts of a nitroso B₁ naphthol-6-sulpho acid, and the resulting mixture is
heated at 60 degrees centigrade, until the separation of the dye stuff, which begins
after some time, is complete. The process can be materially facilitated if, after
heating for several hours, the solution is rendered alkaline by adding a small
quantity of soda lye. In the latter case, ammonia is copiously disengaged, and the
disodium salt of the formed dye stuff separates. This latter salt is filtered off, and
converted into the mono sodium salt, by adding acetic acid.
The coloring matter obtained in this manner is identical with the dyestuff
resulting from nitroso dimethyl aniline, sodium thio sulphate, and a₁ ẞ₁ naphtho-
quinone ẞ sulpho acid.
If the para-amido di methyl aniline thio-sulpho acid employed in the above first
example is replaced by the corresponding quantities of paraamido diethyl-aniline-
thio-sulpho acid, para amido methylethyl aniline thio sulpho acid, or homologues or
analogous amido thio sulpho acids, or substitution derivatives of the said amido
thiosulpho acids (employing, for instance, the thio sulpho acids obtainable from
para amido methyl benzyl-aniline sulpho acid, para amido ethyl-benzyl-aniline
sulpho acid, or the like), analogous dye-stuffs result which, in their general chemical
properties, are similar to the coloring matter obtainable as described in the above
first example.
On the other hand, the a nitroso ß₁ naphthol ẞ sulpho acid used in the above
example, can be replaced by isomeric nitroso naphthol-sulpho acids, analogues or
homologues thereof, or derivatives of nitroso naphthol sulpho acids.
In an analogous manner to the nitroso naphthol sulpho acids, also nitroso-
naphthols (alpha nitroso beta naphthols, or beta nitroso alpha naphthols), the
quinone sulpho acids, or quinones corresponding to the said nitroso naphthol sulpho
acids, and nitroso naphthols, the products (shortly termed quinone-like products)
derived from quinone sulpho acids, or quinones, likewise react with the amido thio
sulpho acids above referred to.
The amido naphthols and amido naphthol sulpho acids (corresponding to the
said nitroso naphthols and nitroso naphtholsulpho acids), and the corresponding
hydroquinones and hydro-quinone sulpho acids, are likewise capable of reacting
with the above amido thio sulpho acids, according to the researches of my foreign
correspondents. Of course, in the latter case, suitable oxydising agents must be
added to the reaction mixture, or the oxidation must be otherwise effected.
It is noticeable that in case the thus obtained products are soluble in water with
difficulty, or insoluble, the former can be easily converted (by treatment with
fuming sulphuric acid or other sulphonating agents producing the like result) into

page_text: products which are soluble, or soluble with greater ease, in water, and therefore
can be employed with better results for dyeing & printing purposes.
As above mentioned, my foreign correspondents have described in the said
Specification of application for Letters Patent No. 6035, dated 21st March 1893,
that in order to produce the coloring matters (suitable for dyeing & printing with
the aid of mordants) resulting by means of the processes described in the above
applications No. 825 and 4757, both of 1893, it is not necessary to start from the
complete naphthoquinone sulpho acids or naphthohydroquinone sulpho acids, and to
act with them in or without the presence of thiosulphates on the nitroso derivatives
of secondary or tertiary amines, or on the condensation products from such nitroso
compounds and thio-sulphates, but, in place of employing naphthoquinone sulpho
acids, or naphthohydroquinone sulpho acids, other products, such as nitroso-
naphthols, nitrosonaphthol sulpho acids, or analogous nitroso derivatives, can
be used.
My foreign correspondents have now found, that the nitroso naphthols, nitroso
naphtholsulpho acids, or the like, employed in the aforesaid Specifications of
applications for Letters Patent, can be replaced by the corresponding azo com-
pounds of naphthols, naphthol sulpho acids, or other hydroxysulpho acids, as,
according to the researches of my foreign correspondents, such, or similar, azo
products are likewise capable of reacting with the nitroso derivatives of secondary
or tertiary amines, or with the thio condensation products obtainable from such
nitroso compounds and thio sulphates, in or without the presence of thio sulphuric
salts. If, for instance, the condensation product from nitrosodimethylaniline and
sodium thio sulphate, is allowed to act on naphthalene sulpho acid, azo naphthol-
sulpho acid (the product which results by combining diazotised naphthionic acid
with beta-naphthol alpha monosulpho acid 2.8), a dye-stuff is obtained which is
identical with that produced by means of the process described in the Specification
of application for Letters Patent No. 4757, dated 4th March 1893, viz. by
acting with beta naphthohydroquinone sulpho acid (1: 2: 8) on the said thio
condensation product which results from sodium thio sulphate and nitroso-
dimethylaniline.
The latter production of the blue coloring matters suitable for dyeing and printing
11
11
TL
DYE
STUFF FROM NAPHTHALENE SULPHO ACID, AZO NAPTHOLSULPHO
ACID, AND THE THIO CONDENSATION PRODUCT OBTAINABLE BY THE
ACTION OF SODIUM THIO SULPHATE ON NITROSO DIMETHYLANILINE.
A solution, in water, of 18-6 parts of nitrosodimethylaniline hydrochlorate is
mixed with 52 parts of sodium thiosulphate, dissolved in 15-6 parts of water. After
adding 36 parts of acetic acid (containing 30 per cent. of pure acetic acid),
40.2 parts of the dye-stuff known in commerce as "Crocein scarlet 3 B X" (which
is the product obtained from diazotised naphthionic acid and beta naphthol alpha
mono sulpho acid 2.8) are introduced into the resulting liquid. The whole mass is
heated by means of a water bath, until the formation of the dye stuff is complete.
The separated dye-stuff is filtered off and pressed.
In an analogous manner to the azo product employed in the above second
example, the other azo products (resulting from the action of diazo compounds on
naphthols, naphtholsulpho acids, dihydroxynaphthalenes, dihydroxynaphthalene
sulpho acids, or the like) react with nitroso compounds of secondary or tertiary
amines, or with the thio condensation products from nitroso derivatives and thio
sulphuric salts, in or without the presence of thio sulphates.
My foreign correspondents do not limit themselves to the directions given in the
last example for the production of the dye-stuffs hereinbefore defined, by means of
azo compounds, as the methods for producing them can be varied.

page_text: If, in carrying out the process in the last named manner, products result which
are insoluble in water, or soluble with difficulty, these products can be easily
converted (by a subsequent treatment with sulphonating agents) into dye-stuff's
which are soluble in water, or soluble with greater case, and therefore can be
employed with better result.
In the above mentioned Specifications of applications for Letters Patent
No. 825, dated 13 January 1893; No. 4757, dated 4 March 1893; No. 6035,
dated 21st March 1893, my foreign correspondents have described valuable
coloring matters suitable for dyeing and printing with the aid of mordants, which
result from the action of nitroso derivatives of secondary or tertiary amines on beta
naphthohydroquinone, beta naphthohydroquinone sulpho acids, amido naphthols,
amidonaphtholsulpho acids, or the like.
In an analogous manner to the nitroso derivatives of secondary or tertiary
amines, also the nitroso compounds of alkylated amido phenols, amido cresols, or
similar alkylated amidohydroxy products (such as nitroso dimethyl meta amido
phenol, nitroso dimethyl meta amido paracresol, or the like), are, according to the
further researches of my foreign correspondents, capable of reacting with beta
naphthohydroquinone, beta amido alpha naphthol, alpha amidobetanaphthol, or
other amido hydroxy compounds, or sulpho- or carboxylic- or hydroxylated
derivatives of all these components.
Coloring matters are thus obtained which are suitable for dyeing and printing
with the aid of mordants, and yield pure blue shades fast against fulling and the
action of light. Amongst these dye-stuffs,-for example, the following may be
mentioned, which results from nitroso dimethyl meta amido phenol, and beta
naphthohydroquinone, and has probably the following composition viz. :-
The coloring matters thus obtainable belong to a series of dye stuffs hitherto
unknown. In case they do not contain sulpho groups, they are soluble in water with
difficulty, and are profitably converted by a treatment with sulphonating agents into
products soluble with greater ease, and therefore being better adapted for dyeing
and printing purposes. On employing, for instance, in place of beta naphthohydro-
quinone, the sulpho acids (such as beta naphthohydroquinone sulpho acid 1:2:6),
soluble dye-stuffs are directly obtained which are similar to the above named
products resulting by subsequently treating with sulphonating agents.
In place of beta-naphtho hydro quinone, the following products can be employed
with a similar result, viz.-beta-naphtho hydro quinone carbonic acids (such as
can be obtained from 3, B-hydroxynaphthoic acid and ẞ B-hydroxynaphthoic
acid, which result by melting, with alkalies, the corresponding ẞ ẞ, sulpho
naphthoic acid and B, B, sulpho naphthoic acid), and likewise hydroxy-beta-
naphtho-hydroquinones, for instance, that which is obtainable from the mono
nitrosoderivative of 2: 7 dihydroxynaphthalene, or the like.
It is, however, noticeable, that for producing the last-defined colouring matters,
it is not necessary to employ the complete beta naphthohydroquinone or its
derivatives, but that a amido B-naphthol, or B₁ amido a naphthol, or the
derivatives thereof, can be directly used. In this case, the amido group is split off
during the reaction, and replaced by oxygen.

page_text: COLOURING-MATTER FROM NITROSODIETHYL-META-AMIDO-PHENOL (NITROSO-
META-HYDROXYDIETHYLANILINE), AND BETA NAPHTHOHYDROQUINONE.
A solution prepared by dissolving 15-8 parts of beta-naphthohydroquinone in
about 23-7 parts of glacial acetic acid, is (whilst cooling) mixed with 23 parts of
nitroso-meta-hydroxydiethylaniline hydrochlorate. The resulting mixture (with
continual stirring) is heated by means of a water bath, until the nitroso_compound
is no longer distinguishable, and the whole mass has assumed a bronze-like lustre.
The thus-formed product is precipitated by an addition of water, filtered off, and
dried. It is then introduced into about 4 parts of fuming sulphuric acid, and the
liquid is heated at from 80 to 100 degrees centigrade, until a test portion perfectly
dissolves in water with pure blue colour. The thus obtained mass is poured on ice,
and the free sulpho acid is then converted by means of sodium acetate into the
sodium salt which forms a mass having a bronze-like lustre.
It produces pure blue shades on wool mordanted with chromium-salts.
DYE-STUFF FROM NITROSO-DIETHYL-META-AMIDOPHENOL
(NITROSO-META-
HYDROXYDIETHYL-ANILINE) AND a-AMIDO ẞ NAPHTHOL ẞ3 SULPHO
ACID.
23 parts of nitroso-meta-hydroxydiethyl-aniline are dissolved in about 20 times
their weight of water, and the resulting solution, after adding 24 parts of
a, amido B naphthol ẞ, sulpho acid, is (with continuous stirring) heated at about
60 degrees centigrade, until the liquid has assumed a pure blue colour. The liquid
is then boiled, and a small quantity of soda lye is added. Ammonia is copiously
disengaged, whilst the disodium salt of the colouring matter, which is soluble with
difficulty in the excess of soda-lye, is separated. The latter salt is filtered off and
converted into the monosodium salt.
The dye stuff thus produced is, in its properties, similar to the product obtainable
as described in the foregoing third example.
Analogous colouring-matters result, if, in the last two examples, in place of
nitroso-meta-hydroxydiethylaniline, the corresponding quantities of the nitroso
derivatives of other alkylated amido hydroxy-compounds are employed, or, if beta
naphthohydroquinone and a-amido-3-naphthol-ß, sulpho acid likewise employed in
the above examples (three and four), are replaced by equivalent quantities of beta-
amido-alpha-naphthol, alpha-amido beta-naphthol, naphthohydroquinone sulpho
acids, naphthohydroquinone carbonic acids, hydroxy-beta-naphthohydroquinones,
or analogous or homologous sulpho acids, carbonic acids, or hydroxy compounds.
The thus-formed products can either be directly employed for dyeing and
printing, or they can be converted by treating with sulphonating agents according
to the usual methods (for instance, by treatment with fuming sulphuric acid) into
dye-stuffs which are soluble, or soluble with greater readiness, in water, and
therefore can be more advantageously employed for dyeing or printing purposes.
Dated this 21st day of April 1893.
NEWTON & SON,
Agents for the Applicant

page_text: '
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 :-
My foreign correspondents have stated in the Specification of application for
Letters Patent No. 4757, dated 4th March 1893, that the condensation products
which can be obtained by the action of thiosulphates on nitroso derivatives of
secondary or tertiary amines, and which, chemically speaking, are alkylated para-
phenylene diamine thio sulphonic acids, or derivatives thereof, are capable of
interacting with alpha, beta, naphthoquinone sulphonic acids, blue dye-stuffs being
thus formed which are suitable for dyeing and printing with the aid of mordants.
My foreign correspondents have further stated in the Specification of application
for Letters Patent No. 6035, dated 21st March 1893, that instead of the alpha,
beta naphthoquinone sulphonic acids used in the process described in the Specifi-
cation of the said application for Letters Patent, orthonitrosonaphthols, ortho-
nitrosonaphtholsulphonic acids, orthonitrosonaphtholcarboxylic acids, or the like,
can be used.
My foreign correspondents have now found that the amido naphthols and amido
naphthol sulphonic acids (corresponding to the orthonitroso naphthols and ortho-
nitrosonaphtholsulphonic acids used in the process described in the Specification of
the said application for Letters Patent No. 6035 of 1893), and the corresponding
hydroquinones and hydroquinone sulphonic acids, are also capable of interacting
with the above-named dialkylated paraphenylene diamine thiosulphonic acids, or
derivatives thereof. Necessarily, however, in this case suitable oxidising agents
must be added, for instance, atmospheric oxygen can be used, failing which, the
oxidation must be otherwise effected.
This method of producing dye-stuffs by joint oxidation of the so-called
dialkylated paraphenylene diamine thiosulphonic acids, or derivatives thereof, and
amidonaphthols, amidonaphtholsulphonic acids, naphthohydroquinones, or naphtho-
hydroquinone sulphonic acids, is illustrated by the following example. The parts
are by weight.
COLORING MATTER FROM DIMETHYL-PARAPHENYLENE DIAMINE THIO
SULPHONIC ACID AND ALPHA1 BETA NAPHTHOHYDROQUINONE BETA3
SULPHONIC ACID.
25 parts of dimethyl paraphenylene diamine thiosulphonic acid and 28 parts of
alpha beta, naphthohydroquinone betas sulphonate of potassium, are suspended in
about 800 parts of water, and 200 parts of soda lye, containing 25 per cent. of
sodium hydroxide, are added. The brownish colored liquid which is produced, is
heated by means of a water bath, and atmospheric air is allowed to pass through
the heated liquid. Heat is applied during several hours, the current of air being
allowed to pass through the liquid during the whole time.
The hot liquid is then acidulated with acetic acid. The neutral sodium salt of
the dye-stuff is thereby precipitated. The coloring matter so formed is separated
by filtering off, pressing, and drying.
The researches of my foreign correspondents have shown, that the coloring
matter thus produced is identical with the dye-stuff obtainable from dimethyl-para-
phenylene diamine thio sulphonic acid and potassium alpha, beta₁ naphthoquinone
beta, sulphonate. The process proceeds in a similar manner, if, instead of alpha

page_text: beta, naphthohydroquinone beta, mono sulphonic acid, alpha, amido beta, naphthol
betaa monosulphonic acid be used, the amido group contained in the alphat
amido beta naphthol beta, monosulphonic acid used being displaced by oxygen,
ammonia being disengaged. According to the researches of my foreign corre-
spondents, the process also proceeds in the manner described in the foregoing
example, if, instead of the alpha, beta, naphthohydroquinone beta, monosulphonic
ncid used in the above example, either other alpha, beta, naphthohydroquinone
sulpho acids are used, corresponding to the orthonitrosonaphtholsulphonic acids
used in the process described in the Specification of application for Letters Patent
No. 60353, or alpha beta, naphthohydroquinone, or alpha, amido beta, naphthol,
or beta, amido alpha, naphthol. or such alpha amido beta, naphtholsulphonic
acids, or beta, amnido alpha, naphthol sulphonic acids, as correspond to the nitroso
naphthol sulphonic acids used in the process described in the Specification of
application for Letters Patent. No. 6035 of 1893; or if other alkylated para-
phenylene diamine thiosulphonic acids, such as diethyl paraphenylene diamine
thiosulphonic acid, para amido monomethylorthotoluidine thiosulphonic acid, para-
amidomonoethylorthotoluidinethiosulphonic acid, sulphobenzylmethylparaphenylene
diaminethiosulphonic acid, sulphobenzylethylparaphenylene diaminethiosulphonic
acid, sulpho para amidomethyldiphenylamine thiosulphonic acid, sulphoparaamido-
ethyldiphenyl aminethiosulphonic acid) are used in place of dimethyl paraphenylene
diamine thio sulphonic acid.
In those cases in which the products dissolve in water with difficulty, or are
insoluble, they can be easily converted, by treatment with fuming sulphuric acid,
or other suitable sulphonating agents, into soluble products, which can be used with
better result for dyeing and printing purposes.
In the above mentioned Specifications of applications for Letters Patent No. 825,
dated 13th January 1893, No. 6035A, dated 21st March 1893, my foreign corre-
spondents have described valuable coloring matters suitable for dyeing and printing
with the aid of mordants, resulting from the action of nitroso derivatives of
secondary or tertiary amines, in the presence of a thio-sulphate, on beta naphtho-
hydroquinone sulphonic acids, amidonaphthol sulphonic acids, or the like.
The nitroso compounds of alkylated amidophenols, amido cresols, or similar
alkylated amido hydroxy compounds (such as nitroso dimethyl metamido phenol,
nitroso dimethyl metamido para cresol, or the like), according to the further
researches of my foreign correspondents, are also capable, like the nitroso
derivatives of secondary or tertiary amines, of interacting with alpha, beta₁
naphthohydroquinone, beta₁ amido alpha, naphthol, alpha, amido beta naphthol, or
such sulphonic or carboxylic or hydroxylated derivatives thereof, as correspond to
the ortho-nitroso derivatives used in the process described in the Specification of
application for Letters Patent No. 6035 of 1893.
Coloring matters are thus obtained which are suitable for dyeing and printing
with the aid of mordants, and yield pure blue shades, withstanding fulling and the
action of light. Of these dye-stuffs, for example, that may be mentioned which is
obtained from nitroso dimethylmeta amidophenol and alpha, beta, naphthohydro-
quinone, which probably has the composition represented by the following.
formula:-

page_text: This dye dissolves with difficulty in water, and is advantageously converted, by
sulphonating agents, into a more soluble sulphonated product, better adapted for
dyeing and printing purposes. On using, for instance, in place of betanaphtho-
hydroquinone, sulphonic acids, such as alpha, beta-naphthohydroquinone beta,
monosulphonic acid, coloring matters which are soluble in water are at once
obtained. These latter coloring matters are similar to the above-named products
formed by a subsequent treatment with sulphonating agents.
The researches of my foreign correspondents have shown, that the same coloring
matters are obtained, if alpha, amido beta, naphthol, beta, amido alpha, naphthol,
or such derivatives thereof as correspond to the orthonitrosonaphthol derivatives
used in the process described in the Specification of application for Letters Patent
No. 6035, are used in place of alpha, beta, naphthohydroquinone, or its
derivatives. In these cases, the amido group becomes displaced by oxygen,-
ammonia being disengaged, as my foreign correspondents have stated.
The production of the coloring matters by means of the nitroso derivatives of
alkylated amidohydroxy compounds, is illustrated by the following examples, the
parts being by weight.
DYE-STUFF FROM NITROSODIETHYLMETAMIDO PHENOL (NITROSO METHYDROXY
DIETHYLANILINE), AND ALPHA BETA, NAPHTHOHYDROQUINONE BETA,
MONO SULPHONIC ACID.
A concentrated solution of 28 parts of the potassium salt of alpha, beta-
naphthohydroquinone-beta, monosulphonic acid and 25 parts of crystallised
sodium acetate, is added to a hot solution of 23 parts of nitroso methydroxy
diethylaniline hydrochloride in about 700 parts of water. The liquid is then
heated to boiling, and continually stirred. It very soon assumes a deep blue
colour, the surface exhibiting a copper-like lustre. The completion of the change
is indicated by the separation of the colouring matter, on cooling a sample of the
liquid, in beautiful yellowish brass coloured crystals, exhibiting a green shimmer.
At this stage the liquid is allowed to cool, and the dyestuff which separates is
filtered off, pressed, and dried.
A further quantity of the dye can be obtained by adding common salt to the
mother-liquor.
This colouring matter easily dissolves in hot water, affording a beautifully blue
coloured solution. It produces, on wool mordanted with chromium salts, bright
and pure blue shades, which withstand the action of light and fulling.
Dye-stuffs similar to that obtainable as described in the above Example B, are
formed, if the isomeric monosulphonic acids, or disulphonic acids of alpha, beta₁
naphthohydroquinone are used in place of the alpha, beta-naphthohydroquinone-
beta-monosulphonic acid specified in the said Example B.
The corresponding dyestuffs derived from nitroso-methydroxydimethyl aniline,
in general yield shades somewhat redder and duller than those produced by means
of the colouring matters from nitrosodiethylaniline.
The colouring-matters prepared from the nitroso derivatives of methydroxy-
dialkyl orthotoluidines, also yield somewhat redder shades than those derived from
nitroso methydroxydialkylanilines.
The production of colouring matters from alpha, beta, naphthohydroquinone, is
effected in glacial acetic acid solution, or, more profitably, in alcoholic solution, as
described in the following example.

page_text: PAANILE
COLOURING-MATTER FROM NITROSO-DIETHYLMETAMIDOPHENOL (NITROSO-
METHYDROXYDIETHYLANILINE) AND ALPHAL BETA-NAPHTHOHYDRO-
-QUINONE.
A solution of 16 parts of alpha, beta-naphthohydroquinone in about 400 parts
of alcohol, is mixed with 23 parts of nitroso methydroxydiethylaniline hydro-
chloride, and a concentrated aqueous solution of 8 parts of crystallised sodium
acetate. The resulting mixture is heated in a vessel provided with a reflux
condenser, by means of a water-bath. After a time, a deep bluish-violet coloured
liquid is obtained, from which the dyestuff begins to separate in crystals, as the
heating is continued. After about 12 hours, the greater part of the alcohol used
is evaporated off, and the residue is mixed with water. The dyestuff separates in
reddish brown crystals insoluble in water. It is filtered off and dried. In order
to render it soluble, it is introduced into about the fourfold quantity of fuming
sulphuric acid (containing 25 per cent. of sulphuric anhydride), and the liquid is
heated at from 90 to 100 degrees centigrade, until a test portion dissolves in water
in the presence of sodium acetate, affording a pure blue coloured solution.
cool, the product is poured into ice-water, and after nearly saturating the solution
so obtained with sodium carbonate, such a quantity of sodium acetate is added as
is necessary for the formation of the sodium salt of the sulphonated product.
The sodium salt so formed, which constitutes the dye stuff, is filtered off. It is
very similar to the colouring matter prepared from nitroso methydroxydiethyl-
aniline and alpha, beta-naphthohydroquinone-beta-monosulphonic acid.
above mentioned, the same dyestuffs are formed, if, instead of alpha, beta-naph-
thohydroquinone, or sulphonic acids thereof, alpha, amido beta, naphthol, or
betai amido alpha-naphthol, or sulphonic acids thereof, are used.
When
As
In preparing these colouring matters, it is desirable, however, to use diluted
solutions, as is evident from the following example.
DYE STUFF FROM NITROSO DIETHYL METAMIDOPHENOL (NITROSOMETHY-
DROXYDIETHYLANILINE)
SULPHONIC ACID.
AND ALPHA
AMIDO-BETA-NAPHTHOL-BETA1-
23 parts of nitroso methydroxydiethylaniline hydrochloride are added to a
solution prepared by dissolving 26 parts of the sodium salt of alpha, amido-beta1
naphthol-betas-sulphonic acid in about from 2000 to 2500 parts of water. The
resulting solution is then boiled until it has assumed a pure blue colour. After
adding 25 parts of crystallised sodium acetate, the liquid is heated, by means of a
water bath, during from about 6 to 8 hours. The action is complete when, on
cooling a sample, and adding a small quantity of common salt and acetic acid, a
precipitate of brass-like lustrous crystals is produced. When this stage is arrived
at, the liquid is allowed to cool. In order to neutralise the ammonia which is
separated from the amido-naphtholsulphonic acid during the action, the requisite
quantity of acetic acid is added, and the colouring matter is then salted out by
means of common salt. It is identical with the dyestuff obtainable as described in
the foregoing Example B.
Analogous colouring matters are formed, if, in the last three examples, in place
of nitroso methydroxydiethylaniline, the corresponding quantities of the nitroso
derivatives of other alkylated amidohydroxy compounds are used.
The products thus formed can either be directly used for dyeing and printing, or
they can be converted, by sulphonating agents, into more soluble dye stuffs, which
can be more advantageously used for dyeing or printing purposes.

page_text: Having now particularly described and ascertained the nature of the said
invention, 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 dyestuffs, which process consists in condensing alkylated'
para phenylene diamine thio sulphonic acids, or derivatives thereof (such as
dimethyl-para-phenylene diamine thiosulphonic acid, diethylpara-phenylene
diamine thio sulphonic acid, para-amidomonomethyl-ortho-toluidine thio sulphonic
acid, para-amidomonoethyl-ortho-toluidinethiosulphonic acid, sulphobenzylmethyl-
para-phenylene diaminethiosulphonic acid, sulphobenzylethyl-para-phenylenc
diaminethio-sulphonic acid, sulpho-para-amidomethyldiphenylamine-thiosulphonic
acid, sulpho-para-amidoethyldiphenylamine thiosulphonic acid), in the presence of
suitable oxidising agents, with alpha-amido-beta; naphthol, beta, amido-alpha,-
naphthol, alpha, beta-naphthohydroquinone, or such amidonaphthol sulphonic acids,
or naphthol-hydroquinonesulphonic acids, as correspond to the orthonitrosonaph-
tholsulphonic acids used in the process described in the Specification of application
for Letters Patent No. 6035 of 1893; subsequently, sulphonating the condensation
products so formed, in case they are found to be insoluble, or slightly soluble in
water.
2. The process for producing dyestuffs, which process consists in condensing
nitroso derivatives of alkylated amidophenols, amidocresols, or the like (such as
nitrosodimethylmeta-amidophenol, nitrosomono-ethyl-metamidophenol, nitrosodi-
ethylmetamidophenol, nitroso-methydroxydimethyl-ortho-toluidine, nitroso-met-
hydroxydiethyl-ortho-toluidine, or the like), with alpha,-amido-beta, naphthol,
beta-amido-alpha-naphthol, alpha, beta-naphthohydroquinone, or such sulphonic,
carboxylic, or hydroxy derivatives thereof, as correspond to the orthonitroso-
naphthol derivatives used in the process described in the Specification of
application for Letters Patent No. 6035A of 1893; subsequently sulphonating
the condensation products so formed, in case they are found to be insoluble, or
difficultly soluble, in water.
3. As new products of manufacture, the new colouring-matters produced by the
process described in the foregoing second claim, or by any other means affording
the same result.
Dated this 20th day of February 1894.
NEWTON & SON,
Agents for the Applicant.