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

page_text: Date of Application, 10th Apr., 1893
Complete Specification Left, 10th Jan., 1894-Accepted, 17th Mar., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of Dye-stuffs.
I HENRY EDWARD NEWTON of The Office for Patents, 6 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 the English Letters Patent No. 13443, dated 26th August
1890, a process is described for producing mixed tetrazo dye-stuffs, which process
consists in the action of tetrazo derivatives of diamines, first on one molecular
proportion of amido naphthol disulpho acid, or a₁ a-amidonaphthol B, ẞ, disulph
acid (obtainable by melting, with alkalies, the alphanaphthylaminetrisulpho acid
produced by subsequently nitrating and reducing from the naphthalenetrisulpho
acid described in the German Patent No. 38281), and in then combining the so-
formed intermediate products with one molecular proportion of an amine, a phenol,
naphthol, dihydroxynaphthalene, or a sulpho or carboxylic acid thereof.
By the expression "amine" used in the Specification of the said Letters Patent
No. 134430, my foreign correspondents of course mean not only the mono amines of
the benzene or naphthalene series, but also the diamines of these two series, for
instance, phenylene diamine, toluylene diamine, naphthylene diamine, and the like.
Such or similar diamines can be employed in the above process, either as such, or
in the state of the derivatives thereof; for example, as sulpho or carboxylic or
alkylated derivatives thereof.
My foreign correspondents have further mentioned in the said Specification, that
the above mixed tetrazo dye stuffs also can be obtained inversely, that is to say, by
combining the tetrazo compounds of diamines, first with one molecular proportion
of an amine, a phenol, naphthol, dihydroxynaphthalene, and so on, and subsequently
acting with the thus formed intermediate products on the amidonaphtholdisulpho
acid (likewise employing one molecular proportion of the latter).
These mixed tetrazo dye stuffs, produced in the one or the other manner, are
capable of dyeing unmordanted cotton, and yield different shades according to
the components employed. For instance, the coloring matters resulting from
equal molecular proportions of a tetrazo compound, amidonaphtholdisulpho acid,
and a diamine or substituted diamine, yield shades varying from greyish-violet to
brown.
My foreign correspondents have now found, that dye stuffs of a much greater
intensity and coloring power are obtained by further acting on the above mixed
tetrazo dye stuffs, either with one molecular proportion of a diazo compound, or
diazoazo compound, or with half a molecular proportion of a tetrazo compound, or
with one molecular proportion of an intermediate product, resulting from the
combination of equal molecular proportions of a tetrazo derivative of "benzidine,
its analogues or homologues," and an amine, a diamine, phenol, amidophenol,
amidophenolether, of the benzene or naphthalene series, or a sulpho or carboxylic
acid thereof.
My foreign correspondents have proved that the products employed in the said
process as last components (viz., diazo compounds, diazoazo products, and so on),

page_text: which can be coupled either in alkaline or in acetic solution (in the latter case in
the presence of sodium acetate), enter into combination with the diamine which forms
a component part of the original dye stuffs.
My foreign correspondents have further found, that, in the above process, the
amidonaphtholdisulpho acid can be replaced by other amidonaphtholsulpho acids
(such as amidonaphtholsulpho acid G or B, or the like), by alphanaphthylamine
betamonosulpho acid (16), alphanaphthylamine delta monosulpho acid (1-7),
alphanaphthylamine orthomonosulpho acid, amidonaphthols, amidonaphtholethers,
amidonaphtholether sulpho acids, amidonaphthoxyacetic acids, amidonaphthoxy-
acetic sulpho acids, dihydroxynaphthalenes, or sulpho derivatives of these com-
ponents. All these components will be briefly termed, in this Specification,
"naphthalene derivatives."
The mixed tetrazo dye stuffs resulting from the combination of one molecular
proportion of a tetrazo compound (in any order) with one molecular proportion of
one of these "naphthalene derivatives," and with one molecular proportion of a
diamine or substituted diamine (such as phenylene diamine, toluylene diamine,
naphthalene diamine, or the like, or sulpho or carboxylic or alkylated derivatives
thereof), can be combined either with one molecular proportion of a diazo com-
pound or diazo azo compound, half a molecular proportion of a tetrazo compound,
or one molecular proportion of a so-called intermediate product hereinbefore defined.
By the expression "benzidine, its analogues or homologues," my foreign
correspondents mean benzidine, tolidine, diamidodiphenytolyl, diamidodiphenol-
ether, diamidoalkylhydroxydiphenyl, diamidoalkylhydroxyphenyltolyl, diamidoazo-
benzene, diamidoazotoluene, diamidoazoxylene, diamidoazoxybenzene, diamido-
azoxytoluene, diamidostilbene, diamidofluorene, diamidonaphthalene, diamido-
carbazol, diamidodiphenylene, oxide, diamidoditoluylene oxide, paraphenylene
diamine, paratoluylene diamine, benzidine sulphone, tolidine sulphone, diamide-
phenyltolyl sulphone, diamidophenoxyacetic acid, diamidodiphenylene ketoxine,
m- p- diamidophenylbenzimidazol, amidobenzeneazoalphanaphthylamine, amido-
tolueneazoalphanaphthylamine, amidoxyleneazoalphanaphthylamine, amidobenzene-
azoparaxylidine, amidotolueneazoparaxylidine, amidoxyleneazoparaxylidine, amido-
-benzeneazometa (or ortho) amidoparacresolalkylether, amidotolueneazometa (or
ortho) amidoparacresolalkylether, amidoxyleneazometa (or ortho) amidopara-
cresolalkylether, amidobenzeneazobetaalkyloxyalphanaphthylamine, amidotoluene-
azobetaalkyloxyalphanaphthylamine, amidoxyleneazobetaalkyloxyalphanaphthyl-
amine, or sulpho and carboxylic derivatives thereof.
Of course, other diamines, or sulpho, derivatives thereof, which can be converted
into tetrazo compounds, either directly, or by means of their monoacetyl compounds,
likewise can be used in the above process. In place of the mono-acetylised
diamines, the corresponding mononitro amines, or substituted mononitro amines,
can be employed; in the latter case, the first obtained nitro azo products must be
reduced, whilst the corresponding acetylised intermediate products must be
treated at the same time in a suitable manner for separating the acetyl group.

page_text: In order to illustrate the method of producing these new coloring matters, the
following examples are given, the parts being by weight :-
COLORING MATTER FROM DIANISIDINE,
DIHYDROXYNAPHTHALENE MONO
SULPHO ACID, META PHENYLENE DIAMINE, AND DIAZO NAPHTHALENE
DISULPHO ACID.
The intermediate product resulting from the combination of the tetrazo
derivative of 244 parts of dianisidine with 26-5 parts of dihydroxynaphthalene-
monosulphonate of sodium, in acidulated solution, in the presence of sodium
0 acetate, is coupled with 10-8 parts of meta phenylene diamine. The diazo
compound obtained from 32 parts of beta naphthylamine disulpho acid is stirred
into the above liquid. After some time, sodium carbonate is added, and the
mixture is heated. The thus-formed dye stuff is salted out, filtered off, and pressed.
It possesses the following composition :
DYE STUFF FROM BENZIDINE, AMIDO
NAPHTHOLDISULPHO ACID, META-
PHENYLENE DIAMINE, AND DIAZO NAPHTHALENE.
184 parts of benzidine, dissolved in 50 parts of muriatic acid (containing 33 per
cent. of pure acid), and in the necessary quantity of water, are converted into
tetrazo diphenylchloride in the known manner, by means of 14 parts of sodium
nitrite dissolved in 70 parts of water. The resulting tetrazo solution is allowed to
flow into a cold solution of amidonaphtholdisulphonate of sodium (corresponding
to 32 parts of amidonaphtholdisulpho acid), to which solution 40 parts of sodium
acetate were added. The formation of the intermediate products proceeds
immediately, and is finished after a short time. A solution prepared by
dissolving 10-8 parts of metaphenylenediamine in the necessary quantity of
muriatic acid, is added, and the resulting mixture is rendered alkaline by means
of sodium carbonate. After heating to the boiling point, the dye stuff is isolated
by salting out, filtering off, pressing, and drying.
The combination of the amido naphtholdisulpho acid also can be effected in
alkaline solution.
The thus formed product is dissolved in water, and after adding sodium carbonate,
a solution of diazonaphthalene prepared from 14.3 parts of alpha naphthyl amine
is allowed to flow into the latter solution. In order to complete the reaction, the

page_text: It produces violet brown shades on unmordanted cotton.
In a manner analogous to that described in the above examples, other coloring
matters can be obtained, viz., either by replacing the dihydroxynaphthalene
sulpho acid, or amidonaphtholdisulpho acid, by other components of the aforesaid
"naphthalene derivatives," or by using, in place of meta phenylene diamine, the
corresponding quantities of meta toluylene diamine, naphthylene diamine, the
sulpho, carboxylic, or alkylated derivatives of these or similar diamines, or by
employing, in place of diazonaphthalene disulpho acid, or diazo naphthalene, one
molecular proportion of another diazo compound, or diazoazo product.
The diazo compounds, or diazoazo compounds, used as last components, may
be replaced either by half a molecular proportion of a tetrazo compound, or
by one molecular proportion of an intermediate product resulting from the
combination of a tetrazo salt with an amine, a diamine, phenol, amido
phenol, amidophenolether of the benzene or naphthalene series, or a sulpho or
carboxylic derivative thereof.
66
These processes consist in acting with one molecular proportion of a dye
stuff from "benzidine, its analogues or homologues," and one of the said
naphthalene derivatives," and a diamine or substituted diamine, either on half
a molecular proportion of tetrazo compound, or on one molecular proportion of
an intermediate product hereinbefore defined.
In this manner, new dye stuffs result, which likewise are distinguishable by
the beauty and intensity of the shades produced therewith.
The production of these dyestuffs can be illustrated by the following examples.
The parts are by weight.
COLORING MATTER FROM BENZIDINE, AMIDO NAPHTHOLDISULPHO
ACID, 3
META PHENYLENE DIAMINE, AND TETRAZO DIPHENYLCHLORIDE.
The coloring matter obtainable (as described in the above second example) from
equal molecular proportions of benzidine amidonaphtholdisulpho acid and metal
phenylene diamine, is dissolved in water with the addition of sodium carbonate. A
solution of tetrazo diphenyl chloride prepared in the usual manner from 9-2 parts 3
of benzidine, is then allowed to flow into the above liquid. The formation of the
dye stuff begins immediately, and is finished after a short time.

page_text: DYE-STUFF FROM BENZIDINE, AMIDO NAPHTHOL DISULPHO ACID, META
PHENYLENE DIAMINE, AND THE INTERMEDIATE PRODUCT FROM EQUAL
MOLECULAR PROPORTIONS OF TETRAZO DIPHENYL CHLORIDE AND
ALPHA NAPHTHYLAMINE-BETA-MONOSULPHO ACID (1.6).
The coloring matter resulting (as described in the above second example) from
tetrazo-diphenylchloride, amido naphtholdisulpho acid, and meta phenylene
diamine, is dissolved in water with the addition of the corresponding quantity of
sodium carbonate. The resulting solution is mixed with a solution obtained by
combining one molecular proportion of tetrazo diphenylchloride with one molecular
proportion of alpha naphthylamine beta monosulpho acid (1-6). After a short
time, the formation of the new dye stuff is completed. The latter is isolated in the
usual manner, and produces on unmordanted cotton, reddish brown shades
characterised by their intensity.

page_text: It is to be noted, that the coloring matters resulting in the manner hereinbefore
defined (in case they are insoluble in water, or soluble with difficulty in water,
which may be the case when employing amido naphthols, amido naphtholethers,
amido naphthoxyacetic acid, or dihydroxynaphthalenes), can, by subsequent
treating with sulphonating agents, be converted into dye stuffs readily soluble, and
therefore possessing great technical value.
The same effect results, if the first produced intermediate products are treated
with sulphonating agents.
As hereinbefore mentioned, the products employed as last components viz., diazo
compounds, diazoazo products, tetrazo compounds, or the so-called intermediate
products containing a free diazo group, and obtainable from the combination of
equal molecular proportions of a tetrazo salt and any component (such as amine,
diamine, phenol, amidophenol, amidophenolether of the benzene or naphthalene
series, or a sulpho or carboxylic derivative thereof), enter into combination with
the diamine or substituted diamine which has been used for producing the original
mixed tetrazo dye-stuff.
It is evident, that the coloring matters obtained by means of the above processes,
contain the residue of the tetrazotised diamine, the "naphthalene derivative," and
a diamido azo compound, or triamido azo compound, or tetra amido azo compound,
or the like, according as diazo products, diazo azo compounds, tetrazo compounds,
or intermediate products from equal molecular proportions of tetrazo compounds, and
other components, have been used.
My foreign correspondents have further found, that the same or similar dye stuffs,
likewise producing on unmordanted cotton brownish shades in general, result by
combining one molecular proportion of a polyamidoazo compound (such as diamido-,
triamido-, or tetraamidc-azo products, or the like), an alkylated derivative thereof, or
another substitution product of amido azo compounds, with one molecular proportion
of an intermediate product, from equal molecular proportions of a tetrazo compound,
and one of the above "naphthalene derivatives."
By the above polyamidoazo products, my foreign correspondents in general
understand the products resulting from the combination of diazo compounds, tetrazo
compounds, or diazo azo products, with diamines or substituted diamines of the
benzene or naphthalene series, such as meta phenylene diamine, meta toluylene

page_text: COLORING
MATTER FROM BENZIDINE, AMIDONAPHTHOLDISULPHO ACID, AND.
CHRYSOIDINE.
9.2 parts of benzidine are dissolved in the necessary quantity of dilute muriatic
acid, and converted into the tetrazo compound by means of a solution, in water,
of 7 parts of sodium nitrite. A solution prepared by dissolving 18.5 parts of
1:8 amidonaphtholbetadisulphonate of sodium, and 20 parts of sodium acetate,.
in 500 parts of water, is allowed to flow into the above tetrazo solution.
The formation of the intermediate product begins immediately and is finished
after some hours. The intermediate product separates as a black precipitate.
A watery solution of 14 parts of the hydrochlorate of the chrysoidine, which is
obtained from diazo benzene and metaphenylene diamine, is added to the above
liquid, and the resulting mixture is stirred for 24 hours at a temperature from 5 to
10 degrees centigrade; the temperature is then raised to from 40 to 50 degrees
centigrade; and after adding common salt, if it be necessary for separating the
dye stuff, the latter is filtered off, pressed, and dried.
The complete coloring matter possesses the following composition
-

page_text: coupling of the amidonaphtholdisulpho acid can be effected in a moderately weak
alkaline solution. In this case, the resulting liquid must be acidulated by means
of acetic or muriatic acid, before the chrysoidine is added.
The dyestuff obtainable as described in the fifth example, produces brown shades
on unmordanted cotton in an alkaline soap bath.
In the same manner as the analogous dyestuffs of amidonaphtholdisulpho acid,
this latter brown coloring matter can also be further diazotised (either direct, or
after being fixed on the fibre), and combined with the known dye stuff components,
such as beta naphthol, meta phenylene diamine, or the like,-dark brown shades
being thus produced, which are perfectly fust against washing, and against the
action of alkalies and acids.
Analogous dye stuffs producing from brown to violet shades result, if the 1:8
amidonaphthol beta disulpho acid used in the last example is replaced by 1:8
dihydroxynaphthalenealphamonosulpho acid, or 1:8 dihydroxynaphthalene alpha
disulpho acid, or other sulpho acids of amidonaphthol or dihydroxynaphthalene, or
amidonaphtholethersulpho acids, or alphanaphthylaminemonosulpho acids (1:2,
1:6, or 1:7), or amidonaphthoxyacetic acid, or amidonaphthoxyacetic sulpho acid,
or if the chrysoidine employed is replaced by other homologous or analogous chry-
soidines, or dye stuffs of the Bismarck-brown series, by alkyl substitution products,
or sulpho or carboxylic derivatives thereof.
Similar results are obtained if, in place of benzidine, other diamines or substituted
diamines or sulnho or corbovulio derivatives thereof are emploved
COLORING MATTER FROM AMIDO BENZENEAZO
ALPHANAPHTHYLAMINE
BISMARCK BROWN SULPHO ACID.
AND
This dyestuff is obtained by allowing the product from the diazo derivative of
26.5 parts of amido benzeneazo alpha naphthylamine, and 24.5 parts of gamma-
amidonaphthol mono sulpho acid (in alkaline solution) to act on the Bismarck
brown sulpho acid which is formed by coupling 10-8 parts of meta phenylene
diamine, with the diazo product of 10 parts of toluylene diamine sulpho acid.
This process is effected in a manner analogous to that described in the above
fifth example.
The dyestuff produces brownish shades.
In an analogous manner, coloring matters are obtained from one molecular propor-
tion of a tetrazo compound of the paradiamines hereinbefore defined, one molecular
::.

page_text: proportion of the above "naphthalene derivatives," and one molecular proportion
of a dye stuff out of the series of the "chrysoidiues" and "Bismarck browns,"
or the alkyl derivatives, or sulpho or carboxylic derivatives thereof. These azo
dyestuffs produce on unmordanted cotton, in a neutral or alkaline bath, shades
from brownish to violet.
In place of starting from the tetrazo compounds of paraphenylene diamine,
para toluylene diamine, or naphthylene diamine, the acetyl derivatives of these
diamines can be used.
These acetyl products are then diazotised, combined with a coloring matter of
the "chrysoidine or "Bismarck brown" series, and, after separating the acetyl
group, and rediazotising by means of one or two molecules of nitrous acid, further
coupled with the above naphthalene derivatives. Of course, the diazo products of
acetylised paraphenylene diamine, paratoluylene diamine, or naphthylene diamine,
can first be coupled with the "naphthalene derivatives," and, after separating the
acetyl group and rediazotising, the coloring matters of the series of "chrysoidines
or Bismarck browns," can be coupled.
66
""
Instead of starting from the above acetylised diamines, the corresponding nitro
amines, can be used such as para nitro aniline, metanitro ortho toluidine, or
nitro-naphthylamines, or the like. In this case, the nitro group must be reduced
to the amido group, this process being effected at the same time, that the acetyl-
group contained in the above intermediate products, is separated. The reduction
is carried out by means of gentle reducing agents.
My foreign correspondents have found that the coloring matters hereinbefore
defined (which contain diazotisable amido groups) are of a special technical value,
as they can be further diazotised and combined with one or two molecular
proportions of dyestuff components (employing, in the latter case, either the same
or two different ones), dyestuffs being thus produced which likewise possess
technically valuable properties.
The last-named process can also be effected on the fibre, as, according to the
researches of my foreign correspondents, the above dyestuffs (in case they contain
diazotisable amido groups), when fixed on the cotton fibre, can be diazotised, and
subsequently combined (likewise on the fibre) with the known dyestuff components
(such as betanaphthol, meta phenylene diamine, or the like), shades being thus
produced which are distinguishable by their fastness against washing, and against
the action of acids and alkalies. The shades, in general, are dark brown, and
possess great intensity.
My foreign correspondents have described in the above examples distinct
methods for practically producing some of these new dye stuffs. Of course, they do
not limit themselves to the directions given therein. The latter can be varied,
without altering the nature of this invention. The dyestuffs hereinbefore defined
can be produced by means of all those methods in use for the production of
analogous or similar dye stuffs.
Dated this 10th day of April 1893
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Dye-stuffs.
I HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
50 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 the English Letters Patent No. 13443, dated 26th August

page_text: 1890, a process is described for producing mixed tetrazo dye-stuffs, the which
process consists in allowing a tetrazo derivative of a diamine to act on one molecular
proportion of the amidonaphtholdisulphonic acid (alpha, alpha, amidonaphthol
beta, beta, disulpho acid) obtainable by fusing with alkalies the alphanaphthylamine
trisulphonic acid produced by nitrating the naphthalene trisulphonic acid described
in the German Patent No. 38281, and reducing the nitro products, and in then
combining the intermediate product so formed with one molecular proportion of
an amine, a phenol, naphthol, dihydroxynaphthalene, or a sulphonic or carboxylic
acid thereof.
By the expression “amine” used in the Specification of the said Letters Patent
No. 134430, my foreign correspondents mean not only the monamines of the
benzene or naphthalene series, but also the diamines of these two series, for
instance, phenylene diamine, toluylene diamine, naphthylene diamine, and the like.
Such or similar diamines can be used in the above process, either as such, or in
the state of derivatives thereof, for example, as sulphonic or carboxylic or alkylated
derivatives thereof.
My foreign correspondents have further mentioned in the said Specification, that
the aforesaid mixed tetrazo dye-stuffs can also be obtained by an inverse process,
that is to say, by combining the tetrazo compounds of diamines, first with one
molecular proportion of an amine, phenol, naphthol, dihydroxy naphthalene, or the
like, and subsequently acting with the intermediate product thus formed, on the
amidonaphtholdisulphonic acid, using one molecular proportion of this latter.
The mixed tetrazo dye-stuffs produced by either method, are capable of dyeing
unmordanted cotton, yielding different shades according to the components employed.
For instance, the coloring matters produced from equi-molecular proportions of a
tetrazo compound, the amidonaphtholdisulphonic acid, and a diamine or sub-
stituted diamine, yield shades varying from greyish-violet to brown.
My foreign correspondents have now found, that dye-stuffs of much greater
intensity and coloring power are obtained by further acting on the aforesaid
mixed tetrazo dye-stuffs, either with one molecular proportion of a diazo compound,
or diazo azo compound, or with half a molecular proportion of a tetrazo compound,
or with one molecular proportion of an intermediate product resulting from the
combination of equi-molecular proportions of a tetrazo derivative of "benzidine, its
analogues or homologues," and an amine, diamine, phenol, amidophenol, or amido-
phenolether of the benzene or naphthalene series, or a sulphonic or carboxylic acid
thereof.
My foreign correspondents have proved that the products used in the said process
as last components (viz., the diazo compounds, diazo-azo compounds, and the like,
which can be coupled either in alkaline or in acetic solution, in the latter case
in the presence of sodium acetate) enter into combination with the diamine, forming
a component part of the original dye-stuffs.
My foreign correspondents have further found, that in the above process the
aforementioned amidonaphtholdisulphonic acid can be replaced by other amido-
naphtholsulphonic acids, such as amidonaphtholsulphonic acid G or B, or the like,
or by alpha, naphthylamine betas mono sulphonic acid (1:6), alpha; naphthylamine
beta monosulphonic acid (1:7), alpha, naphthylamine beta, monosulphonic acid,
amidonaphthols, amidonaphtholethers, amidonaphthol ethersulphonic acids, amido-
naphthoxyacetic acids, amidonaphthoxyacetic sulphonic acids, dihydroxynaphtha-
lenes, or sulphonic derivatives of these components. All these components will be
briefly termed, in this Specification, "naphthalene derivatives."
The mixed tetrazo dye-stuffs formed by the combination of one molecular
proportion of a tetrazo compound in any order, with one molecular proportion of
one of these "naphthalene derivatives," and with one molecular proportion of a
diamine or substituted diamine (such as phenylene diamine, toluylene diamine,
naphthylene diamine, or the like, or sulphonic or carboxylic, or alkylated
derivatives thercof) can be combined either with one molecular proportion of a
diazo compound, or diazo-azo compound, or with half a molecular proportion of a

page_text: tetrazo compound, or with one molecular proportion of a so-called intermediate
product herein before defined.
By the expression "benzidine, its analogues or homologues," my foreign
correspondents mean benzidine, tolidine, dinmido-diphenyltolyl, diamidodiphenol-
ether, diamidoalkylhydroxydiphenyl, diamido-alkylhydroxyphenyltolyl, diamidoazo
benzene, diamidoazotoluene, diamido-azo-xylene, diamido azoxybenzene, diamido-
azoxytoluene, diamidostilbene, diamidofluorene, diamidonaphthalene, diamidocarb-
azol, diamidodiphenylene oxide, diamidoditoluylene oxide, para-phenylenediamine,
para-toluylene diamine, benzidine sulphone, tolidine sulphone, diamido phenyltolyl
sulphone, diamidodiphenoxyacetic acid, diamidodiphenyleneketoxime, diamido
phenylbenzimidazol, amido benzeneazoalphanaphthylamine, amidotolueneazoalpha-
naphthylamine, amidoxylene azoalphanaphthylamine, amidobenzene azoparaxyli-
dine, amidotolueneazoparaxylidine, amidoxylene azoparaxylidine, amidobenzene
azometa (or ortho) amido paracresolalkylether, amidotoluene azo meta (or ortho)
amido paracresolalkylether, amidoxylene azo meta (or ortho) amidoparacresolether,
amidobenzeneazobetaalkyl oxyalpha naphthylamine, amidotoluene, azobeta alkyl-
oxyalphanaphthylamine, amido xyleneazobeta alkyloxyalphanaphthylamine, or
sulphonic and carboxylic derivatives thereof.
Other diamines, or sulphonic derivatives thereof which can be converted into
tetrazo compounds, either directly, or by means of their monacetyl derivatives,
can, as a matter of course, be used in the above process. In place of the
monoacetylated diamines, the corresponding mononitramines, or substituted
mononitramines, can be used, in the latter case the nitroazo products first obtained
must be reduced, whilst the corresponding acetylated intermediate products must
be treated in a suitable manner, to separate the acetyl group.
In order to illustrate the method of producing these new coloring matters, the
following examples are given, the parts being by weight :—
COLORING MATTER FROM TETRAZODIPHENOLDIMETHYLether,
ALPHA1
ALPHA DIHYDROXYNAPHTHALENE ALPHA-MONOSULPHONIC ACID,
METAPHENYLENE DIAMINE, AND DIAZOTISED BETA, NAPHTHYLAMINE
BETA, BETA DISULPHONIC ACID.
The intermediate product formed by the combination of the tetrazo derivative
of 24.4 parts of dianisidine, with 26-2.parts of alpha, alpha, dihydroxynaphthalene
monosulphonate of sodium, is coupled, in an acidulated solution, in the presence of
sodium acetate, with 10-8 parts of metaphenylenediamine. The diazo compound
obtained from 30.3 parts of beta, naphthylamine beta, beta, disulphonic acil is
then stirred into the liquid. After a time, sodium carbonate is added, and the
mixture is heated. The dye-stuff' thus formed is salted out, filtered off, and pressed.
It is represented by the following formula :—

page_text: 5247 ELEME
DYE STUFF FROM TETRAZO DIPHENYL-CHLORIDE, ALPHA ALPHA AMIDO-
NAPHTHOL-BETA, BETAB DISULPHONIC ACID, METAPHENYLENE DIAMINE,
AND DIAZONAPHTHALENE.
18.4 parts of benzidine, dissolved in 50 parts of muriatic acid (33 per cent.), and
the necessary quantity of water, are converted into tetrazodiphenylchloride in the
known manner, by means of 14 parts of sodium nitrite dissolved in 70 parts of
water. The resulting tetrazo solution is allowed to flow into a cold solution of
alpha alpha, amidonaphthol beta, beta, disulphonate of sodium, corresponding
to 32 parts of amido-naphtholdisulphonic acid, to which solution 40 parts of
sodium acetate have been added. The formation of the intermediate product
immediately takes place, and is finished after a short time. A solution prepared
by dissolving 10-8 parts of metaphenylenediamine in the necessary quantity of
muriatic acid, is then added, and the resulting mixture is rendered alkaline by
means of sodium carbonate. After heating to the boiling point, the dye-stuff is 1
isolated by salting out, filtering off, pressing, and drying.
The combination of the amido naphtholdisulphonic acid also can be effected in
alkaline solution.
The product thus formed is dissolved in water, together with sodium carbonate,
and a solution of diazonaphthalene, prepared from 14.3 parts of alpha 2
naphthylamine, is allowed to flow into the solution. In order to complete the
action, the mixture is heated to the boiling point, and the dye-stuff is then salted
out, filtered off, pressed, and dried.
Its composition is represented by the following formula :—
It produces violet-brown shades on unmordanted cotton.
Other coloring matters can be obtained in a manner analogous to that described
in the above examples, viz.: either by replacing the dihydroxynaphthalene
sulphonic acid, or amidonaphthol disulphonic acid, by another of the aforesaid
"naphthalene derivatives," or by using, in place of metaphenylene diamine, the
corresponding quantity of metatoluylene diamine, naphthylene diamine, the
sulphonic, carboxylic, or alkylated derivatives of these or similar diamines, or
by using, in place of diazo naphthalenedisulphonic acid, or diazo naphthalene,
one molecular proportion of another diazo compound, or of a diazo compound.
The diazo compounds, or diazo-azo compounds used as last components, may be
replaced either by half a molecular proportion of a tetrazo compound, or by one
molecular proportion of an intermediate product formed by the combination of a
tetrazo salt with an amine, diamine, phenol, amidophenol, amidophenolether of the
benzene or naphthalene series, or a sulphonic or carboxylic derivative thereof.

page_text: These processes consist in acting with one molecular proportion of a dye stuff
from "benzidine, its analogues or homologues," and one of the said “naphthalene
derivatives," and a diamine or substituted diamine, either on half a molecular
proportion of a tetrazo compound, or on one molecular proportion of an
intermediate product hereinbefore defined.
In this manner, new dye-stuffs are forined, which are also distinguished by the
beauty and intensity of the shades which they afford.
The production of these dye-stuffs can be illustrated by the following examples.
The parts are by weight.
COLORING MATTER FROM TETRAZODIPHENYLCHLORIDE, ALPHA1
AMIDONAPHTHOL BETA2 BETA3 DISULPHONIC
DIAMINE, AND TETRAZO DIPHENYL CHLORIDE.
ALPHA
ACID, METAPHENYLENE-
The coloring matter obtainable (as described in the above second example) from
equi-molecular proportions of benzidine, amidonaphtaoldisulphonic acid, and meta-
phenylene diamine, is dissolved in water, together with sodium carbonate. A
solution of tetrazodiphenylchloride, prepared, in the usual manner, from 9-2 parts
of benzidine, is then allowed to flow into the liquid. The formation of the dyestuff
begins immediately, and is finished after a short time.
The mixture is then heated to boiling, and the dye-stuff is afterwards salted out
and pressed. It produces brownish-violet shades on unmordanted cotton. Its
composition is represented by the formula :—

page_text: DYE-STUFF FROM TETRAZODIPHENYLCHLORIDE, ALPHA ALPHA AMIDO-
ACID, META PHENYLENE
DIAMINE, AND THE INTERMEDIATE PRODUCT FROM EQUI-MOLECULAR
NAPHTHOL ВЕТА2 BETA DISCLPHONIC
PROPORTIONS OF TETRAZO DIPHENYLCHLORIDE AND ALPHA NAPHTHYL-
AMINE BETA3 MONOSULPHONIC ACID (1:6).
The coloring matter prepared (as described in the above second example) from
tetrazo diphenylchloride, alpha, alpha4 amidonaphthol beta, beta, disulphonic acid,
and meta phenylene diamine, is dissolved in water, together with the corresponding
quantity of sodium carbonate. The resulting solution is mixed with a solution
obtained by combining one molecular proportion of tetrazo diphenylchloride with
one molecular proportion of alpha, naphthylamine beta, monosulphonic acid (1:6).
The formation of the new dye-stuff is soon completed. The dye-stuff is isolated in
the usual manner. It produces, on unmordanted cotton, reddish-brown shades
characterised by their intensity.
It is represented by the following formula :—
It is to be noted that coloring matters produced in the manner hereinbefore
defined, such as are formed from certain of the aforementioned "naphthalene
derivatives," viz., amidonaphthols, amidonaphtholethers, amido naphthoxyacetic
acid, or dihydroxynaphthalenes, which are either insoluble, or but slightly soluble
in water, can, by subsequent treatment with sulphonating agents, be converted into
dye-stuffs which are readily soluble, and therefore of greater technical value.
The same effect is obtained, if the intermediate products first produced are
treated with sulphonating agents.
The products used as last components, viz. :-diazo compounds, diazoazo
compounds, tetrazo compounds, or the so-called intermediate products containing
a free diazo group, obtainable by combining equi-molecular proportions of a tetrazo
salt and any component (such as an amine, diamine, phenol, amidophenol, amido-
phenolether of the benzene or naphthalene series, or a sulphonic or carboxylic
derivative thereof), as hereinbefore mentioned, enter into combination with

page_text: the diamine or substituted diamine which has been used in producing the original
mixed tetrazo dye-stuff.
The coloring matters obtained by means of the above processes obviously
contain the residues of the tetrazotised diamine, the "naphthalene derivative," and
a diamidoazo compound, or triamido azo compound, or the like.
My foreign correspondents have further found, that the same or similar dye-
stuffs, capable of producing chiefly brownish shades on unmordanted cotton, are
formed by combining one molecular proportion of a polyamido azo compound (such
as diamido azo, triamido azo products or the like), or alkylated derivatives thereof,
or another substitution product of an amidoazo compound, with one molecular
proportion of an intermediate product from equi-molecular proportions of a tetrazo
compound, and one of the above mentioned "naphthalene derivatives."
By the above mentioned polyamido azoproducts, my foreign correspondents, in
general, understand the products resulting from the combination of diazocompounds,
tetrazocompounds, or diazoazo compounds with diamines or substituted diamines
of the benzene or naphthalene series, such as metaphenylene diamine, metatoluylene-
diamine, naphthylenediamines, the mono- or polyalkylated diamines (containing
alkyl radicles, such as methyl, ethyl, amyl, benzyl, phenyl, toly 1, xylyl, alpha or
beta naphthyl, or the like, in the amido group), sulphonic acids of such or similar
diamines, including the products technically known as " chrysoidines," " Bismarck
brown," the analogues or homologues thereof, the alkylated products derived
therefrom, and the sulphonic or carboxylic acids thereof.
The dyestuffs are excluded which are formed as described in the Specification of
Letters Patent No. 15725, dated 16th September 1891, by combining one molecular
proportion of a tetrazo compound with one molecular proportion of amidonaphthol-
disulphonic acid H in alkaline solution, and then with one molecular proportion of
meta toluylene diamine, or chrysoidine, or Bismarck brown.
In order to produce these dyestuffs, the tetrazo compounds of the above defined
paradiamines can be combined first with one of the said "naphthalene derivatives,"
and then with an amidoazo product, or the process can be effected inversely, viz., by
coupling a tetrazo compound first with an amidoazo product, and then with one of
the said "naphthalene derivatives," using, in either case, molecular proportions of
these components.
If the resulting colouring-matters dissolve with difficulty, or are insoluble in
water, which is the case when the so-called "naphthalene derivatives," amido-
naphthols, amidonaphtholethers, amidonaphthoxyacetic acid, or dihydroxynaph-
thalene, are used, such insoluble products can be converted into products which
dissolve in water, by subsequently treating them with sulphonating agents, such
as fuming sulphuric acid, or agents which produce the same or a similar result.
The production of these colouring matters is illustrated by the following
examples. The parts are by weight.
COLOURING
MATTER FROM TETRAZO-DIPHENYLCHLORIDE, ALPHA ALPHA4
AMIDONAPHTHOL-ALPHA, BETA, DISULPHONIC ACID AND CHRYSOIDINE.
9.2 parts of benzidine are dissolved in the necessary quantity of diluted muriatic
acid, and converted into the tetrazo compound by means of a solution, in water, of
7 parts of sodium nitrite. A solution prepared by dissolving 18-2 parts of alpha
alpha, amidonaphthol alpha, beta, disulphonate of sodium and 20 parts of sodium
acetate in 50.) parts of water, then added.
The forination of the intermediate product begins immediately, and is finished
after some hours. The intermediate product separates as a black precipitate.
A solution, in water, of 14 parts of the hydrochloride of the chrysoidine
obtained fron diazobenzene and metaphenylene diamine, is next added to the liquid,

page_text: and the resulting mixture is stirred, during 24 hours, at a temperature from 5 to
10 degrees centigrade.
The temperature is then raised to from 40 to 50 degrees centigrade, and after
adding common salt, if necessary, to separate the dye stuff, the latter is filtered off,
pressed, and dried.
:-
The colouring matter is represented by the following formula :-
Instead of producing the above intermediate product in an acetic solution, the
coupling of the amidonaphthol disulphonic acid can be effected in a moderately
weak alkaline solution, in which case the liquid must be acidulated by means of
acetic or muriatic acid, before the chrysoidine is added.
The dye-stuff obtainable as described in the fifth example, produces brown
shades on unmordanted cotton in an alkaline soap bath.
As in the case of the analogous dye-stuffs of amidonaphtholdisulphonic acid,
this brown colouring matter can be further diazotised, either directly, or when
fixed on the fibre, and combined with the known dye-stuff components, such as
betanaphthol, metaphenylene diamine, or the like, dark brown shades being thus
produced which withstand washing, alkalies, and acids.
Analogous dye-stuffs, producing from brown to violet shades, are formed, if the
alpha, alpha-amidonaphthol-alphag betai-disulphonic acid used in the last example,
be replaced by alpha, alpha-dihydroxynaphthalene alpha, monosulphonic acid, or
alpha, alpha-dihydroxynaphthalene-alpha, beta,-disulphonic acid, alpha, alpha,
dihydroxynaphthalene-beta, beta, disulphonic acid, or other sulphonic acids of
amido naphthol, or dihydroxynaphthalene, or amidonaphtholether sulphonic acids,
or alphanaphthylamine beta monosulphonic acids (1:2, 1:6, or 1:7), or amido-
naphthoxyacetic acid, or amidonaphthoxyacetic sulphonic acid, or if the
chrysoidine be replaced by other homologous or analogous chrysoidines, or dye-
stuffs of the Bismarck brown series, by alkyl-substitution products, sulphonic or
carboxylic derivatives thereof.
Similar results are obtained, if, in place of benzidine, other diamines or
substituted diamines, or sulphonic or carboxylic derivatives thereof, are used.
DYE STUFF FROM TETRAZODITOLYLCHLORIDE, ALPHA1 ALPHA-AMIDO-
NAPHTHOL, AND BISMARCK BROWN.
21-2 parts of tolidine are converted into tetrazoditolylchloride, by means of 35
14 parts of sodium nitrite, and the resulting tetrazo solution is allowed to flow into
an alkaline solution of 16 parts of alpha, alpha-amidonaphthol. As soon as the
formation of the intermediate product is at an end, the liquid is acidulated, and is

page_text: then mixed with a solution of 34 parts of Bismarck brown. After some time,
heat is applied, and the tetrazo product is then filtered off, pressed, and dried.
This product is slowly introduced into four times its weight of fuming sulphuric
acid, containing 20 per cent. of anhydride (the temperature being kept at from
0 to 30 degrees centigrade), and the mass is stirred until a sample proves to be
entirely soluble in dilute alkaline lye. The mixture is then poured onto ice, and
the dyestuff, after having been separated by filtration, is dissolved in a solution of
sodium carbonate, and precipitated by adding common salt to the alkaline solution.
It yields brownish shades on unmordanted cotton.
COLOURING-MATTER
FROM EQUIMOLECULAR PROPORTIONS OF AMIDO-
BENZENEAZOALPHANAPHTHYLAMINE, AMIDONAPHTHOLMONOSULPHONIC
ACID G, AND BISMARCK-BROWN SULPHONIC ACID.
This dyestuff is obtained by coupling the tetrazo-derivative of 26-2 parts of
amidobenzene azo alphanaphthylamine, with 23.9 parts of gamma-amido naphthol-
monosulphonic acid (in alkaline solution), and allowing the product to act on the
Bismarck-brown sulphonic acid formed by combining 10-8 parts of metaphenylene-
diamine with the diazo derivative of 10 parts of toluylene diamine sulphonic acid.
The dye-stuff produces brownish shades.
Colouring matters are obtained in an analogous manner from one molecular
proportion of a tetrazo-compound of the paradiamines herein before defined, one
molecular proportion of one of the above "naphthalene derivatives," and one
molecular proportion of a dye-stuff of the "chrysoidine" and "Bismarck-
brown series, or the alkyl derivatives, or sulphonic or carboxylic derivatives
thereof. These azo dye-stuffs produce on unmordanted cotton, in a neutral or
alkaline bath, shades varying from brownish to violet.
"
Instead of starting from the tetrazo-compounds of para-phenylenediamine,
paratoluylene diamine, or naphthylene diamine, the acetyl derivatives of these
diamines can be used. These acetyl derivatives are then diazotised, combined
with a colouring matter of the "chrysoidine" or "Bismarck-brown" series, and,
after separating the acetyl group, and rediazotising in a suitable manner, by means
of nitrous acid, are further coupled with the above "naphthalene derivatives."
The diazo derivatives of acetylated paraphenylene diamine, para-toluylene
diamine, or naphthylene diamine, can be first equally coupled with the "naph-
thalene derivatives," and, after separating the acetyl group, and rediazotising, can
be coupled with the colouring matters of the "chrysoidine or * Bismarck-
brown series. _
"
Instead of starting from the acetylated diamines, the corresponding nitramines
can be used, such as paranitraniline, metanitroortho toluidine, or nitronaphthyl-
amines, or the like. In such cases, the nitro group must be reduced to the amido
group, this process being effected at the same time that the acetyl-group contained
in the intermediate product is separated. The reduction is carried out by means
of mild reducing agents.
My foreign correspondents have found that the colouring matters hereinbefore
defined (which contain diazotisable amido-groups) are of special technical value,
as they can be further diazotised, and combined with one or two molecular
proportions of dyestuff components (employing, in the latter case either one or two
different components), dye-stuffs being thus produced which also possess technically
valuable properties.
According to the researches of my foreign correspondents, all dyestuff
components capable of combining with diazo or tetrazo compounds can be used,
viz., amines, diamines, phenols, amidophenols, amidophenolethers of the benzene
or naphthalene series, sulphonic or carboxylic derivatives thereof. Naturally
C

page_text: those of the resulting combinations are not claimed, which owing to their insolu-
bility cannot be used for dyeing purposes.
The last named process can also be effected on the fibre, as the researches of
my foreign correspondents shew that the above defined dyestuffs, in cases in which
they contain diazotisable amido groups, can be diazotised when fixed on the cotton
fibre, and can subsequently be combined, also, while on the fibre, with known
dyestuff components (such as betanaphthol, metaphenylene diamine or the like),
shades being thus produced which are distinguished by the manner in which they
withstand washing and the action of acids and alkalies. The shades they produce
are generally dark brown, and of great intensity.
My foreign correspondents have described in the above examples, distinct
methods for practically producing some of these new dyestuffs, but they do not
limit themselves to the directions therein given. These can be varied without
altering the nature of this invention, and in fact the dyestuffs hereinbefore defined
can be produced by means of all the methods in use for the production of analogous
or similar dyestuffs.
Having now particularly described and ascertained the nature of this 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 production of polyazo dyestuffs by means of the following naphthalene
derivatives, viz., amidonaphthol-sulphonic acids, alpha,-naphthylamine-beta-
monosulphonic acid, alpha-naphthylamine-betas-mono-sulphonic acid, alpha-
naphthylamine-beta4-monosulphonic acid, amidonaphthols, amidonaphtholethers,
amidonaphtholethersulphonic acids, amidonaphthoxyacetic acid, amido-naphthoxy-
aceticsulphonic acids, dihydroxynaphthalenes, or dihydroxynaphthalenesulphonic
acids, which process consists in combining one molecular proportion of the tetrazo-
derivatives of "benzidine, its analogues or homologues," in any order, with one
molecular proportion of the said "naphthalene derivatives," and with one
molecular proportion of a diamine or substituted diamine of the benzene or
naphthalene series (including alkylated diamines containing the alkyl groups in
place of the hydrogen of the amido groups, diamine sulphonic acids, and alkylated
diamine sulphonic acids), sulphonating the so-formed mixed products, or not, as
may be desirable, and in subsequently allowing the compounds thus obtained to
act on one molecular proportion of a diazo compound, or a diazo-azo compound,
or half a molecular proportion of a tetrazo compound, or on one molecular
proportion of a so-called intermediate product formed from equi-molecular
proportions of a tetrazo compound, and an amine, phenol, amido phenol, amido-
phenolether, diamine of the benzene or naphthalene series, a sulphonic or carboxylic
acid thereof, finally sulphonating the products, or not, as the case may require.
2. The manufacture of polyazo dye-stuffs, the which process consists in
combining one molecular proportion of the tetrazo derivatives of "benzidine, its
analogues or homologues," in any order, with one molecular proportion of one of
the aforesaid "naphthalene derivatives," and with one molecular proportion of a
diamidoazo, triamidoazo, tetramidoazo compound, or a substitution derivative
thereof (including the alkyl derivatives thereof containing the alkyl groups in
place of the hydrogen of the amido-groups, the sulphonic and carboxylic acids
derived from alkylated or non alkylated diamidoazo-, triamidoazo-, or tetr-
amidoazo compounds, and the members of the chrysoidine and Bismarck-brown series,
or the like), if necessary subsequently sulphonating the products. (The process
for producing colouring-matters as described in the Specification of Letters Patent
No. 15725, dated 16th September 1891, by combining one molecular proportion
of a tetrazo compound with one molecular proportion of amidonaphtholdisulphonic
acid H, and with one molecular proportion of meta toluylene diamine, or
chrysoidine or Bismarck-brown, is not claimed.)
3. The conversion of the colouring matters obtainable by means of the processes
claimed in the foregoing first and second claims (excluding those which do not

page_text: contain diazotisable amido groups) into new polyazo dyestuffs by diazotising, and
combining with one or two molecular proportions (employing, in the latter case,
either one or two different components) of amines, diamines, phenols, amidophenols,
amido phenol ethers of the benzene or naphthalene series, sulphonic or carboxylic
derivatives thereof. (Those of the resulting combinations which, owing to their
insolubility, cannot be used for dyeing purposes, are excluded.)
4. The process for producing polyazo dyestuffs on fibres, the which process
consists in dyeing cotton fibre or material with such colouring matters as are
obtainable as described in the foregoing first and second claims, and which contain
dinzotisable amido groups, and subsequently introducing the so dyed fibre or
material, first into a moderately acidulated bath of sodium nitrite, and then into
suitable alkaline or acidulated baths of amines, diamines, phenols, amidophenols,
amidophenolethers of the benzene or naphthalene series, sulphonic or carboxylic
acids thereof.
5. As new products of manufacture-
a. The new colouring matters produced by the processes hereinbefore defined,
or by any other means affording the same result;
b. The cotton fibre or materials dyed in the manner hereinbefore defined.
Dated this 10th day of January 1894.
NEWTON & SON,
Agents for the Applicant.