The Manufacture or Production of New Azo Colouring Matters.
Year: 1892

page_text: Date of Application, 2nd Nov., 1892
Complete Specification Left, 31st July, 1893-Accepted, 9th Sept., 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Azo 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:-
In the Specification of Letters Patent No. 16484, dated 30th November 1887, a
process is described for producing valuable dye stuff's capable of dyeing cotton,
which consists in first combining the diazo derivatives of mono acetyl paraphenylene
diamine, or mono acetylnaphthylene diamine, with alpha naphthylamine, diazotising
the so-formed amidoazo compounds, and coupling the resulting diazo products with
certain components, viz. phenols, naphthols, sulpho or carboxylic acids thereof,
splitting off the acetyl group, rediazotising, and combining the so-formed diazo
compounds with amines, diamines, phenols, and sulpho or carboxylic acids
thereof.
My foreign correspondents have now found that new valuable colouring-matters
producing on cotton from bluish-black, violet- black, to greenish-black shades, can
be obtained from paraphenylene diamine or naphthylene diamines, by combining
the diazo compounds of the mono acetyl derivatives of the said diamines, with
alpha naphthylamine, or substitution products thereof, or analogous amines,
diazotising the so-produced amidoazo compounds, coupling the resulting diazo
products with amido naphtholsulpho acids or dihydroxynaphthalene sulpho acids,
and subsequently splitting off the acetyl group. By substitution products of
alphanaphthylamine or analogous amines," my foreign correspondents understand
the following products, viz., aniline, toluidine, xylidine, cresidine; and the like,
amidonaphthols, amidonaphtholethers, amidonaphthol-sulpho acids, amidonaphthol-
ether sulpho acids, amidonaphthoxy acetic acids, amidonaphthoxyaccitic sulpho
acids alphanaphthylamine ortho mono sulpho acid, alphanaphthylamine mono-sulpho
acids and 8 of Clève. The last named compounds are briefly termed in this
Specification "middle components."
"
The colouring matters produced in the manner hereinbefore specified, and
representing the series A, possess high value, as they yield on unmordanted cotton,
from bluish black, violet black, to greenish black shades, of great fastness and
intensity. They differ from the products described in the German Patent No. 42814,
as the latter dye cotton a violet, and are of the general formula :

page_text: It is also noticeable that the above dye stuffs of the series A, yield shades which
perfectly withstand the action of diluted acids and alkalies, whilst the products of
the German Patent No. 42814 are fast only against the action of soap and acetic
acid.
My foreign correspondents have further found, that the dye stuffs of the series A
are of high value, as they can be further diazotized, and then combined with two
or one molecular proportion of an amine, a phenol, amidophenol, amidophenolether
of the benzene or naphthalene series, a sulpho- or carboxylic acid thereof, dye
stuffs being thus formed which are superior to the colouring matters of the series A,
by the greater intensity of their shades, and which will be briefly termed in this
Specification "dye stuffs of the series B."
Valuable products, viz.,-those of the series A, result by combining diazotised
mono acetyl paraphenylene diamine, or mono acetylnaphothylene diamines, with
one of the above enumerated "middle components," rediazotising the thus obtained
intermediate products, coupling the resulting diazo derivatives with amidonaphthol
mono sulpho acid G., 1.8 amidonaphthol betadisulpho acid, or other amidonaphthol-
sulpho acids, or dihydroxynaphthalene sulpho acids, and subsequently splitting off
the acetyl group.
:
C.H. (or C₁, H.)
10
N = NY,
are obtained by further diazotising the products of the series A, and combining the
resulting tetrazo- or diazo compounds with relatively two or one of the known dye
stuff components. Amongst the latter, for instance, the following can be
employed Alphanaphthol alpha monosulpho acid (1.4, 1.5, or 1-8), alphanapththol-
disulpho acid $ described in the German Patent No. 40571, alpha naphtholepsilon-
disulpho acid (German Patent No. 45776), alphanaphthol disulpho acid (German
Patent No. 38281), betanaphtholalphamonosulpho acid (2.8), beta naphthol beta
monosulpho acid (2-6), beta naphtholdeltamonosulpho acid (2.7), betanaphthol-
disulpho acid R or G, 1-8-dihydroxynaphthalene alpha monosulpho acid S, 1-8-di-
hydroxynaphthalene alphadisulpho acid, 18-dihydroxynaphthalene beta disulpho
acid, amidonaphthol monosulpho acid G., 1-8-amido naphthol beta disulpho acid
obtained from alphanaphthylamine trisulpho acid of the German Patent No. 56058,
or diamido naphthalene alpha disulpho acid. Other naphtholsulpho acids, dihy-
droxynaphthalene sulpho acids, amido naphthol sulpho acids, or, in general, amines,
phenols, amido phenols, amido phenols, amido phenolethers of the benzene or
naphthalene series, sulpho or carboxylic acids thereof, likewise can be employed.
All these products, which can be used, are briefly termed in this Specification
"last components."
Of course, in employing amido naphtholsulpho acids as "middle" or "last
components," different dye stuffs are obtained, according to the solution (whether
alkaline or acid) used.

page_text: The method for producing the dye-stuffs of the series A, is illustrated by the
following examples, the parts being by weight :-
ACID G,
IN
DYE-STUFF OBTAINED FROM MONO ACETYLPARAPHENYLENEDIAMINE, ALPHA-
NAPHTHYLAMINE, AND AMIDONAPHTHOLMONOSULPHO
.EQUIMOLECULAR PROPORTIONS.
A solution cooled by ice, and prepared by dissolving 1.5 parts of mono acetyl
paraphenylene diamine in about 20 parts of water and 4-5 parts of hydrochloric
acid (21 degrees Baumé), is mixed with a concentrated watery solution of 0.7 parts
of sodium nitrite. After about one hour, the formation of the diazo compound is
finished. The latter is introduced into a hydrochloric solution of 1.43 parts of
alphanaphthylamine, and sodium acetate is added, in order to complete the reaction.
The resulting amido azo product of the formula :-
is filtered off, mixed with about 30 parts of water, and after the addition of 6 parts
of soda lye (35 degrees Baumé), heated to boiling, until the acetyl group is
5 completely split off.
Out of the alkaline solution, the dye stuff is isolated, in the usual manner, by
salting out, filtering off, pressing, and drying. It possesses the following com-

page_text: DYE STUFF RESULTING FROM MONO ACETYL-14 NAPHTHYLENE DIAMINE,
ALPHA NAPHTHYLAMINE, AND 18-AMIDONAPHTHOL. BETA DISULPHO
ACID IN EQUIMOLECULAR PROPORTIONS.
2 parts of pulverized mono acetyl-14 naphthylene diamine are dissolved in
30 parts of water and 2-7 parts of muriatic acid (30 per cent.), avoiding any rise of
temperature, as the separation of the acetyl group otherwise easily takes place.
The resulting solution, advantageously cooled by ice, is mixed with a cold solution
of 0.7 parts of sodium nitrite in 3.5 parts of water, in order to produce the diazo
compound of mono acetyl-1-4-naphthylene diamine. When the diazotation is
complete, the solution is added to a solution of 1.43 parts of alpha naphthylamine in
diluted bydrochloric acid, and the combination is advanced by the addition of
2 parts of sodium acetate dissolved in a small quantity of water. The amido azo
product thus formed, is filtered off, and mixed with about 20 parts of water.
adding a concentrated watery solution of 0.7 parts of sodium nitrite the mixture is
acidulated by means of hydrochloric acid, and then allowed to stand for 24 hours.
The whole liquid containing the diazo derivative of the intermediate product of the
formula-
After
NH CO CH,.
In order to separate the acetyl group, it is mixed with about 30 parts of water, 2
and after the addition of 6 parts of soda lye (at 35 degrees Baumé) heated to
boiling for so long a time until the reaction is complete.
Out of the resulting alkaline solution, the dye-stuff is isolated in the well known
manner, by salting out, filtering off, pressing, and drying. Its composition
corresponds to the following formula :--—
30

page_text: acid G, or 18 amidonapthol beta disulpho acid, other amidonaphthol sulpho acids
are employed, or alpha naphthylamine is replaced by another of the above "middle
components," or mono acetyl-1-4-naphthylenediamine, is replaced by the mono
acetylderivatives of isomeric naphthylene diamines, the analogous coloring matters
result. They shew only little differences in the shades produced by them on
unmordanted cotton.
The amidonaphtholsulpho acids can also be coupled in acid solution, and dye
stuffs are thus produced which yield, on unmordanted cotton, violet black shades,
and in general possess the same valuable properties as the analogous colouring
matters resulting when the amidonaphthol sulpho acids are combined in alkaline
solution.
Of course, the separation of the acetyl group can also be effected in the above,
and likewise in the following relative examples, by heating with diluted acids, riz.,
according to all those methods used in chemistry for such purposes.
In order to explain the production of the dye stuffs which contain, in place of
amido naphthol sulpho acid, a dihydroxynaphthalene sulpho acid, the following
example is given :-
THIRD EXAMPLE.
COLOURING
MATTER
ACETYL
RESULTING FROM EQUI-MOLECULAR
PARAPHENYLENE
DIAMINE, ALPHA
MONO
PROPORTIONS
NAPHTHYLAMINE,
OF
AND 18 DIHYDROXYNAPHTHALENE ALPHA MONO SULPHO ACID S.
1.5 parts of mono acetyl para phenylene diamine are mixed with 5 parts of water
and 2.5 parts of hydrochloric acid (30 per cent.), and the resulting mixture is then
cooled by ice. A. solution of 0-7 parts of sodium nitrite in a small quantity of
water is added, and when the diazotation is finished, the mixture is added to a
cooled solution of 1-43 parts of alpha naphthylamine in the necessary quantity of
water, and 12 parts of muriatic acid (30 per cent.). On stirring, a solution of
sodium acetate is added, in order to neutralize the free mineral acids. After about
12 hours, 2-5 parts of hydrochloric acid, and thereupon 0-7 parts of sodium nitrite,
dissolved in a small quantity of water, are added, whilst the temperature is kept at
0 degrees centigrade. The thus obtained diazo derivative, after about 12 hours, is
filtered off, and introduced into a watery solution of 2.4 parts of the sodium salt
of 18 dihydroxynaphthalene alpha monosulpho acid S, and 4 parts of sodium
acetate. Then sodium.carbonate is added, in order to render the mixture again
alkaline, and it is heated to 60 degrees centigrade. In this manner, the formation
of the intermediate product is completed. It corresponds to the formula :-

page_text: It dyes unmordanted cotton, in an alkaline soap bath, a bluish black.
By means of mono acetyl paraphenylene diamine, or para amido acetanilide, in
the same manner as described in the foregoing third example, the analogous dye-
stuffs are obtained, if, in place of 1-8-dihydroxynaphthalene alpha mono sulpho
acid, other dihydroxyuaphthalene sulpho acids are employed, or if the alpha
naphthylamine is replaced by another of the above middle components. The
production of the analogous dye stuffs derived from naphthylene diamines, is also
effected in the manner explained by the preceding third example. The shades
produced by these colouring matters of the series A on unmordanted cotton in
alkaline soap baths, are from bluish-black to greenish black, and possess a high
intensity and fastness.
The same colouring matters, the production of which is illustrated by the
preceding three examples, can also be obtained, as my foreign correspondents have
found, by employing paranitro aniline, or nitronaphthylamines, in place of the
mono acetyl derivatives of phenylene diamine or naphthylenediamines, coupling
the diazo products of the said mono nitro amines with one of the above "middle
components," rediazotising, combining the thus formed diazo compounds with
amido naphthol sulpho acids or dihydroxynaphthalene sulpho acids, and subsequently
reducing the resulting nitro dyes by means of suitable reducing agents.
This method of producing the colouring matters of the series A is illustrated by
the following examples. The parts are by weight.
DYE STUFF FORMED FROM PARA NITRO ANILINE, ALPHA NAPHTHYLAMINE
MONO-SULPHO ACID ẞ OF CLÈVE, AND AMIDONAPHTHOL MONO SULPHO
ACID G.
1·38 parts of paranitraniline are diazotised in the usual manner, and the resulting
diazo compound is allowed to act on 2.45 parts of the sodium salt of Clève's
alphanaphthylamine monosulpho acid 3, dissolved in water, and mixed with about
5 parts of sodium acetate. When the combination is complete, the mixture is
rendered alkaline, and the intermediate nitro product having the formula :-

page_text: reduction, or until a portion, after mixing with the said reducing agent, on heating,
does not shew a further alteration. Mineral acid is added, and the dye stuff is
isolated by sålting out, filtering off, pressing, and drying.
Of course, this product is identical with the coloring matter obtained by
combining diazotised mono acetyl phenylenediamine with Clève's alphanaphthyl-
amine mono sulpho acid 3, rediazotising, combining the so-formed diazo compound
with amidonaphtholmonosulpho acid G, and finally splitting off the acetyl group.
It produces on cotton, in an alkaline soap bath, a bluish black.
Its composition corresponds to the following formula:
-
In an analogous manner, the other dye stuffs are obtained from paranitroaniline,
by coupling its diazo derivative with one of the above "middle components,"
rediazotising, coupling the so-formed diazo compounds with amidonaphtholsulpho
acids, or dihydroxyuaphthalenesulpho acids, and subsequently reducing the so
formed nitro dye stuffs.
The process is also effected in the same manner, if nitronaphthylamines are
employed for producing the corresponding dye stuff's derived from naphthylene
diamines, as described in the following example
COLORING-MATTER FROM 1.4
NITRONAPHTHYLAMINE,
ALPHAAMIDO BETA-
NAPHOLETHER BETA MONO SULPHO ACID, AND 1.8 DIHYDROXYNAPHTHA-
LENE ALPHADISULPHO ACID.
The diazo compound obtained from 1-88 parts of 1.4 uitronaphthylamine in the
usual manner, is allowed to act on 2-67 parts of the sodium salt of alphaamido
betanaphtholetherbetamonosulpho acid (derived from betanapholbetamono sulpho
acid, 26, by ethylising, nitrating, and reducing), in moderately acetic or alkaline
solution. When the combination is complete, a watery solution of 0-7 parts of
sodium nitrite is directly added, and the mixture is slowly acidulated by means
of muriatic acid. After about 24 hours, the so-formed diazo compound is filtered
off, and then introduced into a solution in water of 3.64 parts of 1.8 dihydroxy-
In
naphthalene alphadisulphonate, of sodium, and about 7 parts of sodium acetate.
order to complete the reaction, the mixture is heated for a short time at about
90 degrees centigrade, and the nitro dyestuff having the formula:

page_text: To reduce the nitro dyestuff, it is dissolved in hot water, and the resulting
solution is mixed with sodium sulphide until the reduction is complete. After
acidulating, the complete dyestuff is salted out, filtered off, pressed, and dried.
It possesses the following formula:
In the same manner as described in the preceding fifth example, analogous dye-
stuffs are obtained from 1-4 nitronaphthylamine, or isomeric nitronaphthylamines,
if, in place of 1-4 nitronaphthylamine, the isomeric nitronaphthylamines are employed,
or if alphaamidobetanaphtholetherbetamonosulpho acid is replaced by another of
the above "middle components," or if, in place of 1.8 dihydroxynaphthalene alpha-
disulpho acid, other dihydroxynaphthalene sulpho acids, or amidonaphtholsulpho
acids, are employed.
My foreign correspondents have described in the above five examples, certain
methods for producing the coloring matters of the series A. Of course, they do
not limit themselves to the proportions given in the said examples, for they can be
varied, and all methods in use for producing analogous dyestuffs can also be
employed. For instance, in starting from nitroamines, the reduction of the first
obtained nitro dye stuffs may also be effected by means of other reducing agents,
and especially, amongst the alkaline reducing agents, ammonium hydro sulphide,
ammonium sulphide, and the like, can be employed.
These dyestuffs of the series A, hereinbefore defined, possess a high value, as
they are capable of being further diazotised, and combined with two or one
molecular proportion of the known dyestuff components, coloring mutters being
thus obtained which produce still more intense shades.
The production of these new coloring matters of the series B, is illustrated by the
following two examples:
FORMED AS
MOLE-
DYE STUFF OBTAINED BY REDIAZOTISING THE PRODUCT
DESCRIBED IN THE FIRST EXAMPLE, AND COUPLING WITH TWO
CULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENEALPHAMONO-
SULPHO S.
5.34 parts of the dye stuff obtained as described in the preceding first example,
are mixed with about 50 parts of water, and after the addition of a concentrated
solution, in water, of 14 parts of sodium nitrite, the mixture is slowly acidulated
by means of hydrochloric acid, and then allowed to stand for some hours, with
occasional stirring. It is then added to a solution, in water, of 5.24 parts of the
sodium salt of 1-8 dihydroxynaphthalenealphamonosulpho acid and about 10 parts
of sodium acetate. The combination is complete, after heating for some time at
about 60 degrees centigrade. When rendered alkaline, the complete dyestuff is
isolated by salting out, filtering off, pressing, and drying.

page_text: and produces, on unmordanted cotton, greenish black shades.
In the same manner as described in the preceding sixth example, the analogous
dyestuffs derived from paraphenylene diamine, or naphthylenediamines, containing
two diazotable amido groups, and belonging to the series A, are converted into the
corresponding new coloring matters of the series B.
Of course, in place of 1.8 dihydroxynaphthalenealphmonosulpho acid, other
1-8 dihydroxynaphthalene sulpho acids, or, in general, the above named "last
components," viz. :-amines, phenols, amidophenols, amidophenolethers, sulpho or
carboxylic acids thereof, can be employed.
Coloring matters are thus obtained which produce on unmordanted cotton, in
an alkaline soap bath, from bluish black, greenish black, to pure black shades,
the latter being in general darker than those produced by the products of the
series A.
Of course, two different components can be employed, viz., by acting on the tetrazo
derivatives of the dyestuffs of the series A, which contain two diazotable amido
groups, at first with one molecular proportion of one of the above specified "last
components," and then with one molecular proportion of another of these "last
components."
"
The transformation of those coloring matters of the series A containing only
one free amido group, into the corresponding dyestuffs of the series B, by rediazo-
tising and coupling with one molecular proportion of the known dyestuff components,
is explained in the following example.
COLORING MATTER PRODUCED BY DIAZOTISING THE PRODUCT OBTAINED AS
DESCRIBED IN THE ABOVE THIRD EXAMPLE, AND COMBINING THE 80-
FORMED DIAZO COMPOUND
MOLECULAR
WITH ONE
PROPORTION
1.8 DIHYDROXYNAPHTHALENE ALPHAMONOSULPHO ACID S.
OF
5-35 parts of the dyestuff resulting as described in the above third example, are
mixed with about 50 parts of water, and a concentrated solution in water of
0-7 parts of sodium nitrite is added. The resulting mixture is then slowly acidu-
lated by means of hydrochloric acid, and allowed, after stirring, to stand for some
hours. It is then poured into a solution in water of 2.62 parts of the sodium salt
of 18 dihydroxynaphthalenealphamonosulpho acid and about 5 parts of sodium
acetate, and the combination is completed by careful heating at about 60 degrees
centigrade. When rendered alkaline, the dyestuff is isolated in the known manner,
by salting out, filtering off, pressing and drying.
R

page_text: It produces on unmordanted cotton, on in an aikamme soap ban, a pure brack
high intensity.
UL
In an analogous manner, the other dyestuffs of the series A derived from
phenylene diamine, or naphthylene diamines, and containing only one diazotable
amido group, are transformed by diazotising and combining with one molecular
proportion of 18-dihydroxynaphthalenealphamonosulpho acid. In place of the
latter, other dihydroxynaphthalenesulpho acids, or naphtholsulpho acids, amido-
naphtholsulpho acids or, in general, amines, phenols, amidophenols, amidophenol
ethers, sulpho or carboxylic acids thereof, can be employed.
The so formed dyestuffs in general yield from violet black, bluish black, greenish
black, to pure black shades of great intensity and fastness.
My foreign correspondents have further found, that by means of the above
enumerated components, other new and valuable dyestuffs can be produced from
the monoacetylderivatives of paraphenylenediamine and naphthylenediamines, or
from paranitroaniline and nitronaphthylamines.
A group of new coloring matters, the series C, results by combining one molecular
proportion of the diazotised monoacetylparaphenylene diamine, or monoacetyl-
naphthylene diamines, with one molecular proportion of one of the above "middle
components." rediazotising, coupling the so formed diazo products with one molecular
proportion of the same or another "middle component," rediazotising, combining
the resulting diazo compounds with one molecular proportion of dihydroxynaphtha-
lenesulpho acids or amidonaphtholsulpho acids, and subsequently splitting off the
acetyl group.
The last named dyestuffs of the series C, can also be prepared by employing the
diazo derivatives of paranitraniline or nitronaphthylamines, coupling them with
one molecular proportion of the above "middle components," rediazotising, com-
bining the so-formed " diazoproducts with one molecular proportion of the same
or a different "middle. component," rediazotising, coupling the diazo compounds
so obtained with one molecular proportion of a dihydroxynapthalene sulpho acid,
or amidonaphthol sulpho acid, and subsequently reducing the so-formed nitro dye
stuffs by means of suitable reducing agents.
The production of these new dye stuffs belonging to the series C, is illustrated
by the following example :-
DYESTUFF FROM EQUIMOLECULAR PROPORTIONS OF
PARAPHENYLDIAMINE,
1.8 AMIDO-
ALPHANAPHTHYLAMINE, ALPHAAMIDONAPHTHOL (1.5), AND
NAPHTHOLBETADISULPHO ACID.
The amido azo compound obtained from 1.5 parts of monoacetylparaphenylene-

page_text: diamine and 1.43 parts of alphanaphthylamine, as described in the foregoing first
example, and having the formula:
:
is filtered off, mixed with about 30 parts of water and, after the addition of 6 parts
of soda lye (35 degrees Baumé), heated to boiling, until the acetyl group has been
separated. Out of the resulting alkaline solution, the so-formed dyestuff is isolated
by salting out, filtering off, pressing, and drying. It possesses the following
composition
and produces, on unmordanted cotton, bluish black shades.
"
By means of the same method illustrated in the foregoing eighth example,
analogous dyestuffs are obtained by employing, in place of 18 amidonaphthol-
betadisulpho acid, other amidonaphtholsulpho acids, or dihydroxynaphthalene
sulpho acids, or by replacing the "middle components," alphanaphthylamine and
amidonaphthol (15), by either of the above enumerated "middle components
(employing either two equal or two different ones), or by employing, in place of
mono acetyl paraphenylene diamine, monoacetylnaphthylene diamines. If the
nitro products, viz., paranitroaniline, or nitronaphthylamines, are employed, the
nitro groups contained in the nitro dyestuffs inust be reduced, the process being
carried out when the corresponding acetyl dyestuffs are saponified, as described in.
the above eighth example.
"

page_text: In like case with the dye-stuffs of the series A. the coloring matters of the
series Calso possess the ability of being again'diazotised, and then combined with
two or one of the known dye-stuff components. If two components be coupled,
either two equal or two different ones, of course, can be employed, In this manner,
the coloring matters of the new series D are obtained, as my foreign correspondents
have found. The production of the latter dye stuffs, viz., the conversion of the
coloring matters of the series C into the corresponding products of the series D, is
effected in an analogous manner, as described in the above sixth example, for the
transformation of the products of the series A into those of the series B. The
resulting products are similar in their dyeing properties to those of the above
series B, and likewise yield shades of great intensity and fastness.
My foreign correspondents mention, for example, the dyestuff which is obtained
by further diazotising the product obtained as described in the above eighth
example, and combining the resulting tetraze compound with two molecular pro-
portions of 1-8 dihydroxynaphthalene alpha monosulpho acid. This member of
the series D possesses, according to its production, the following composition.
-
DYE STUFF OBTAINED BY FURTHER DIAZOTISING THE PRODUCT FORMED AS
DESCRIBED IN THE PRECEDING EIGHTH EXAMPLE, AND COUPLING THE
RESULTING TETRAZO COMPOUND WITH TWO MOLECULAR PROPORTIONS
OF 18 DIHYDROXYNAPHTHALENEALPHAMONOSULPIO ACID.
8 parts of the coloring matter obtained as described in the preceding last
example are mixed in water. After the addition of a concentrated solution in
water of 14 parts of sodium nitrite, the mixture is acidulated by means of hydro-
chloric acid, and when the diazotation is complete, it is introduced into a solution,
in water, of 5.24 parts of 1.8 dihydroxynaphthalenealphamonosulphonate of sodium,
and about 10 parts of sodium acetate. In order to complete the reaction, the
mixture is heated for a short time at 60 degrees centigrade, and after being
rendered alkaline, the dye stuff is isolated by salting out, filtering off, pressing, and
drying.
My foreign correspondents have further prepared a new group of dye stuffs by
combining the diazo derivatives of monoacetylparaphenylenediamine, or mono-
acetylnaphthylenediamines, with one molecular proportion of one of the above
"middle components," splitting off the acetyl group, or reducing the nitro group
contained in the thus produced acetyl- or nitro compounds, rediazotising the
so-formed diamidoazo products, and coupling the resulting tetrazo derivatives with
two molecular proportions of the above enumerated "last components," employing
either the same or two different ones.

page_text: ONE
COLORING MATTER OBTAINED FROM MONO ACETYL 14 NAPHTHYLENE
DIAMINE, BY COUPLING THE DIAZO-DERIVATIVE THEREOF WITH
MOLECULAR PROPORTION OF ALPHA AMIDO BETA NAPHTHOLETHER, BY
SPLITTING OFF THE ACETYL GROUP, REDIAZOTISING, AND COMBINING THE
SO-FORMED TETRAZO COMPOUND WITH TWO MOLECULAR PROPORTIONS OF
AMIDONAPHTHOLMONOSULPHO ACID G.
The diazo compound obtained from 2 parts of mono acetyl 1-4 naphthylene
diamine, as described in the foregoing second example, is added to a hydrochloric
solution of 187 parts of alpha amido beta naphtholether. When the combination
is completed, the acetyl group is separated. A concentrated solution, in water,
of 14 parts of sodium nitrite is then added, and the mixture is acidulated by
means of hydrochloric acid, in order to produce the tetrazo derivative of the first
formed diamido azo compound, having the formula :-
It produces, on unmordanted cotton, greenish-black shades.
The other dye-stuffs of this series E are obtained in an analogous manner, as
described in the foregoing tenth example, viz., by replacing the "middle
component " used in the last named example, by another of the above enumerated
"middle components," or by employing, in place of amidonaphtholmonosulpho
acid G, other amidonaphtholsulpho acids, or dihydroxynaphthalene sulpho acids, or
by starting from another mono acetylnaphthylene diamine, or from mono acetyl
paraphenylenediamine.
Of course, the same coloring matters can be obtained by employing, in the
foregoing tenth example, the diazo compounds of para nitro aniline or nitro
naphthylamines, and reducing the nitro products, always carrying out this latter
process when, in the employment of the said mono acetyl products, the acetyl group
must be separated.

page_text: The latter is rediazotised by means of 0-7 parts of sodium nitrite, in hydro-
chloric solution, and the thus obtained diazo compound is introduced into a solution,
in water, of 2.45 parts of the sodium salt of Clève's alphanaphthylamine mono- 3.
sulpho acid 8, and about 5 parts of sodium acetate. In order to complete the
reaction, the mixture is heated for a short time at 60 degrees centigrade, and after
alkalisation, the resulting intermediate product of the following formula :

page_text: mixed with water, and after the addition of a concentrated solution, in water,
of 0-7 parts of sodium nitrite, the mixture is slowly acidulated by means of hydro-
chloric acid. When the diazotation is complete, the whole mixture is introduced
into a solution prepared by dissolving 2.62 parts of the sodium salt of 1.8 dihy-
droxynaphthalenealphamonosulpho acid S, and about 5 parts of sodium acetate, in
water. In order to complete the reaction, its is then gently heated at about
60 degrees centigrade. After alkalisation, the complete dye stuff is salted out,
filtered off, pressed, and dried. Its composition corresponds to the following
formula
It produces, on cotton, a bluish-black of high intensity.
If, in the preceding eleventh example, paranitroaniline is replaced by nitro-
naphthylamines, the corresponding dye stuffs derived from napthylenediamines are
obtained.
The same products, of course, are obtained in starting from mono acetyl para-
phenylene diamine, or monoacetylnaphthylene diamines, but the acetyl group must
then be separated when the nitro group is reduced, as described in the last
example.
The alphanaphtholal phamonosulpho acid (1.4) employed in the preceding eleventh
example, can be replaced by other naphthol sulpho acids, or in general by phenols,
naphthols, dihydroxynaphthalenes, sulpho or carboxylic acids thereof, and the
alpha naphthalamine monosulpho acid (Clève's 8-acid) employed in the same
example can be replaced by the isomeric ẞ acid, or the alphanaphthylamine ortho-
monosulpho acid, or another of the above enumerated "middle components," and
the 1.8 dihydroxynaphthalenealphamonosulpho acid used in the same example can
be replaced by other dihydroxynaphthalenesulpho acids, or by amidonaphtholsulpho
acids.
My foreign correspondents have further converted the dye stuffs of the series F
which contain, as last components, an amido naphthol sulpho acid, into new
valuable coloring matters of the series G, by further diazotising and combining
with amines, phenols, amidophenols, amidophenolethers, sulpho or carboxylic acids
thereof.
The production of these coloring matters is carried out by employing the original
products used in the foregoing examples, viz.: mono acetyl paraphenylenediamine,
paranitro aniline, mono acetylnaphthylene diamines, or nitro naphthylamines, by
further using the above enumerated "middle components," and amido naphthol- .
or dihydroxynaphthalene sulpho acids, whilst, as further components, phenols,
naphthols, dihydroxy naphthalenes, sulpho and carboxylic acid derived therefrom,
or, in general, the above "last components are employed.
"1

page_text: COLORING MATTER OBTAINED FROM EQUIMOLECULAR PROPORTIONS OF MONO
ACETYL 14-NAPHTHYLENEDIAMINE, BETANAPHTHOL BETAMONOSULPHO 5
ACID (2.6), ALPHAAMIDO BETANAPHTHOLETHERDELTAMONOSULPHO ACID,
AMIDONAPHTHOLMONOSULPHO ACID G., AND ALPHANAPHTHOLALPHAMONO-
SULPHO ACID (1.5).
The diazo derivative obtained from 2 parts of mono acetyl 1.4 naphthylenediamine,
is coupled with 2.46 parts of the sodium salt of betanaphtholbetamonosulpho
acid (2.6) in a watery solution, rendered and kept alkaline by the addition of sodium
carbonate. When the combination is complete, the acetyl group is split off (for
instance, by heating the thus formed acetyl product with diluted alkalies), and the
resulting intermediate amido azo compound having the formula:
COLORING MATTER OBTAINED FROM EQUIMOLECULAR PROPORTIONS OF MONO
ACETYL 14-NAPHTHYLENEDIAMINE, BETANAPHTHOL BETAMONOSULPHO 5
ACID (26), ALPHAAMIDO BETANAPHTHOLETHERDELTAMONOSULPHO ACID,
AMIDONAPHTHOLMONOSULPHO ACID G., AND ALPHANAPHTHOLALPHAMONO-
SULPHO ACID (1.5).
The diazo derivative obtained from 2 parts of mono acetyl 1.4 naphthylenediamine,
is coupled with 2.46 parts of the sodium salt of betanaphtholbetamonosulpho
acid (2.6) in a watery solution, rendered and kept alkaline by the addition of sodium
carbonate. When the combination is complete, the acetyl group is split off (for
instance, by heating the thus formed acetyl product with diluted alkalies), and the
resulting intermediate amido azo compound having the formula:
OH
NN CH¸´
-
C1H6
SO,Na
NH,
is isolated by salting out and filtering off. In order to diazotise the same, it is
mixed with water, and after adding a watery solution of 0.7 parts of sodium nitrite,.
the mixture is acidulated by means of hydrochloric acid. The diazotation being
finished, the mixture is introduced into a moderately alkaline or acetic solution of
2.67 parts of the sodium salt of alphaamido betanaphthol etherdeltamonosulpho acid 2
(obtained from betanaphtholdeltamonosulpho acid 2.7, by ethylising, nitrating, and
reducing). When the combination is complete, the resulting mixture is rendered
alkaline, if an acetic solution be used, and the intermediate product is isolated
by salting out, if it be necessary, and filtered off. It possesses the following
formula
It is mixed with water, and after adding a watery solution of 0.7 parts of sodium
nitrite, hydrochloric acid is slowly added, until the resulting mixture assumes a
lasting acid reaction. When the diazotation is complete, the above mixture is
introduced into a watery solution prepared by dissolving 2'61 parts of the sodium 3
salt of amido naphthol monosulpho acid G., and adding sodium carbonate. After

page_text: SO,Na
SO,Na,
is isolated, by salting out and filtering off. It is then diazotised by means of
5 0-7 parts of sodium nitrite in hydrochloric solution, and the thus obtained mixture
containing the diazo derivative of the last-named intermediate product, is introduced
into a solution prepared by dissolving 2.46 parts of the sodium salt of alphanaphthol
alpha monosulpho acid (1.5) in water, and alkalising it by the addition of sodium
carbonate. The resulting dye stuff, of the formula:
is isolated by salting out, filtering off, pressing, and drying. It produces, on
unmordanted cotton, in an alkaline soap bath, a bluish black.
According to the method described in the foregoing twelfth example, analogous
dye stuffs are obtained by employing, in place of betanaphtholbetamonosulpho
acid (26) and alpha naphtholalphamonosulpho acid (1.5), other naphtholsulpho
acids, or, in general, phenols, naphthols, dihydroxynaphthalenes, sulpho or carboxylic
acids thereof (speaking broadly, the above enumerated and specified "last com-
ponents"), or by starting from the mono acetyl products of the isomeric naphthylene
diamines or para phenylene diamine, or by replacing the alpha amidobetanaphthol-
ether delta mono sulpho acid by the isomeric alpha amido beta naphtholetherbeta-
monosulpho acid, or by employing, in place of amidonaphtholsulpho acid G, other
amidonaphtholsulpho acids."
Of course, the nitro amines, paranitroaniline, and nitronaphthylamines, can
likewise be employed as original products, but the nitro group must then be
converted into the amido group, and this process is to be carried out when the
acetyl group contained in the corresponding acetyl products is separated.
My foreign correspondents have further produced a series of new dye stuffs,
"the series H," by a method analogous to that described in the last-named
example, riz., by coupling not only one "middle component," but two "middle
components," the one after the other, and further treating the so formed intermediate
products containing two "middle components," in the manner illustrated by the
above twelfth example, and specified hereinbefore. The production of these new
C

page_text: dye stuffs of the series H, is effected in manner analogous to that described in the
last example. The resulting coloring matters produce shades similar to those
obtained by means of the dye stuffs of the series G.
My foreign correspondents have found that the coloring matters hereinbefore
specified, and belonging to the series A, B, C, D, E, F, G, and H, are not
only suitable for dyeing unmordanted cotton, but likewise can be advantageously
employed for dyeing wool, possess the capability of dyeing, in equal manner, half
woollen materials, and can be discharged, when dyed on wool.
The coloring matters are superior to the analogous products, by reason of these
valuable properties.
My foreign correspondents have described in the above twelve examples,
certain methods for producing the coloring matters belonging to the series A-H.
Of course, the dye stuffs named in these examples, and the analogous products
herein before defined, can also be obtained in other manner, viz. :-by means of all
those methods generally in use for the production of analogous coloring matters.
It is evident that the nature of this invention is not altered by such variations, as
this invention communicated to me by my foreign correspondents, relates to the
manufacture of eight series of analogous dye stuffs derived from paraphenylene
diamine or naphthylene diamines, and containing, as components, amido naphthol
sulpho acids, or dihydroxy naphthalene sulpho acids; the above specified "middle
components;" and finally, the products above enumerated, and briefly termed "last
components."
Dated this 2nd day of November 1892
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of New Azo Colouring Matters.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of Middlesex, 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 :—
In the Specification of Letters Patent No. 16484, dated 30th November 1887, a
process is described for producing valuable dye-stuffs capable of dyeing cotton,
which consists in first combining the diazo derivatives of monacetyl paraphenylene
diamine, or monacetyl naphthylene diamine, with alpha naphthylamine, diazotising
the amido azo compounds so formed, and coupling the resulting diazo products
with certain components, viz. :-phenols, naphthols, sulpho or carboxylic acids
thereof, splitting off the acetyl group, rediazotising and combining the diazo com-
pounds so formed with amines, diamines, phenols, and sulpho or sulpho carboxylic
acids thereof.
.
My foreign correspondents have now found that new valuable colouring matters,
producing, on cotton, shades varying from bluish-black, or violet-black, to greenish-
black, can be obtained from para phenylene diamine, or naphthylene diamines, by
combining the diazo compounds of the monacetyl derivatives of the said diamines,
with alpha naphthylamine, or substitution products thereof, or analogous amines,
diazotising the amido azo compounds so produced, coupling the resulting diazo
products with amidonaphtholsulpho acids, or dihydroxynaphthalene sulpho acids,
and subsequently splitting off the acetyl group. By the expression "substitution
products of alpha naphthylamine or analogous amines," my foreign correspondents
mean, in general, such amido compounds as will, when combined with diazo
derivatives, yield true amido azo products, which can be further diazotised, for
instance, para-xylidine, orthamido paracresolether, metamido paracresolether, or
the like, amidonaphthols, amidonaphtholethers, amidonaphthol sulpho acids, amido-
naphtholether sulpho acids, amidonaphthoxyacetic acids, amido naphthoxyacetic

page_text: sulpho acids, alpha naphthylamine, ortho mono sulpho acid, alpha naphthylamine
beta mono sulpho acids (beta and delta of Clève). The last named compounds
are hereinafter briefly termed "middle components.'
"
The colouring matters resulting in the manner hereinbefore specified, and
belonging to the so called "A" series, are of high value, as they produce, on
unmordanted cotton, shades varying from bluish-black or violet black to greenish
black, of great fastness and intensity. They are different from the products
described in the German Patent No. 42814, as the latter dye-stuffs yield violet
shades on cotton, and are represented by the general formula
It is also noticeable that the said dye-stuffs of the A series yield shades which
perfectly withstand the action of dilute acids and alkalies, while the products
described in the German Patent No. 42814 withstand only the action of soap and
acetic acid.
My foreign correspondents have further ascertained, that the dye-stuffs of the
A series are very valuable, as they can be further diazotised, and combined with
either two or a single molecular proportion of either an amine or a phenol, amido-
phenol, amidophenolether of the benzene or naphthalene series, or a sulpho or
carboxylic acid thereof, dye-stuffs being thus formed which are superior to the
colouring matters of the A series, owing to the greater intensity of the shades of
colour they produce, and which will be briefly termed in this Specification "dye
stuffs of the B series."
"
"
Valuable products belonging to the "A series' are formed by combining
diazotised monacetyl paraphenylene diamine, or monacetylnaphthylene diamines,
with one of the above specified "middle components,' rediazotising the
intermediate products thus obtained, coupling the resulting diazo derivatives
with either amido naphtholmono sulpho acid G, or 1 : 8 amidonaphthol beta disulpho
acid, or other amido naphthol sulpho acids, or dihydroxynaphthalene sulpho acids,
and subsequently splitting off the acetyl group.
The dye stuffs of the "B series," the composition of which is represented by the
general formula :

page_text: are obtained on further diazotising the products of the "A series," and combining
the resulting tetrazo or diazo compounds, as the case may be, respectively, with
either two or one of the known dye-stuff components. Amongst the latter, the
following, for instance, can be employed: Alpha naphthol alpha mono sulpho acid
(1:4, 1:5 or 1:8), alpha naphthol disulpho acid S, described in the German
Patent No. 40571, alpha naphthol epsilon disulpho acid (German Patent No. 45776),
alpha naphthol disulpho acid (German Patent No. 38281), beta naphthol alpha
mono sulpho acid (2:8), beta naphthol beta mono sulpho acid (2:6), beta
naphthol delta mono sulpho acid (27), beta naphthol disulpho acid R or G,
1:8 dihydroxynaphthlene alpha monosulpho acid S, 1:8 dihydroxynaphthalene
alpha disulpho acid, 1:8 dihydroxynaphthalene-beta-disulpho acid, amidonaphthol
monosulpho acid G, 1:8 amido naphthol-beta-disulpho acid obtained from alpha
naphthylamine trisulpho acid of the German Patent No. 56058, or diamido-
naphthalene alpha disulpho acid. Other naphthol sulpho acids, dihydroxy-
naphthalene sulpho acids, amidonaphthol sulpho acids, or, in general, amines,
phenols, amidophenols, amidophenolethers of the benzene or naphthalene series,
and sulpho or carboxylic acids thereof, can also be employed. The last named
products available for the purpose of this invention, are briefly termed in this
Specification, "last components."
"
"
When amido naphthol sulpho acids are used as "middle or "last components,"
different dye stuffs are obtained, according as the solution is alkaline or acid.
The method of producing the dye stuffs of the "A series" is illustrated by the
following examples, the parts being by weight.
FIRST EXAMPLE.
PARA
DYE STUFF FROM EQUIMOLECULAR PROPORTIONS OF MONACETYL
PHENYLENE DIAMINE, ALPHA NAPHTHYLAMINE, AND AMIDO NAPHTHOL-
MONO SULPHO ACID G.
A solution prepared by dissolving 1-5 parts of monacetyl para phenylene diamine
in about 20 parts of water and 4.5 parts of muriatic acid (21 degrees Baumé),
having been cooled by means of ice, is mixed with a concentrated solution, in
water, of 0-7 parts of sodium nitrite. The formation of the diazo compound is
completed at the end of about an hour. The diazo compound thus obtained is
introduced into a solution of 1-43 parts of alpha naphthylamine in muriatic acid,
and sodium acetate is added, in order to complete the action. The resulting amido
azo product is represented by the formula:
NH CÓ CHẠ
It is filtered off, washed, and mixed with about 20 parts of water, and a concentrated
solution, in water, of 0.7 parts of sodium nitrite having been added, the mixture is
acidulated with muriatic acid. At the end of about 24 hours, the mixture
containing the diazo derivative is added to a solution, in water, of 2-61 parts of
the sodium salt of amidonaphthol mono sulpho acid G, and a sufficient quantity of
sodium carbonate or other suitable alkali. When the combination is complete, the
product is filtered off. Its composition is represented by the following formula:

page_text: It is mixed with about 30 parts of water and 6 parts of soda lye (35 degrees
Baumé), and the liquid is boiled until the acetyl group is split off.
The dye-stuff thus formed is separated from the alkaline solution in the usual
manner, viz., by salting out, filtering off, pressing, and drying. It is represented by
the following formula:
DYE-STUFF FROM EQUIMOLECULAR PROPORTIONS OF MONACETYL-1 : 4 NAPH-
THYLENE DIAMINE ALPHA NAPHTHYLAMINE, AND 1:8 AMIDONAPHTHOL
BETA DISULPHO ACID.
2 parts of powdered monacetyl 1: 4 naphthylenediamine are dissolved in 30 parts
of water, and 2: 7 parts of muriatic acid (30 per cent.), the liquid being cooled, in
order to prevent the temperature rising, as the separation of the acetyl group
otherwise easily takes place. The resulting solution, which is advantageously
cooled by ice, is mixed with a cold solution of 0:7 parts of sodium nitrite in
3:5 parts of water. When the diazotisation is complete, the liquid is added to a
solution of 1-43 parts of alpha naphthalamine in dilute muriatic acid, and the
combination is facilitated by the addition of 2 parts of sodium acetate, dissolved in
a small quantity of water. The amido azo product thus formed, is filtered off, and
mixed with about 2 parts of water. After adding a concentrated solution, in
water, of 07 parts of sodium nitrite, the mixture is acidulated by means of
muriatic acid, and then allowed to stand during about 24 hours. The liquid thus
obtained contains the diazo derivative of the intermediate product represented by

page_text: In order to separate the acetyl group, it is mixed with about 30 parts of water
and 6 parts of soda lye (35 degrees Baumé), and the liquid is boiled until the action
is complete.
The dye-stuff is isolated from the resulting alkaline solution in the known
manner, viz., by salting out, filtering off, pressing, and drying. Its composition is
represented by the following formula:
It produces greenish black shades on unmordanted cotton in alkaline soap baths.
The analogous colouring matters are obtained if, in the preceding first and
second example, in place of the amidonaphthol monosulpho acid G, or 1 : 8 amido-
naphthol beta disulpho acid, other amidonaphthol sulpho acids are employed, or
alpha naphthylamine is replaced by another of the above "middle components,'
or monacetyl-1:4 naphthylendiamine is replaced by the monacetylderivatives of
isomeric naphthylene diamines. The shades produced by these new dye-stuffs on
unmordanted cotton in alkaline soap baths, differ but slightly.
"
The amidonaphtholsulpho acids can also be coupled in acidulated solutions, dye
stuffs being thus formed which produce violet-black shades on unmordanted cotton,
and in general possess valuable properties, similar to those of the analogous
colouring matters which are formed when the amidonaphthol sulpho acids are
combined in alkaline solution.
The separation of the acetyl group can be effected in the above and likewise in
the following examples, by heating with diluted acids, viz., by means of all methods
known and used in chemistry for such purposes.
The following example is given in order to illustrate the production of the dye-
stuffs which contain a dihydroxynaphthalene sulpho acid in place of amidonaphthol
sulpho acid. The parts are by weight.
OF
COLOURING MATTER RESULTING FROM EQUIMOLECULAR PROPORTIONS
MONACETYL PARA-PHENYLENE DIAMINE, ALPHA NAPHTHYLAMINE, AND
1:8 DIHYDROXYNAPHTHALENE ALPHA MONOSULPHO ACID S.
1.5 parts of monacetyl para-phenylene diamine arc mixed with 5 parts of water
and 25 parts of muriatic acid (30 per cent.). The resulting mixture is cooled by
ice, and a solution of 0.7 parts of sodium nitrite in a small quantity of water is
added. When the diazotisation is finished, the mixture is added to a cooled
solution prepared by dissolving 1-43 parts of alphanaphthylamine in 1-2 parts of
muriatic acid (30 per cent.), and the necessary quantity of water. A solution of
sodium acetate is then stirred in, in order to neutralize the mineral acid. At the
end of about 12 hours, 2-5 parts of muriatic acid, and thereupon 0.7 parts of
sodium nitrite, dissolved in a small quantity of water, are added, the mixture being
maintained at about ( degrees centigrade during, say, about 12 hours. The diazo
derivative thus formed is filtered off, and introduced into a solution, in water, of
2.62 parts of the sodium salt of 18 dihydroxynaphthalene alpha mono sulpho acid S,

page_text: and 4 parts of sodium acetate.
Sufficient sodium carbonate is then added to make
the mixture alkaline, and it is heated to about 60 degrees centigrade, whereby the
formation of the intermediate product is rendered complete. Its composition is
represented by the following formula :
It is introduced into a solution prepared by dissolving 0.5 parts of sodium
hydrate in 5 parts of water, and the alkaline mixture is heated until the acetyl
group is separated. The dye-stuff thus formed has the following formula :-
bath.
Analogous dye stuffs are obtained by employing, in place of 1:8 dihydroxy-
naphthalene alpha mono sulpho acid used in the above third example, other
dihydroxynaphthalene sulpho acids, or if the alpha naphthylamine be replaced by
another of the above "middle components."
In place of monacetyl paraphenylene diamine, the homologues thereof, for
instance, the acetyl derivative of the toluylene diamine, melting at 64 degrees
centigrade, or of the xylylene diamine melting at 104 degrees centigrade, or sulpho
derivatives of such acetyl derivatives, can be employed in a like manner.
The production of the analogous dye-stuffs derived from naphthylene diamines
(including naphthylene diamine sulpho acids), is effected in the manner illustrated
by the preceding third example.
The shades produced by these colouring matters of the "A series" on
unmordanted cotton in alkaline soap baths, are from bluish-black to greenish-black,
and are remarkable for their intensity and fastness.
My foreign correspondents have ascertained that the colouring matters, the
production of which is illustrated by the preceding first, second, and third example,
can also be obtained by employing the corresponding nitro amido compounds, such
as para nitraniline, nitrortho toluidine, melting at 134 degrees centigrade, nitro
para xylidine, melting at 143 degrees centigrade, or nitro naphthylamines, or
sulpho derivatives thereof, in place of the monacetyl derivatives of the above
diamines. In this case, the diazo products of the said mononitro amines are
coupled with one of the above "middle components;" the resulting products are
rediazotised, and after combining the diazo compounds thus formed with amido
naphtholsulpho acids or dihydroxynaphthalene sulpho acids, the resulting nitro dyes
are reduced by means of suitable reducing agents.
This method of producing the colouring matters of the "A series," is illustrated
by the following examples. The parts are by weight.

page_text: DYE STUFF FORMED FROM EQUIMOLECULAR PROPORTIONS OF PARA NITR-
ANILINE, ALPHA NAPHTHYLAMINE MONO SULPHO ACID BETA OF CLÈVE,
AND AMIDONAPHTHOL MONO SULPHO ACID G.
1-38 parts of paranitraniline are diazotised in the usual manner, and the resulting
diazo compound is allowed to act on 2:45 parts of the sodium salt of Clève's
alpha naphthylamine mono sulpho acid beta, dissolved in water, together with about
5 parts of sodium acetate. The combination being complete, the mixture is
reudered alkaline, and the intermediate nitro product is filtered off. It possesses
the following composition
It is mixed with a small quantity of water, and a solution in water of 0.7 parts
of sodium nitrite. The mixture having been acidulated with muriatic acid, is
allowed to stand during about 12 hours, until the diazotisation is finished. The
whole liquid mixture is then introduced into a solution prepared by dissolving, in 1
water, 261 parts of the sodium salt of amidonaphthol mono sulpho acid G, and a
sufficient quantity of sodium carbonate. In this manner; the nitro dye stuff of the
following composition is formed :-
The nitro compound is then reduced by dissolving it in hot water, maintaining
the solution at about 60 degrees centigrade, and adding such a quantity of a
solution of sodium sulphide as is necessary for complete reduction, viz., until a
portion, when taken out and mixed with more of the said reducing agent, and
heated, no longer shews an alteration. Mineral acid is then added, and the mixture
is heated. After rendering the solution alkaline, the dye-stuff is isolated by salting
out, filtering off, pressing, and drying.
The researches of my foreign correspondents have shown that the product thus
obtained is identical with the colouring matter obtained by combining diazotised
monacetylphenylene diamine with Clève's alpha naphthylamine mono sulpho acid
beta, rediazotising, combining the diazo compound with amidonaphthol mono sulpho
acid G, and finally splitting off the acetyl group. It produces bluish-black shades

page_text: The other dye-stuffs are obtained in an analogous manner from para nitraniline,
5 its homologues or sulpho derivatives, viz., by coupling the diazo derivatives thereof
with one of the above "middle components," rediazotising, coupling the diazo
compounds so formed with amidonaphthol sulpho acids, or dihydroxynaphthalene
sulpho acids, and subsequently reducing the nitro dye-stuffs so produced.
The process is also effected in a similar manner, if nitronaphthylamines are
employed in order to produce the corresponding dye-stuffs derived from naphthylene
diamines. The production of the latter coloring matters is illustrated by the
following example, the parts being by weight.
COLOURING-MATTER
FROM 14 NITRONAPHTHYLAMINE, ALPHAAMIDOBETA-
NAPHTHOL ETHER BETA MONO SULPHO ACID, AND 1:8 DIHYDROXYNAPH-
THALENE ALPHA DISULPHO ACID.
The diazo compound obtained from 1.88 parts of 1:4 nitronaphthylamine, in the
usual manner, is allowed to act on 2.89 parts of the sodium salt of alpha amido
beta naphthol ether beta inono sulpho acid derived from beta naphthol beta mono
sulpho acid (2-6), by ethylating, nitrating, and reducing either in moderately acetic
or alkaline solution. When the combination is complete, a solution in water of
0-7 parts of sodium nitrite is directly added, and the mixture is slowly acidulated
by means of muriatic acid. After about 24 hours, the diazo compound so formed
is filtered off, and then introduced into a solution, in water, of 3.64 parts of
1-8 dihydroxynaphthalene alpha disulphonate of sodium, and about 7 parts of
sodium acetate. In order to complete the action, the mixture is heated during a
short time, at about 90 degrees centigrade. The nitro dye-stuff thus formed
possesses the following formula :

page_text: in an alkaline soap bath.
In a manner analogous to that described in the preceding fifth example, the
other dye-stuffs are obtained from 14 nitronaphthylamine, or isomeric nitro-
naphthylamines, or nitronaphthylamine sulpho acids, if, in place of 14 nitro
naphthylamine, the isomeric nitronaphthylamines, or nitro naphthylamine sulpho
acids, are employed, or if alpha amido beta naphthol ether beta mono sulpho acid
is replaced by another of the above "middle components," or if, in place of
18 dihydroxynaphthalene alpha disulpho acid, other dihydroxynaphthalene sulpho
acids, or amido naphthol sulpho acids, are employed.
My foreign correspondents have described in the above five examples, certain
methods of producing some of the colouring matters of the A series, but they do
not limit themselves to the directions given in the said examples, as all methods of
producing analogous or similar dye stuffs known to chemists, can also be employed.
For instance, when using nitramines, the reduction of the resulting nitro dye-stuffs
may be effected by means of other reducing agents, such as, for example, ammonium
hydrosulphide, ammonium sulphide, and the like.
The dye-stuffs of the A series herein before defined, are of high value, as they
are capable of being further diazotised, and combined with two or with a single
molecular proportion of the known dye-stuff components, colouring matters being
thus obtained which produce shades of greater intensity.
The production of these new colouring matters of the B series, is illustrated by
the following two examples, the parts being by weight.
DYE STUFF OBTAINED' BY REDIAZOTISING THE PRODUCT FORMED AS
DESCRIBED IN THE FIRST EXAMPLE, AND COUPLING WITH TWO MOLE-
CULAR PROPORTIONS OF 1.8 DIHYDROXYNAPHTHALENE ALPHA ΜΟΝΟ
SULPHO ACID S.
5.34 parts
of the dye-stuff obtained as described in the preceding first example,
are mixed with about 50 parts of water, and after adding a concentrated solution in
water of 14 parts of sodium nitrite, the mixture is acidulated by slowly adding
muriatic acid, and is then allowed to stand during several hours, occasionally stirring
it. It is then added to a solution, in water, of 5.24 parts of the sodium salt of
1.8 dihydroxynaphthalene alpha mono sulpho acid, and about 10 parts of sodium
acetate. The combination is rendered complete by maintaining the liquid, during
some time, at about 60 degrees centigrade. After rendering the solution alkaline,
the dye stuff is isolated by salting out, filtering off, pressing, and drying.

page_text: This dye-stuff produces greenish-black shades on unmordanted cotton.
The analogous dye-stuffs of the "A series," which are derived from para
phenylene diamine, or naphthylene diamines, or the like, containing two diazotisable
amido groups, are converted into the corresponding new colouring matters of the
"B series," in a manner analogous to that described in the preceding sixth example.
In place of 18 dihydroxynaphthalene alpha mono sulpho acid, other 1-8 dihydroxy-
naphthalene sulpho acids, or, speaking generally, the before named "last
components," viz., amines, phenols, amidophenols, amidophenolethers, sulpho- or
carboxylic acids thereof, can be employed.
Colouring matters are in this manner obtained which produce shades on
unmordanted cotton, in an alkaline soap bath, varying from bluish-black or
greenish-black to pure black. The shades thus obtained are in general darker than
those produced by the dye-stuffs of the A series.
The researches of my foreign correspondents show also that two different
components can be combined with the tetrazo derivatives of the dye-stuffs of the
"A series," containing two diazotisable amido groups, viz., on coupling the said
tetrazo compounds at first with one molecular proportion of one of the above
specified "last components," and then with one molecular proportion of another
of these "last components."
The transformation of the colouring matters of the A series which contain but
one free amido group, into the corresponding dye-stuffs of the "B series," by
rediazotising them, and coupling the resulting diazo compounds with one molecular
proportion of the known dye-stuff components, is illustrated by the following
example. The parts mentioned are by weight.
THE
COLOURING MATTER PRODUCED BY DIAZOTISING THE PRODUCT OBTAINED AS
DESCRIBED IN THE ABOVE THIRD
COMBINING
EXAMPLE, AND
DIAZO COMPOUND SO FORMED WITH ONE MOLECULAR
PROPORTION
OF 1.8 DIHYDROXYNAPHTHLENE ALPHA MONO SULPHO ACID S.
5.35 parts of the dye-stuff produced as described in the above third example, are
mixed with about 50 parts of water, and a concentrated solution, in water,
of 0-7 parts of sodium nitrite is added. The resulting mixture is then acidulated
by slowly adding muriatic acid, and allowed to stand during several hours, stirring
it repeatedly. It is then poured into a solution, in water, of 2.62 parts of the
sodium salt of 1.8 dihydroxynaphthalene alpha mono sulpho acid, and about 5 parts
of sodium acetate. The combination is completed by carefully heating, at about
60 degrees centigrade. After rendering the solution alkaline, the dye-stuff is
isolated in the known manner by salting out, filtering off, pressing, and drying.

page_text: The other dye stuffs of the "A series," derived from phenylene diamine, or
naphthylene diamines, or the like, containing but one diazotisable amido group, are
transformed in a manner analogous to that described in the last example, viz., by
diazotising them, and combining the resulting diazo products with one molecular
proportion of 18 dihydroxynaphthalene alpha mono sulpho acid. In place of the
latter acid, other dibydroxynaphthalene sulpho acids, or naphthol sulpho acids,
amidonaphthol sulpho acids, or, speaking generally, amines, phenols, amido phenols,
amido phenolethere, sulpho or carboxylic acids thereof, can be employed.
The dye-stuffs so formed in general yield shades varying from violet black,
bluish black, or greenish black, to pure black, remarkable for their great intensity
and fastness.
A group of new colouring matters, hereinafter called the "C series," results on
combining one molecular proportion of the diazotised monacetyl para phenlene
diamine, or monacetyl naphthlene diamine, or the like, with one molecular propor-
tion of one of the above middle components," diazotising, coupling the so-formed
diazo products with one molecular proportion of the same or another "middle
component," rediazotising, combining the resulting diazo compounds with one
molecular proportion of a dihydroxynaphthalene sulpho acid, or amidonaphthol
sulpho acid, and subsequently splitting off the acetyl group.
The dye stuffs of the "C series " can also be prepared by coupling the diazo
derivatives of para nitraniline, or nitronaphthylamines, or the like, with one
molecular proportion of one of the above "middle components," diazotising, com-
bining the diazo products so formed with one molecular proportion of the same, or
another "middle component," rediazotising, coupling the diazo compounds thus
obtained with one molecular proportion of a dihydroxynaphthalene sulpho acid, or
amidonaphthol sulpho acid, and subsequently reducing the nitro dye stuff so
formed by means of suitable reducing agents.
The production of these new dye-stuffs which belong to the "C series," is
illustrated by the following example. The parts are by weight.
DYE
STUFF FROM EQUIMOLECULAR PROPORTIONS OF PARA PHENYLENE 3
DIAMINE, ALPHA NAPHTHYLAMINE, ALPHA AMIDONAPHTHOL (1.5), AND
1.8 AMIDONAPHTHOL BETA DISULPHO ACID.
The amidoazo compound used is that produced from 1-5 parts of monacetyl para
phenylene diamine and 1-43 parts of alpha naphthylamine, as described in the

page_text: It is filtered off, mixed with about 30 parts of water, and 6 parts of soda lye
(35 degrees Baumé), and the mixture is heated to boiling, until the acetyl group
has been separated. The dye stuff so formed is separated from the resulting
alkaline solution by salting out, filtering off, pressing, and drying. It possesses the
O following formula :-
1
The shades produced therewith on unmordanted cotton, are bluish-black.
The analogous dye stuffs are obtained on employing, in place of 1-8-amido-
naphthol beta disulpho acid used in the last example, other amidonaphthol sulpho
acids or dihydroxynaphthalene sulpho acids, or on replacing the "middle
components," alpha naphthylamine, and. amidonaphthol (1-5), by other of the
above enumerated "middle components" (employing either the same or two
different ones), or on employing, in place of monacetyl para phenylene diamine,
monacetylnaphthylene diamines. It the nitroproducts, viz., para nitraniline, or
nitronaphthylamines, are employed, the nitro groups contained in the nitro dye
stuffs are reduced at the appropriate time, this process being carried out when the
corresponding acetylated dye-stuffs have been hydrolized, as described in the above
eighth example.

page_text: "
"
Just as in the case of the dye-stuffs of the "A series, the colouring matters
of the C series can also be rediazotised, and then combined either with one or
two of the known dye-stuff components (employing in the latter case either the
same or two different compounds), colouring matters of a new "D series' are
obtained in this manner. The production of these latter dye stuffs, viz., the con-
version of the colouring matters of the "C series" into the corresponding products
of the D series, is effected in a manner analogous to that whereby the products of
the A series are converted into those of the "B series," which process is illustrated
by the above sixth example. The resulting products possess dyeing properties
similar to those of the above "B series," and likewise yield shades remarkable
for their intensity and fastness.
My foreign correspondents describe, by way of example, the dye-stuff which is
obtained by further diazotising the product obtained as described in the above
eighth example, and combining the resulting tetrazo compound with two molecular
proportions of 1:8 dihydroxynaphthalanealphamono sulpho acid. This coloring
matter of the "D series" may be be represented, in accordance with the manner
in which it is produced, by the following formula:
DYE STUFF OBTAINED BY FURTHER DIAZOTISING THE PRODUCT FOrmed as
DESCRIBED IN THE PRECEDING EIGHTH EXAMPLE, AND COUPLING THE
RESULTING TETRAZO COMPOUND WITH TWO MOLECULAR PROPORTIONS
OF 1:8 DIHYDROXYNAPHTHALANE-ALPHA-MONO SULPIO ACID.
8 parts of the coloring matter obtained as described in the preceding las
example, from equal molecular proportions of monacetylated para-phenylene
diamine, alpha-naphthylamine, amidonaphthol (1-5), and 1:8 amidonaphthol beta
disulpho acid, are mixed with water.
After the addition of a concentrated solution, in water, of 1-4 parts of sodium
nitrite, the mixture is acidulated with muriatic acid, and, when the diazotisation is
complete, it is introduced into a solution, in water, of 5.24 parts of 1-8 dihydroxy-
naphthalene alpha-monosulphonate of sodium, and about 10 parts of sodium
acetate. To complete the action, the mixture is heated during a short time at
about 60 degrees centigrade, and the solution having been made alkaline, the dye
stuff is isolated by salting out, filtering off, pressing, and drying.
}
My foreign correspondents have further produced a new group of dye stuffs by
combining the diazo-derivatives of the aforesaid monaceto-diamido compounds, or
nitramido products, with one molecular proportion of one of the so called "middle
components," either splitting off the acetyl group, or reducing the nitro group
contained in the acetyl or nitro compounds thus produced; rediazotising the
diamidoazo products so formed, and coupling the resulting tetrazo derivatives with
two molecular proportions of the so called "last components," employing either the
same or two different compounds.

page_text: by the following example. The parts are by weight.
TENTH EXAMPLE.
UL
ScriCS
:
COLOURING
1:4 NAPHTHYLENE
ONE
MATTER OBTAINED FROM MONACETYL
DIAMINE, BY COUPLING THE DIAZO DERIVATIVE THEREOF WITH
MOLECULAR PROPORTION OF ALPHA-AMIDO-BETA-NAPHTHOLETHER,
SPLITTING OFF THE ACETYL GROUP, REDIAZOTISING, AND COMBINING.
THE TETRAZO COMPOUND SO FORMED, WITH TWO MOLECULAR PROPOR-
TIONS OF AMIDONAPHTHOL MONO SULPHO ACID G.
The diazo compound obtained from 2 parts of mono acetyl 1:4 naphthylene
diamine, as described in the foregoing second example, is added to a solution of
1-87 parts of alpha-amido beta naphtholether, made acid by adding muriatic acid.
When the combination is complete, the acetyl group is separated. A concentrated
solution, in water, of 14 parts of sodium nitrite is then added, and the mixture is
acidulated with muriatic acid. The tetrazo derivative of the diamido azo
compound first formed is thus, obtained, the said diamido compound having the
formula:
OC,H
SO,Na.
It produces greenish-black shades on unmordanted cotton.
The other dye stuffs of the "E series are obtained in a manner analogous to
that described in the foregoing tenth example, viz.-on replacing the "middle
component" used in the last named example, by another of the above defined
"middle components," or on employing, in place of amidonaphtholmono sulpho.
acid G., other amidonaphthol sulpho acids, or dihydroxynaphthalene sulpho acids,
or on starting from another monacetylnaphthylene diamine, or from monacetyl para
phenylene diamine.
The researches of my foreign correspondents also show that the same colouring
matters can be obtained by employing, in the foregoing tenth example, the diazo
compounds of para-nitraniline, or nitronaphthylamines, or the like, and reducing the
nitro product at the appropriate time.
My foreign correspondents have ascertained that the number of the dye-stuffs
herein before specified can be increased, inasmuch as either the same or two

page_text: different amido naphthol sulpho acids, or dihydroxynaphthalene sulpho acids, or
one of these acids together with another dye-stuff component from the series of
amines, phenols, amidophenols, amidophenolethers, sulpho or carboxylic derivatives
thereof, can be employed.
The colouring matters thus produced yield shades remarkable for their great
intensity and fastness.
My foreign correspondents have further obtained a new group of analogous
colouring matters hereinafter called dye-stuffs of the F series, by combining,
⚫for instance, diazotised monacetyl-para-phenylene diamine, monacetylnaphthalene
diamines, paranitraniline, or mononitronaphthylamines, with phenols, naphthols,
dihydroxynaphthalenes, and the like, or sulpho or carboxylic acids thereof, then
splitting off. the acetyl group, if acetylated diamines be employed, or reducing the
nitro products, if nitroamines be used, rediazotising, coupling the diazo-products
thus obtained with one molecular proportion of a so-called "middle component,"
further diazotising, and subsequently combining with amidonaphthol sulpho acids,
or dihydroxynaphthalene sulpho acids.
The method of producing these new dye-stuffs of the "F series," is illustrated
by the following example, the parts being by weight.
COLOURING MATTER OBTAINED FROM EQUAL MOLECULAR PROPORTIONS OF
PARANITRANILINE, ALPHANAPHTHOL ALPHA MONOSULPHO ACID (1:4),
CLEVE'S ALPHANAPHTHYLAMINE ΜΟΝΟ SULPHO ACID DELTA, AND
1.8 DIHYDROXYNAPHTHALENE ALPHA MONO SULPHO ACID, S.
The diazo compound obtained from 1.38 parts of paranitraniline in the usual
manner is combined with 2.46 parts of the sodium salt of alphanaphtholalpha-
mono sulpho acid (1:4), in a solution rendered and kept alkaline by the addition
of sodium carbonate. When the combination is complete, the resulting nitro azo
product is suitably reduced (profitably by means of alkaline reducing agents),
and converted into the corresponding amido azo product represented by the
following formula:
This amido azo compound is rediazotised in presence of muriatic acid by means
of 0-7 parts of sodium nitrite, and the diazo compound thus obtained is introduced
into a solution, in water, of 2.45 parts of the sodium salt of Cleve's alphanaphthyl-
amine beta mono sulpho acid delta, and about 5 parts of sodium, acetate. To 3
complete the action, the mixture is heated during a short time at about 60 degrees
centigrade, and after rendering the liquid alkaline, the resulting interinediate
product is isolated by salting out and filtering off. It possesses the following
formula :-

page_text: It is mixed with water, and a concentrated solution, in water, of 0-7 parts of
sodium nitrite, and the mixture is then acidated with muriatic acid. When the
diazotisation is complete, the mixture is introduced into a solution prepared by
dissolving 2.62 parts of the sodium salt of 1:8 dihydroxynaphthalene alphamono
5 sulpho acid S., and about 5 parts of sodium acetate in water. In order to complete
the action, it is then gently heated at about 60 degrees centigrade. After rendering
the liquid alkaline, the dyestuff is salted out, filtered off, pressed, and dried. Its
composition is represented by the following formula:
It produces, on cotton, bluish-black shades of high intensity.
The corresponding dye-stuffs derived from naphthylenediamines are obtained if, in
the preceding eleventh example, paranitraniline is replaced by nitronaphthylamines.
The same products are obtained on starting from monacetylparaphenylenediamine,
or monacetylnaphthylenediamines, and separating the acetyl group at the
appropriate time.
The alpha naphthol alpha mono sulpho acid (1-4) employed in the preceding
eleventh example, can be replaced by other naphthol sulpho acids, or, in general,
by phenols, naphthols, dihydroxynaphthalenes, sulpho or carboxylic acids thereof,
and the alpha naphthylamine mono sulpho acid (Clève's delta acid) employed in
the same example can be replaced by the isomeric beta acid, or the alphanaphthyl-
amine ortho mono sulpho acid, or another of the above enumerated "middle com-
ponents," and in place of the 1.8 dihydroxynaphthalene alpha mono sulpho acid
used in the same example, other dihydroxynaphthalene sulpho acids, or amido
naphthol sulpho acids, can be employed.
"
My foreign correspondents have further converted the dye-stuffs of the "F. series
which contain, as last components, an amidonaphthol sulpho acid, into new valuable
colouring matters of the "G. series," by further diazotising, and combining with
amines, phenols, amidophenols, amidophenolethers, sulpho or carboxylic acids
thereof.
The production of these new colouring matters of the "G. series," is carried out
by employing monacetyl para phenylene diamine, para nitraniline, monacetyl
naphthylene diamines, or nitro-naphthylamines, as original products, using the
above defined "middle components" and amidonaphthol, or dihydroxynaphthalene
sulpho acids, while, as further components, phenols, naphthols, dihydroxynaph-
thalenes, sulpho and carboxylic acid derived therefrom, or, speaking generally, the
above "last components can be employed.
"
The manufacture of the new dye-stuff's belonging to the "G. series," is illustrated
by the following example; the parts are by weight.

page_text: diamine, is coupled with 2:46 parts of the sodium salt of beta naphthol-beta-mono
sulpho acid (26), the solution being profitably rendered and kept alkaline by the
addition of sodium carbonate. When the combination is complete, the acetyl
group is split off (for instance, by heating the acetyl derivative thus formed with
diluted alkalies), and the resulting intermediate amido azo compound is isolated by
salting out and filtering off. It possesses the following formula:
It is mixed with water, and after adding a solution of 0.7 parts of sodium nitrite,
muriatic acid is slowly introduced, until the mixture is acid. The diazotisation
being complete, the mixture is introduced into a solution of 2.61 parts of the
sodium salt of amido naphthol mono sulpho acid G., and a suitable quantity of
sodium carbonate is added. After several hours, the combination is completed by
slowly heating. The product is isolated by salting out and filtering off. Its
composition is represented by the following formula:
It is diazotised by means of 0.7 parts of sodium nitrite in presence of muriatic
acid, and the mixture thus obtained, containing the diazo derivative of the aforesaid
intermediate product, is introduced into a solution of 2.46 parts of the sodium salt

page_text: of alpha naphthol alpha mono sulpho acid (1:5) in water, rendered alkaline by the
addition of sodium carbonate. The resulting dye-stuff is isolated by salting out,
filtering off, pressing, and drying. It possesses the following formula:
It produces, on unmordanted cotton, bluish-black shades in an alkaline soap bath.
My foreign correspondents have prepared dye-stuffs analogous to the last named,
by following the directions given in the last example, viz., by employing, in place of
beta naphthol beta mono sulpho acid (2: 6) and alpha naphthol alpha mono sulpho
acid (15), other naphthol sulpho acids, or, in general, phenols, naphthols,
dihydroxynaphthalenes, sulpho or carboxylic acids thereof, or by starting from the
monacetyl products of the isomeric naphthylene diamines, or para phenylene
diamine, or by replacing the alpha amido beta naphthol ether delta mono sulpho
acid, by the isomeric alpha amido beta naphthol ether beta mono sulpho acid, or
other "middle components," or by employing, in place of amido naphthol sulpho
acid G., other amido naphthol sulpho acids.
If the nitramines, for instance, para nitraniline, or nitro naphthylamines, be
employed in the first instance, the nitro group must be converted into the amido
group at the appropriate time.
My foreign correspondents have further produced a series of new dye-stuffs
("the H series"), by a method analogous to that described in the last named
example, viz., by coupling not only one "middle component," but two "middle
components,"
"the one after the other, and further treating the intermediate
products so formed, containing two "middle components," in the manner illustrated
by the above twelfth example, and specified herein before.
The production of these new dye-stuffs of H series is effected in a manner
analogous to that described in the last example. The resulting colouring matters
produce shades similar to those obtained by means of the dye stuffs of the
"G series."
The researches of my foreign correspondents have shown that the colouring
matters herein before specified, and belonging to the A. B. C. D. E. F. G.
and H series, are not only suitable for dyeing unmordanted cotton, but that they
can be profitably employed for dyeing wool, and are also capable of dyeing half
woollen materials in equal shades, and that they can be discharged when dyed on
wool.
The said colouring matters are superior to other analogous products by reason of
these valuable properties.
My foreign correspondents have described in the above twelve examples, certain
methods of producing the colouring matters belonging to the said series, but the
dye-stuffs named in these examples, and the analogous products hereinbefore
defined, can also be obtained in other ways, viz., by means of all the methods known
to chemists, and generally in use for the production of analogous colouring matters.
The nature of . this invention is not altered by such variatious, as this invention
communicated to me by my foreign correspondents, in general relates to the
manufacture of eight series of analogous dye stuffs derived from diamido compounds

page_text: of the benzene or naphthalene series, and containing, as chief components, amido
naphthol sulpho acids, or dihydroxynaphthalene sulpho acids, the above specified
"middle components," and the substances which are above enumerated, and briefly
termed "last components."
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 hereinbefore described processes for producing azo dye-stuffs from
diazotised monaceto diamines, or mononitro monamido compounds of the benzene or
naphthalene series, and the herein before defined "middle components" (para
xylidine, orthamido para cresolether, metamido para cresolether, amidonaphthol,
amidonaphtholether, amidonaphthol sulpho acid, amidonaphtholether sulpho acid,
amidonaphthoxyacetic acid, amidonaphthoxyacetic sulpho acid, alpha naphthyl-
amine-ortho-mono sulpho acid, Clève's alpha naphthylamine-beta-mono sulpho
acid, beta or delta, or other amido products of the benzene or naphthalene series,
excluding, however, those amido compounds which, when combined with diazo
derivatives, do not yield true amido azo products, which can be further diazotised),
and amidonaphthol sulpho acids, or dihydroxynaphthalene sulpho acids.
a
2. The production of dye-stuffs by coupling one molecular proportion of a
diazotised monaceto diamine of the benzene or naphthalene series, with one
molecular proportion of "middle component," rediazotising the amido azo products
so formed, combining the resulting diazo compound with one molecular proportion
of an amidonaphtholsulpho acid, or a dihydroxynaphthalene, sulpho acid, and
subsequently separating the acetyl group.
3. The manufacture of colouring-matters by combining one molecular proportion
of a diazotised mononitro monamido compound of the benzene or naphthalene series,
with one molecular proportion of a "middle component,” rediazotising the amidoazo
product so formed, combining the resulting diazo product with one molecular
proportion of an amidonaphol sulpho acid, or a dihydroxynaphthalene sulpho acid,
and subsequently converting the nitrazo products so formed into the corresponding
amidoazo dye-stuffs, by treatment with suitable reducing agents.
4. The conversion of the colouring-matters produced in the manner described in
the foregoing second and third claims, or by any other process, into new dye stuffs,
by rediazotising them, and coupling the tetrazo or diazo products so formed,
respectively, with either two or a single molecular proportion of the known
dye-stuff components (employing in the former case either the same or two different
compounds).
5. The production of dye-stuffs which process consists in combining one molecular
proportion of a diazotised monaceto diamine of the benzene or naphthalene series,
with one molecular proportion of a "middle component," diazotising the amidoazo
compound so formed, combining the resulting diazo product with one molecular
proportion of the same or another "middle component," rediazotising the amidoazo
compound thus obtained, coupling the resulting diazo products with one molecular
proportion of an amidonaphthol sulpho acid, or a dihydroxynaphthalene sulpho
acid, and subsequently separating the acetyl group.
6. The manufacture of colouring-matters by combining one molecular proportion
of a diazotised mononitromonamido compound of the benzene or naphthalene series,
with one molecular proportion of a "middle component," diazotising the amidoazo
compound so formed, combining the resulting diazo product with one molecular
proportion of the same or another "middle component," rediazotising the amidoazo
compound thus obtained, coupling the resulting diazo product with one molecular
proportion of an amidonaphthol sulpho acid, or a dihydroxynaphthalene sulpho
acid, and converting the nitroso product so formed into the corresponding amidoazo
dye-stuff by a subsequent treatment with suitable reducing agents.
7. The conversion of the dye-stuffs, produced as described in the foregoing fifth
and sixth claims, or by any other process, into other colouring-matters, by

page_text: rediazotising them, and coupling the resulting tetrazo or diazo products, respectively,
with either two or a single molecular proportion of the known dye-stuff components
(employing in the former case either the same or two different compounds).
8. The manufacture of colouring-matters by combining one molecular proportion
of a diazotised monaceto diamine of the benzene or naphthalene series, with one
molecular proportion of a "middle component," separating the acetyl group,
rediazotising the resulting diamidoazo products, and coupling the tetrazo compounds
so formed with two molecular proportions of the known dye-stuff components
(employing either the same or two different compounds).
9. The production of dye-stuffs by coupling one molecular proportion of a
diazotised mononitromonamido compound of the benzene or naphthalene series, with
one molecular proportion of a "middle component," reducing the nitro group
contained in the resulting nitroazo products, rediazotising the diamidoazo products
so formed, and combining the resulting tetrazo compounds with two molecular
proportions of the known dye-stuff components (employing either the same or two
different compounds).
10. The process for producing colouring-matters, by combining one molecular
proportion of a diazotised monoaceto diamine of the benzene or naphthalene series,
with one molecular proportion of phenol, naphthol, dihydroxynaphthalene, a sulpho
or carboxylic acid thereof, or another derivative thereof, destitute of the amido
group, separating the acetyl group, diazotising the resulting amidoazo compound,
coupling the diazo product so formed with one molecular proportion of a "middle
component," rediazotising and coupling the diazo product so formed with one
molecular proportion of an amido naphthol sulpho acid, or a dihydroxynaphthalene
sulpho acid.
11. The production of dye-stuffs by coupling one molecular proportion of a
diazotised mononitromonamido compound of the benzene or naphthalene series,
with one molecular proportion of a phenol, naphthol, dihydroxynaphthalene, a
sulpho or carboxylic acid thereof, or another derivative thereof, destitute of the
amido group, reducing the nitro group contained in the resulting nitrazo compound,
diazotising the amidoazo product so formed, coupling the resulting diazo product
with one molecular proportion of a "middle component," rediazotising, and coupling
the diazo product so formed, with one molecular proportion of an amidonaphthol
sulpho acid, or a dihydroxynaphthalene sulpho acid.
12. The conversion of the dye-stuffs which result in the manner described in the
foregoing teuth and eleventh claims, or by any other process, and which contain an
amido group which is further diazotisable, into new dye-stuffs, by rediazotising
them, and combining the resulting diazo products with one molecular proportion of
the known dye-stuff components.
13. The manufacture of colouring-matters by combining one molecular proportion
of a diazotised monaceto diamine of the benzene or naphthalene series with one
molecular proportion of a phenol, naphthol, dihydroxynaphthalene, or a sulpho or
carboxylic acid thereof, or another derivative thereof destitute of the amido group,
separating the acetyl group, diazotising, combining the resulting diazo product with
one molecular proportion of a "middle component," rediazotising, combining the
diazo product thus formed with one molecular proportion of the same or another
"middle component," rediazotising, and subsequently combining the diazo compound
so formed with one molecular proportion of an amidonaphtholsulpho acid, or a
dihydroxynaphthalene sulpho acid, or another dye-stuff component.
14. The production of dye-stuffs by coupling one molecular proportion of a
diazotised mononitromonamido compound of the benzene or naphthalene series, with
one molecular proportion of a phenol, naphthol, dihydroxynaphthalene, or a sulpho
or carboxylic acid thereof, or another derivative thereof destitute of the amido
group, reducing the nitro group, diazotising, combining the resulting diazo product
with one molecular proportion of a "middle component," rediazotising, combining
the diazo product thus formed with one molecular proportion of the same or
another "middle component," rediazotising, and subsequently combining the diazo

page_text: product so formed with one molecular proportion of an amidonaphthol sulpho acid,
or dihydroxynaphthalene sulpho acid, or another dye-stuff component.
15. As new products of manufacture, the new colouring-matters produced in the
manner hereinbefore described, or by any other process producing the same result.
Dated this 31st day of July 1893.
NEWTON & SON,
Agents for the Applicant.