The Production or Manufacture of Colouring Matters.
Year: 1893

page_text: Date of Application, 21st Mar., 1893
Complete Specification Left, 22nd Jan., 1894-Accepted, 24th Feb., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Production or Manufacture 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 described in the Specification of application
for Letters Patent No. 825, dated 13th January 1893, a process for the production
of dyestuffs (capable of dyeing with the aid of mordants), which process consists
either in acting with betanaphthoquinone sulpho acid, or betanaphthohydroquinone
sulpho acid, or salts thereof, on nitroso derivatives, in or without the presence of
thiosulphates, or in acting with beta naphthoquinonethiosulpho acid, or beta-
naphthohydroquinonethiosulpho acid, or salts thereof, on nitroso compounds.
In addition thereto, my foreign correspondents have described in the Specification
of application for Letters Patent No. 4757, dated 4th March 1893, a process for
producing analogous coloring matters, which is effected by allowing the cop-
densation products from nitroso compounds and thiosulphates, to act on beta-
naphthoquinonesulpho acid, betanaphohydroquinonesulpho acid, betanaphtho-
quinonethiosulpho acid, hetanaphthohydroquinonethiosulpho acid, or analogous
sulpho acids derived from naphthoquinones, naphthohydroquinone, or substitution
products thereof, in or without the presence of thiosulphates.
My foreign correspondents have now found, that in the production of the dye-
stuffs (suitable for dyeing with the aid of mordants, blue shades) described in the
two Specifications No. 825 and 47573, it is not necessary to start from the
complete naphthoquinone sulpho acids, or naphthohydroquinone sulpho acids, but
that nitroso naphthols and nitrosonaphtholsulpho acids, or the corresponding amido-
naphthols and amidonaphtholsulpho acids, can be used, and that in the same
manner as nitroso naphthols, nitroso-naphtholsulpho acids, amidonaphthols or amido-
naphtholsulpho acids, other nitroso compounds, or amido compounds, of the
naphthalene or benzene series, and likewise the corresponding quinones, or
quinonelike products, are capable of reacting with the condensation products from
nitroso derivatives and thiosulphates, in or without the presence of salts of
thiosulphuric acid.
If, for instance, a ß-naphthoquinone-u, sulpho acid, is replaced by ẞ₁-nitroso a₁
naphthol-os sulpho acid, or by a nitroso Bi-naphthol, and either of these latter two
products is allowed to act on the condensation products from nitroso derivatives
and thio sulphates, dyestuff's result which are identical with those produced in the
analogous manner by means of the said a Bi-naphthoquinone a-sulpho acid.
My foreign correspondents account for this peculiar fact, by assuming, that,
during the said reaction, nitroso-naphtholsulpho acid, by reduction, is first con-
verted into amidonaphtholsulpho acid; that the latter acid effects the combination,
and that, in the further reaction, the amido group contained in the first-formed
condensation product is separated again, and replaced by oxygen.
In order to illustrate this new process, the following example is given. The
narts are by weight.

page_text: COLORING MATTER OBTAINED BY ACTING WITH THE CONDENSATION PRODUCT
FROM NITROSODIMETHYLANILINE AND SODIUM THIOSULPHATE
ON a
NITROSO NAPHTHOL-, SULPHO ACID.
9.3 parts of nitroso-dimethylaniline hydrochlorate are dissolved in 200 parts of
water mixed with 18 parts of acetic acid (containing 33 per cent. of pure acid).
The resulting liquid is added to a hot solution of 26 parts of sodium thiosulphate
in 100 parts of water. Heating is continued until the liquid becomes colorless.
The formation of the condensation product is then completed. 14 parts of the
sodium salt of a nitroso-B₁ naphthol ẞs sulpho acid are gradually stirred in. The
formation of the dye stuff soon begins, and the formed coloring matter separates
in little crystals, shewing bronze-like lustre. When the production of the dye
stops, the mixture, whilst still hot, is filtered, and the dyestuff remaining on the
filter is dried. The coloring matter thus produced is sufficiently pure to be directly
employed for dyeing purposes.
The dyestuff obtainable as above described, has been found by my foreign
correspondents to be identical with the coloring matter resulting from nitroso
dimethylaniline, sodium thiosulphate, and a ẞi naphthoquinone ẞs sulpho acid.
The same coloring matter results, if, in the preceding example, the nitroso
naphtholsulpho acid is replaced by the corresponding a₁ amido B₁ naphthol B
sulpho acid.
Analogous dye stuffs are formed, if, in place of the above-used nitroso com-
pound, or of the corresponding amido product, other nitroso naphtholsulpho acids,
or nitrosonaphthols, nitroso naphthylamines, amidonaphthols, amidonaphtholsulpho
acids, or derivatives thereof, are employed.
It has been mentioned. above, that other nitroso or amido compounds belonging
to the benzene or naphthalene series, or the corresponding quinones or quinonelike
products, can be used in this process; for instance, nitroso dihydroxynaphthalenes
(especially nitroso 26 dihydroxynaphthalene, nitroso 27 dihydroxynaphthalene),
nitroso dihydroxynaphthalene sulpho acids, nitroso naphthol carbonic acids, nitroso
compounds of alkylated amido naphthols (containing fatty or aromatic radicles,
such as methyl, ethyl, and the like, phenyl, tolyl, and the like, including the benzyl
group), nitroso compounds of substituted alkylated amidonaphthols, the amido
compounds corresponding to these or analogous nitroso derivatives, and the
quinones, or quinone-like compounds derived from these or analogous nitroso or
amido products. Amido-dihydroxynaphthalene sulpho acids react in a manner
analogous to that of the amido naphthol sulpho acids.
Of nitroso compounds of the benzene series, for instance, nitrosophenol, the
analogues, homologues, and substitution products thereof (for example, nitroso-
salicylic acid) can be used. The corresponding amido products, and the quinones
or quinonelike substances derived from these or analogous nitroso or amido
compounds, react in the same or a similar manner.
Of course, in place of nitroso dimethylaniline used in the foregoing example,
the nitro derivatives of other tertiary amines, or of secondary amines, or
substitution products thereof, can be employed, with the same or a similar result.
My foreign correspondents do not limit themselves to the employment of the
nitroso compounds or amido products herein before enumerated, as other nitroso or
amido compounds belonging to the benzene or naphthalene series likewise can be
used. By such alterations, the nature of this invention is not changed, as the
invention in general relates to the production of dye stuffs capable of dyeing
with the aid of mordants, by the action of the condensation products from these
nitroso compounds, and thiosulphates on nitroso or amido products of the naphtha-

page_text: lene or benzene series, or on the quinones or quinonelike products derived from such
nitroso or amido products in or without the presence of thiosulphates.
The process for producing these coloring matters, in general, is illustrated by the
above example.
It is to be observed that, if, in the process hereinbefore explained, coloring
matters soluble in water with difficulty, or insoluble, result, these products, by a
subsequent treatment with sulphonating agents, can be readily converted into dye-
stuffs which dissolve with comparative ease, and possess a high value in practice.
Dated this 21st day of March 1893.
NEWTON & SON,
Agents for the Applicant.
CODIL DELE
VATION
The Production or Manufacture of Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Brean'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 Specification of application for
Letters Patent No. 825, dated 13th January 1893, a process for the production of
dye-stuffs (capable of dyeing with the aid of mordants), which process consists in
acting with salts of alpha, beta,-naphthaquinone-alpha, monosulphonic acid, or
alpha, beta, naphthahydroquinone-alpha, monosulphonic acid, on nitroso derivatives
of secondary or tertiary aromatic amines, or substituted amines, in the presence of
thio sulphuric salts, and subsequently sulphonating the products so fornied, in case
they are found to be insoluble or slightly soluble.
In addition thereto, my foreign correspondents have described in the Specification
of application for Letters Patent No. 4757, dated 4th March 1893, a process for
producing colouring matters which consists in allowing certain sulphonic acids of
alpha, beta, naphtha quinone to act on alkylated paraphenylene diamine thio
sulphonic acids, or substitution derivatives thereof, obtainable from the condensation
of nitroso compounds of secondary or tertiary amines, or substituted amines, and
thio sulphuric salts.
My foreign correspondents have now found, that in order to produce the dye stuffs
(suitable for dyeing blue shades with the aid of mordants) described in the two
Specifications No. 825" and 47573, it is not necessary to first prepare the naphtha-
quinone sulphonic acids, or naphthahydroquinone sulphonic acids, but that nitroso
naphthols and nitroso naphthol sulphonic acids can be used, and that, like the
nitroso naphthols and nitrosonaphtholṣulphonic acids, other nitroso compounds of
the naphthalene series, and also the corresponding quinone derivatives, are capable
of entering into action with the condensation products from nitroso derivatives and
thiosulphates.
If, for instance, instead of alpha, beta, naphthaquinone alpha, sulphonic acid,
either beta, nitroso-alpha, naphthol alpha, sulphonic acid, or alpha, nitroso beta
naphthol, be allowed to act on the condensation products from nitroso derivatives
of secondary or tertiary amines and thio sulphates, dye-stuffs are formed which are
identical with those produced in an analogous manner by means of the said alpha,
beta, naphthaquinone alpha, sulphonic acid.
My foreign correspondents account for this peculiar fact, by assuming that,
during the said interaction, the nitroso group of the nitrosonaphthol derivatives is
first converted by reduction into the amido group, and that the amido group
subsequently becomes displaced by oxygen.
In order to illustrate this new process, the following example is given. The parts
are by weight.

page_text: PHAMIDE
COLOURING MATTER FROM ALPHA NITROSO BETA1 NAPHTHOL BETA,
SULPHONIC ACID AND THE DIMETHYL PARAPHENYLENE DIAMINE THIO
SULPHONIC ACID WHICH JS OBTAINABLE BY CONDENSING NITROSO-
DIMETHYLANILINE HYDROCHLORIDE AND A THIO SULPHURIC SALT.
93 parts of nitroso dimethylaniline hydrochlorate are dissolved in 300 parts of
water, mixed with 18 parts of acetic acid (containing 33
per
cent. of pure acid), and
to this solution is added a hot solution of 26 parts of sodium thio sulphate in
100 parts of water. The mixture is heated until the liquid becomes colourless.
The formation of the condensation prodnet, viz., dimethyl para phenylene diamine
thio sulphonic acid is then complete. 14 parts of the sodium salt of alpha, nitroso
beta, naphthol beta3 sulphonic acid are now gradually stirred in. The formation
of the dye-stuff very soon begins, the colouring matter separating in small lustrous
bronze-coloured crystals. When the production of the dye is at an end, the mixture
is filtered whilst still hot, and the dye-stuff remaining on the filter is dried. The
colouring matter thus produced is sufficiently pure to be directly used for dyeing
purposes.
The dye-stuff obtained in the manner above described, has been found by my
foreign correspondents to be identical with the colouring matter formed from
nitrosodimethylaniline, sodium thiosulphate, and alpha beta naphthoquinone-
betaa-sulphonic acid. It probably possesses the following formula.
Analogous dye-stuffs are formed if, in place of the aforementioned nitroso-
compound, other ortho nitroso naphthol sulphonic acids, or ortho nitroso naphthols
containing the nitroso group in the ortho position relatively to the hydroxylic
group, or derivatives thereof, are used, and in the production of the last named
dye stuffs, any foreign correspondents having found that the nitroso derivatives
corresponding to the quinone compounds used in the process described in the
application for Letters Patent No. 47573, yield colouring matters identical with
those afforded by the corresponding quinone products.
The researches of my foreign correspondents have also shown, that in place of
nitroso naphthols, or nitrosonaphthol sulphonic acids, other nitroso compounds of
the naphthalene series, or the quinone derivatives corresponding to those nitroso
compounds, can be used; for instance, nitroso dihydroxynaphthalenes, nitroso
derivatives of mono substituted dihydroxynaphthalenes (such as nitroso mono
methyl-dihydroxy-naphthalenes, nitrosomono ethyl-dihydroxynaphthalenes, nitroso
hydroxynaphthoxyacetic acids of the formula NO.C₁₂H, (OH) OCH COOH),
nitroso naphtholcarboxylic acids, alpha, beta, naphthaquinone, some mono or
disulphonic acids of alpha, beta, naphthaquinone, viz., such as are not mentioned in
the Specification of application No. 47573, hydroxy alpha, beta, naphthaquinones,
or substitution derivatives thereof, alpha, beta, naphthaquinone carboxylic acids or
the like.
:
It is to be noted that, in producing dye-stuffs by means alpha, beta, naphtha-

page_text: quinone, it is necessary to previously isolate the above mentioned diaminethio
sulphonic acids before the condensation is effected.
According to the researches of my foreign correspondents, the following ortho
nitroso derivatives and quinones (when condensed with alkylated phenylene diamine
thio sulphonic acids, or substitution products thereof), give results of special value,
viz., beta, nitroso-alpha, naphthol, alpha, nitroso beta, naphthol, nitroso alpha₁
naphthol alpha, mono sulphonic acid, beta, nitroso alpha, naphthol beta, mono-
sulphonic acid, beta, nitroso alpha, naphthol beta, monosulphonic acid, beta,
nitroso alpha, naphthol alpha, mono sulphonic acid, heta, nitroso alpha, naphthol
alpha, alpha, disulphonic acid, beta, nitroso alpha, naphthol alpha, beta, disulphonic
acid, beta, nitroso alpha, naphthol alpha, beta, disulphonic acid, beta, nitroso alpha,
naphthol beta, alpha, disulphonic acid, nitroso beta, naphthol beta, monosulphonic
acid, nitroso beta, naphthol beta, monosulphonic acid, nitroso beta, naphthol alpha-
beta, disulphonic acid (derived from beta, naphthol alpha, beta, disulphonic acid,
which can be obtained by diazotising the corresponding beta, amidonaphthalene
alpha, beta, disulphonic acid, and boiling the diazo compound with water or acids),
nitroso beta, beta, dihydroxynaphthalene, nitroso-beta, beta, dihydroxy naphthalene,
nitroso beta, alpha, dihydroxynaphthalene, the nitroso derivatives of monoalkyl-
beta, beta, dihydroxynaphthalenes, or mono alkyl beta, beta, dihydroxynaphthalenes,
which are formed by the interaction of one molecular proportion of an alkyl
haloid, and one molecular proportion of the mono sodium salt of beta, beta
dihydroxynaphthalene, or beta, beta, dihydroxynaphthalene, the nitroso derivatives
of hydroxynaphthoxyacetic acid, which can be obtained by acting with one
molecular proportion of mono chloroacetic acid on one molecular proportion of the
disodium salt of either beta, beta, dihydroxynaphthalene, or betai beta, dihydroxy-
naphthalene, nitroso beta, naphthol beta, carboxylic acid, the nitroso compounds of
the two acids: beta, naphthol beta, carboxylic acid and beta, naphthol beta
carboxylic acid (which can be produced by diazotising respectively beta, naphthyl-
amine beta mono sulpho acid and beta, naphthylamine beta, mono sulpho acid,
converting the diazo compounds into the cyano compounds, transforming the
resulting cyano sulphonic acids into the corresponding sulpho carboxylic acids,
and fusing the latter with alkalies), alpha, beta, naphthaquinones, alpha, beta₁
naphthoquinone alpha, beta, disulphonic acid, and, alpha, beta, naphthaquinone
alpha, beta, disulphonic acid, which acids can be produced from beta, amido alpha,
naphthol alpha, beta, disulphonic acid and beta, amido alpha, naphthol alpha, beta
disulphonic acid, respectively, by means of the process described in the Berichte
der Deutschen Chemischen Gesellschaft, volume 24, page 3157, & beta, hydroxy
alpha, beta, naphthaquinone described in the Berichte der Deutschen Chemischen
Gesellschaft, volume 23, page 522.
In place of the nitroso dimethylaniline used in the foregoing example, the
nitroso derivatives of other tertiary amines, or of secondary amines, or substitution
products thereof, can, as a matter of course, be used with the same or a similar
result. In this manner, other alkylated para-phenylene diamine thio sulphonic
acids, or substitution derivatives thereof, are first formed, which are subsequently
allowed to act on the above nitroso compounds, or on the quinone derivatives
corresponding to these nitroso compounds. Those naphthaquinone sulphonic acids,
however, are excluded, which are used in the process claimed in the Specification
No. 4757, dated 4th March 1893.
My foreign correspondents do not limit themselves to the directions given
in the above example, as these can be varied. The nature of this invention is
not changed by such alterations, as the invention, in general, relates to the
production of dye-stuffs capable of dyeing with the aid of mordants, by the action
of the condensation products from nitroso. derivatives of secondary or tertiary
aromatic amines, or substituted amines, and thio sulphates, on nitroso derivatives
of the naphthalene series, or on the quinones corresponding to such nitroso
derivatives (excluding, however, the alpha, beta, naphthoquinone sulphonic acids
used in the process claimed in the Specification No. 4757").

page_text: The process for producing these colouring matters, in general, is illustrated by the
above example.
My foreign correspondents have also found, that if, in the process hereinbefore
explained, colouring matters are formed which dissolve in water with difficulty, or
which are insoluble, these products can, by a subsequent treatment with sulphonating
agents, be readily converted into dye-stuffs dissolving with comparatively ease, and
possessing a higher value in practice.
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, declare that what I claim is :-
1. The production of colouring matters from alkylated paraphenylene diamine
thio sulphonic acids, or substitution derivatives thereof, and nitrosonaphthols,
nitrosonaphthol sulphonic acids, nitrosodihydroxy naphthalenes, nitroso derivatives
of dihydroxynaphthalenes, substituted in the hydroxylic group, nitrosonaphthol
carboxylic acid, or quinones corresponding to these nitroso derivatives (excluding,
however, the naphthaquinone sulpho acids used in the process claimed in the
Specification No. 4757³).
2. The process for producing dye-stuffs, which process consists in condensing one
molecular proportion of dimethyl-para-phenylene diamine thio sulphonic acid,
diethyl-para-phenylene diamine thio sulphonic acid, para amido mono-methyl ortho
toluidine sulphonic acid, para-amido monethyl-ortho toluidine sulphonic acid,
sulphobenzylmethyl-para-phenylene diamine thio sulphonic acid, sulphobenzylethyl
para phenylene diamine thio sulphonic acid, sulpho par-amido methyldiphenylamine
thio sulphonic acid, or sulpho par-amido ethyldiphenylamine thio sulphonic acid,
with one molecular proportion of the ortho nitroso compounds derived from alpha
naphthol, beta naphthol, alpha, naphthol alpha, monosulphonic acid, alpha,
naphthol betas monosulphonic acid, alpha naphthol beta, monosulphonic acid,
alpha naphthol alpha, monosulphonic acid, alpha, naphthol alpha, alpha disul-
phonic acid, alpha, naphthol alpha, beta, disulphonic acid, alpha, naphthol alpha,
beta, disulphonic acid, alpha, naphthol beta, alpha, disulphonic acid, beta, naphthol-
beta, monosulphonic acid, beta, naphthol beta, monosulphonic acid, beta, naphthol
alpha beta disulphonic acid, beta, beta, dihydroxynaphthalene, beta, beta,
dihydroxynaphthalene, beta, alpha, dihydroxynaphthalene, mono alkylated beta
beta, or beta, beta, dihydroxynaphthalene, the hydroxynaphthoxyacetic acid
obtainable from beta, beta dihydroxynaphthalene, or beta beta, dihydroxy-
naphthalene, or with one molecular proportion of the nitroso derivatives of beta₁
naphthol beta, carboxylic acid, beta, naphthol beta, carboxylic acid, or beta,
naphthol beta, carboxylic acid, or with one molecular proportion of alpha, beta₁
naphthaquinone (in which case the aforesaid diamine thio sulphonic acids must be
previously isolated), alpha, beta, naphthoquinone alpha, beta, disulphonic acid,
alpha beta, naphthaquinone alpha, beta, disulphonic acid, beta, hydroxy alpha
beta, naphthaquinone, and subsequently sulphonating the products, in case they are
found to be insoluble, or soluble with difficulty.
3. As new products of manufacture, the new colouring matters produced by the
process hereinbefore defined, or by any other way affording the same result.
Dated this 20th day of January 1894.
NEWTON & SON,
Agents for the Applicant.

page_text: Date of Application, 21st Mar., 1893
Complete Specification Left, 22nd Jan., 1894-Accepted, 24th Feb., 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 Colouring Matters.
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 described in the Specification of application for
Letters Patent No. 825, dated 13th January 1893, a process for the production of
dye stuffs (capable of dyeing with the aid of mordants), which process consists
either in acting with betanaphthoquinone sulpho acid or beta naphthohydroquinone
sulpho acid, or salts thereof, on nitroso derivatives, in or without the presence of
thio sulphates, or in acting with betanaphthoquinone thio sulpho acid, or beta-
naphthohydroquinone thio sulpho acid, or salts thereof, on nitroso compounds.
In addition thereto, my foreign correspondents have described in the Specification
of application for Letters Patent No. 4757, dated 4th March 1893, a process for
producing analogous colouring matters, which is effected by allowing the
condensation products from nitroso compounds and thio sulphates to act on
betanaphthoquinone sulpho acid, betanaphthohydroquinone sulpho acid, beta-
naphthoquinonethiosulpho acid, beta naphthohydroquinonethiosulpho acid,
analogous sulpho acids derived from naphthoquinones, naphthohydroquinones, or
substitution products thereof, in or without the presence of thiosulphates.
or
My foreign correspondents have now found, that in the production of the dye-
stuffs (suitable for dyeing with the aid of mordants blue shades) described in the
two Specifications No. 825" and No. 4757", it is not necessary to start from the
complete naphthoquinone sulpho acids, or naphthohydroquinone sulpho acids, but
that nitrosonaphthols and nitrosonaphtholsulpho acids, or the corresponding amido-
naphthols and amidonaphtholsulpho acids, can be used, and that, in the same
manner as nitroso naphthols, nitrosonaphtholsulpho acids, amidonaphthols, or
amidonaphtholsulpho acids, other nitroso compounds or amido compounds of the
naphthalene or benzene series, and likewise the corresponding quinones or quinone-
like products, are capable of reacting with nitroso derivatives of tertiary or
secondary amines, in or without the presence of salts of thio sulphuric acid.
If, for instance, a B₁ naphtho quinone a, sulpho acid is replaced by ẞ₁ nitroso-a,-
naphthol a, sulpho acid, or by a₁ nitroso-ẞ, naphthol, and either of these latter two
products is allowed to act on nitroso compounds in or without the presence
of thiosulphates, dyestuffs result which are identical with those produced in an
analogous manner by means of the said a₁ ẞ, naphtho quinone as sulpho acid.
My foreign correspondents account for this peculiar fact by presuming, that
during the said reaction nitrosonaphthol sulpho acid by reduction is first converted
into amidonaphtholsulpho acid, that the latter acid effects the combination, and
that in the further reaction the amido group contained in the first formed
condensation product is separated again and replaced by. oxygen.
In order to illustrate this new process the following example is given. .The
parts are by weight.
EXAMPLE.
COLOURING MATTER FROM NITROSODIMETHYLANILINE AND a NITROSO B₁.
NAPHTHOL-B, SULPHO ACID.
9.3 parts of nitroso dimethylaniline hydrochlorate and 14 parts of the sodium

page_text: the resulting liquid is mixed with a hot solution of 26 parts of sodium thiosulphate
in 100 parts of water. On heating, the formation of the dyestuff very soon begins,
and the formed colouring matter separates in little crystals shewing bronze-like
lustre. When the production of the dye stops, the mixture, whilst still hot, is
filtered, and the dye stuff remaining on the filter is dried. The colouring matter
thus produced is sufficiently pure to be directly employed for dyeing purposes.
The dyestuff obtainable as above described has been found by my foreign
correspondents to be identical with the colouring matter resulting from nitroso
dimethylaniline, sodium thiosulphate, and a₁ B₁ naphthoquinone Bẞ, sulpho acid.
The same colouring matter results if, in the preceding example, the nitroso-
naphtholsulpho acid is replaced by the corresponding quantity of a₁ amido B₁
naphthol-, sulpho acid, or a salt thereof.
Analogous dyestuffs are formed if, in place of the above used nitroso compound,
or of the corresponding amido product, other nitrosonaphtholsulpho acids, or nitroso
naphthols, nitrosonaphthylamines, amido naphthols, amido naphthol sulpho acids, or
derivatives thereof, are employed.
It has been mentioned above that also other nitroso or amido compounds
belonging to the benzene or naphthalene series, or the corresponding quinones or
quinone-like products, can be used in this process; for instance, nitroso dihydroxy-
naphthalenes (especially nitroso 2: 6 dihydroxynaphthalene, nitroso 2: 7 dihydroxy-
naphthalene), nitroso dihydroxynaphthalene sulpho acids, nitroso naphthol
carboxylic acids, nitroso compounds of alkylated amidonaphthols (containing fatty
or aromatic radicles, such as methyl, ethyl, and the like, phenyl, tolyl, and the like,
including the benzyl group), nitroso compounds of substituted alkylated amido-
naphthols, the ainido compounds corresponding to these or analogous nitroso
derivatives, and the quinones or quinone-like compounds derived from these or
analogous nitroso or amido products. Amido-dihydroxynaphthalene sulpho acids
react in a manner analogous to that of the amido naphthol sulpho acids.
Of nitroso compounds of the benzene series, for instance, nitroso phenol, the
analogues, homologues, and substitution products thereof (for example, nitroso
salicylic acid), can be used. The corresponding amido products, and the quinones
or quinone-like substances derived from these or analogous nitroso or amido
compounds react in the same or a similar manner.
Of course, in place of nitroso dimethylaniline used in the foregoing example, the
nitroso derivatives of other tertiary amines, or of secondary amines, or substitution
products thereof, can be employed with the same or a similar result.
My foreign correspondents do not limit themselves to the employment of the
nitroso compounds or amido compounds hereinbefore enumerated, as other nitroso
or amido compounds belonging to the benzene or naphthalene series likewise can be
used. By such alterations, the nature of this invention is not changed, as the
invention in general relates to the production of dye-stuffs capable of dyeing with
the aid of mordants, by the action of nitroso derivatives of tertiary or secondary
amines, or substitution products thereof, on nitroso or amido. products of the
naphthalene or benzene series, or on the quinones or quinone-like compounds
derived from such nitroso or amido products, in or without the presence of thio
sulphates.
The process for producing these colouring matters in general is illustrated by
the above example.
It is to be observed that, if in the process hereinbefore explained, colouring
matters soluble in water with difficulty, or insoluble, result, these products, by a
subsequent treatment with sulphonating agents, can be readily converted into such
dyestuffs which dissolve with comparative ease, and possess a high value in
practice.
Dated this 14th day of September 1893.

page_text: 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 Specification of application for
Letters Patent No. 825, dated 13th January 1893, a process for the production of
dyestuffs (capable of dyeing with the aid of mordants), which process consists
either in acting with salts of alpha, beta, naphthaquinone alpha,-monosulphonic
acid, or alpha, beta-naphthahydroquinone-alpha, monosulphonic acid, on nitroso
derivatives of secondary or tertiary aromatic amines, or substituted amines, in the
presence of thio sulphuric salts, and subsequently sulphonating the products so
formed, in case they are found to be insoluble, or but slightly soluble.
My foreign correspondents have now found, that in order to produce the dye
stuffs (suitable for dyeing blue shades with the aid of mordants) described in the
Specification No. 825", it is not necessary to first prepare the naphthaquinone
sulphonic acid, or naphthahydroquinonesulphonic acid, but that nitrosonaphthols
and nitrosonaphtholsulphonic acids, or the corresponding amidonaphtholsulphonic
acids, or naphthahydroquinone sulphonic acids, can be used, and that, like the
nitrosonaphthols, nitrosonaphtholsulphonic acids, amidonaphtholsulphonic acids,
and hydroquinone sulphonic acids, other nitroso compounds, or the corresponding
amido compounds or hydroquinone compounds of the naphthalene series, and also
the corresponding quinone derivatives, are capable of entering into action with
nitroso derivatives of tertiary or secondary amines, in the presence of salts of thio
sulphuric acid.
If, for instance, instead of alpha, beta-naphthaquinone alpha, sulphonic acid,
either beta, nitroso alpha, naphthol alpha, sulpho acid, or alpha, nitroso-beta,
naphthol, be allowed to act on nitroso compounds in the presence of thiosulphates,
dyestuffs are formed which are identical with those produced in an analogous
manner, by means of the said alpha, beta, naphthaquinone-alpha, sulphonic acid.
My foreign correspondents account for this peculiar fact, by assuming, that
during the said interaction, the nitroso group of the nitrosonaphtholsulphonic acid
is first converted, by reduction, into the amido group, and that the amido group
subsequently becomes displaced by oxygen.
In order to illustrate this new process, the following example is given. The
parts are by weight.
COLOURING MATTER OBTAINED FROM NITROSODIMETHYLANILINE, ALPHA₁
NITROSO-BETA1 NAPHTHOL BETA, SULPHONIC ACID, AND SODIUM
THIOSULPHATE.
9.3 parts of nitrosodimethylanilinehydrochloride, and 14 parts of the sodium salt
of alpha, nitroso-beta, naphthol beta, sulphonic acid, are dissolved in 300 parts of
hot water.
After adding 18 parts of acetic acid (containing 33 per cent. of pure
acid), the liquid is mixed with a hot solution of 26 parts of sodium thiosulphate in
100 parts of water. The formation of the dyestuff very soon begins, the resulting
colouring matter separating in small lustrous, bronze-coloured crystals. When the
production of the dye is at an end, heating is discontinued, and the mixture is
filtered whilst still hot. The dyestuff collected on the filter, when dried, is
sufficiently pure to be directly used for dyeing purposes.

page_text: The dyestuff obtained in the manner above described, has been found by my
foreign correspondents to be identical with the colouring matter formed from
nitrosodimethylaniline, sodium thiosulphate, and alpha, beta, naphthoquinone beta,
sulphonic acid. Its composition is probably represented by the following formula:
'
The same colouring matter is formed if, in the preceding example, instead of
nitrosonaptholsulphonic acid, the corresponding quantity of ether alpha, amido
beta, naphthol-beta, sulphonic acid, or of alpha beta, naphthahydroquinone beta,
sulphonic acid, be used."
Analogous dyestuffs are formed, if, in place of the above prescribed nitroso
compounds, or of the corresponding amido product, other nitroso naphthol
sulphonic acids, or nitrosonaphthols or amido naphtholsulphonic acids, or derivatives
thereof, are used.
As above mentioned, other nitroso compounds of the naphthalene series can also
be used in this process; for instance, nitrosodihydroxynaphthalenes, nitroso
derivatives of monosubstituted dihydroxynaphthalenes (such as nitrosomonomethyl
-dihydroxynaphthalenes, nitrosomonoethyldihydroxynapthalenes, nitrosohydroxy-
naphthoxy acetic acids of the formula NO CH, (OH) OCH, COOй), and
nitrosonaphthol carboxylic acids.
According to the researches of my foreign correspondents, the following
orthonitroso compounds containing the nitroso group in the ortho position relatively
to the hydroxyl group (when condensed with nitroso derivatives of secondary or
tertiary amines, or substituted amines, in the presence of thiosulphuric salts),
give useful results, viz., beta₁-nitroso-alpha,-naphthol, alpha,-nitroso-beta,-naphthol,
nitroso-alpha naphthol-alpha-monosulphonic acid, beta,-nitroso-alpha-naphthol-
beta-monosulphonic acid, beta-nitroso-alpha,-naphthol-beta, monosulphonic acid,
beta, nitroso-alpha-naphthol-alpha, monosulphonic acid, nitroso-alpha-naphthol-
alpha, alpha, disulphonic acid, nitroso-alpha-naphthol-alpha, beta, disulphonic
acid, beta-nitroso alpha, naphthol-alpha, beta, disulphonic acid, beta₁-nitroso-
alpha-naphthol-beta, alpha-disulphonic acid, nitroso-beta,-naphthol-beta,-mono-
sulphonic acid, nitroso-beta-naphthol-beta-monosulphonic acid, nitroso-beta,
naphthol-alpha, beta, disulpbonic acid (derived from beta,-naphthol-alpha, beta-
disulphonic acid, which can be obtained by diazotising the corresponding beta-
amido-naphthalene-alpha, beta, disulphonic acid, and boiling the diazo compound
with water or acids), nitroso-beta, beta, dihydroxynaphthalene, nitroso-beta, beta-
dihydroxynaphthalene, nitroso beta, alpha-dihydroxynaphthalene, the nitroso deriva-
tives of monoalkyl-beta, beta, or beta, beta, dihydroxynaphthalenes, formed by the
interaction of one molecular proportion of alkylhaloids and one molecular proportion
of the monosodium salt of beta, beta, or beta, beta,-dihydroxynaphthalene, the nitroso
compound of hydroxynaphthoxyacetic acid, which can be obtained by the action of
one molecular proportion of monochloroacetic acid on one molecular proportion of the
disodium salt of beta, beta, or beta, beta, dihydroxynaphthalene, the nitroso
derivative of beta-naphthol-beta,-carboxylic acid, the nitroso derivatives of the
two acis beta-naphthol-beta-carboxylic acid, and beta,-naphthol-beta-carboxylic
acid (which can be produced by diazotising beta,-naphthylamine-beta1-monosulphonic
acid and beta-naphthylamine-beta,-monosulphonic acid respectively, and converting

page_text: the diazo derivatives into the corresponding cyano derivatives, subsequently con-
verting the resulting cyanosulphonic acids into the corresponding sulpho carboxylic
acids, and fusing the latter with alkalies).
The amido compounds corresponding to the aforesaid derivatives of the ortho
nitrosonaphthols, can also be used. Instead of the latter products, the corresponding
naphthahydroquinone, or quinone derivatives, can also be used, the use of alpha,
beta-naphthahydroquinone-alpha,-monosulphonic acid, and alpha, beta, naphtho-
quinone-alpha, monosulphonic acid used in the process described in the Specification
No. 825 being excluded, however.
The researches of my foreign correspondents have also shown, that the following
quinone derivatives can be profitably used, viz., alpha, beta, naphthaquinone-alpha-
monosulphonic acid, alpha, beta, naphthaquinone beta-monosulphonic acid, alpha,
beta-naphthaquinone-beta, monosulphonic acid, alpha, beta,-naphthaquinone-alpha,
alpha, disulphonic acid, alpha, beta-naphthaquinone-alpha, beta, disulphonic acid,
alpha, beta-naphthaquinone-alpha, heta,-disulphonic acid, alpha, beta, naphtha-
quinone beta, alpha, disulphonic acid, and beta, hydroxy-alpha, beta,-naphtha-
quinone.
As above mentioned, the corresponding naphthahydroquinone derivatives can
also be used.
The researches of my foreign correspondents have shewn that the colouring
matters obtainable by means of the process herein before defined, are identical
with the corresponding dyestuffs which are formed by means of the process described
in the Specification of application for Letters Patent No. 6035, dated 21st March
1893, provided that the same nitrosonaphthols, nitrosonaphtholsulphonic acids, or
the like, are used in the two processes.
In place of nitrosodimethylaniline used in the foregoing example, the nitroso
derivatives of other tertiary amines or of secondary amines, or substitution
products thereof, can, as a matter of course, be used with the same or a similar
result.
My foreign correspondents do not limit themselves to the directions given in the
above example, as these can be varied. By such alterations, "the nature of this
invention is not changed, as the invention, in general, relates to the production of
dyestuffs capable of dyeing with the aid of mordants, by the action of nitroso
derivatives of tertiary or secondary amines, or substitution products thereof, on
orthonitroso or amido derivatives of the naphthalene series, or on the quinones or
hydroquinone derivatives obtained from such nitroso or amido products in the
presence of thiosulphate.
The process for producing these colouring matters, in general, is illustrated by
the above example.
My foreign correspondents have also found that if, in the process hereinbefore
explained, colouring matters are formed which dissolve in water with difficulty, or
are insoluble, these products can. by a subsequent treatment with sulphonating
agents, be readily converted into dyestuffs which dissolve with comparative ease.
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 colouring-matters, which process consists in
allowing nitroso derivatives of secondary or tertiary amines, or substituted amines,
to act in the presence of thiosulphuric salts on the orthonitroso derivatives of
alphanaphthol, betanaphthol, alpha, naphthol,-alpha, monosulphonic acid, alpha
naphthol beta-monosulphonic acid, alpha-naphthol-beta-monosulphonic acid,
alpha-naphthol-alpha-monosulphonic acid, alpha-naphthol-alpha, alpha-disul-
phonic acid, alpha,-naphthol-alpha,-beta,-disulphonic acid, alpha-naphthol-alpha,
beta,-disulphonic acid, alpha,-naphthol-beta, alpha-disulphonic acid, beta-naphthol-
beta,-monosulphonic acid, beta,-naphthol-beta-monosulphonic acid, beta,-naphthol-
alpha, beta-disulphonic acid, beta beta or beta, beta, dihydroxynaphthalene, betai

page_text: alpha-dihydroxynaphthalene, mono-alkylated beta, beta, or beta, beta, dihydroxy-
naphthalene, the hydroxynaphthoxy acetic acid derived from beta, beta, or beta
beta, dihydroxynaphthalene, beta-naphthol-beta,-carboxylic acid, beta, naphthol-
beta-carboxylic acid, or beta, naphthol-beta,-carboxylic acid, and subsequently
sulphonating the products so formed, in case they are found to be insoluble, or
soluble with difficulty.
2. The production of dyestuffs, which process consists in using in the process
claimed by the foregoing first, claim, either in place of the orthonitrosonaphthol
derivatives named therein, the corresponding derivatives of alpha, amido-beta,
naphthol or beta-amido-alpha-naphthol, or the corresponding naphthaquinone or
naphthahydroquinone derivatives, excluding, however, the alpha, beta-naphtho
quinone-alpha-monosulpho acid and alpha beta-naphthohydroquinone alpha,
monosulphonic acid.
3. The process for producing colouring matters, which process consists in allowing
the nitroso derivatives of secondary or tertiary amines, or substituted amines, to
act, in the presence of thiosulphuric salts, either on alpha beta, naphthaquinone-
alpha-monosulphonic acid, alpha, beta-naphthaquinone-beta-monosulphonic acid,
alpha, beta, naphthaquinone-beta-monosulphonic acid, alpha, beta-naphthaquinone-
alpha, alpha,-disulphonic acid, alpha, beta-naphthaquinone-alpha, beta, disulphonic
acid, alpha beta₁-naphthaquinone-alpha, beta, disulphonic acid, alpha, beta-
naphthaquinone-beta, alpha-disulphonic acid, beta-hydroxy-alpha, beta-naphtha-
quinone, or on the naphthahydroquinone compounds, or orthoamido naphthol
compounds corresponding to these naphthaquinone products, and subsequently
sulphonating the products so formed, in case they are found to be insoluble, or
soluble with difficulty.
Dated this 22nd day of January 1894
NEWTON & SON,
Agents for the Applicant.