The Manufacture or Production of Poly-azo Dye-stuffs.
Year: 1894

page_text: Date of Application, 17th Mar., 1894
Complete Specification Left, 17th Dec., 1894-Accepted, 19th Jan., 1895
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Poly-azo 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:-
The present invention relates to the production of polyazo dye-stuffs from such
amidonaphtholsulphonic acids as contain the hydroxylic group and a sulphonic
group in the relative position OH: SO,H = 1:3.
The researches of my foreign correspondents have shown that the polyazo dye-
stuff's resulting from the amidonaphtholsulphonic acids above mentioned, give
shades of great fastness.
Of the said amidonaphtholsulphonic acids, for instance, the following can be
used, riz. Bamido a, naphthol ẞ, monosulphonic acid and B₁ amido a naphthol
a, 8, disulphonic acid.
The above mentioned ẞ, amido a naphthol ẞ monosulphonic acid can be
obtained, for example, by melting with alkalies the B₁ amido a3 ẞ, disulphonic
acid, or salts thereof, and the said B, ainido a, naphthol a, ẞ, disulphonic acid can
be produced, for example, by heating with fuming sulphuric acid the ẞ, naphthyl-
amine a, sulphonic acid, or B₁ naphthylamine a, 3, disulphonic acid, or ẞ, naph-
thylamine a a, disulphonic acid, and subsequently melting with alkalies the
B, naphthylamine a, a, ß, trisulphonic acid so formed.
As above mentioned, these or similar amidonaphthol sulphonic acids containing
the hydroxylic group and a sulphonic group in the relative position OH:
SO,H=1:3 can be profitably used for producing valuable polyazo dye-stuffs, and
my foreign correspondents assume that the valuable properties of these polyazo
dye-stuffs are caused by the circumstance, that the amidonaphthol sulphonic acids
used contain the hydroxylic group and a sulphonic group in the aforesaid relative
position.
For instance, from blue to bluish-black dye-stuffs, distinguished for their
intensity and fastness to the action of alkalies, acids, and light, are obtained, if one
molecular proportion of the tetrazo compound of a paradiamine is combined with
one molecular proportion of "amido compounds, which, when coupled, are rediazo-
tisable," and if the so-formed intermediate product, after being diazotised, is
allowed to act on two molecular proportions of the aforementioned B, amido a
naphthol B monosulphonic, or ẞ, amido a, naphthol a₁ ẞ, disulphonic acid. These
and the analogous polyazo dye-stuffs also possess the valuable property of being
further diazotisable (both in substances, and when fixed on the fibre), and also of
combining with phenols, amines, diamines, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic or other derivatives thereof,
new dye-stuffs or shades being thus obtained which are distinguished for great
intensity and fastness.
Of tetrazo compounds of diamines, my foreign correspondents use those resulting.

page_text: for instance, from the following diamido products, viz. :-Benzidine, tolidine,
diamidophenyltolyl, diamidodiphenolether, diamidoalkylhydroxydiphenyl, diamido-
alkylhydroxyphenyltolyl, diamidoazobenzene, diamidoazotoluene; diamidoazo
xylene, diamidoazoxybenzene, diamidoazoxytoluene, diamidostilbene, diamido
fluorene, diamidonaphthalene, diamidocarbazol, diamidodiphenyleneoxide, diamido-
ditoluylene oxide, diamidodiphenylamine, paraphenylene diamine, paratoluylene
diamine, benzidine sulphone, tolidine sulphone, diamidophenyltolyl sulphone,
diamidodiphenoxyacetic acid, amidobenzene azo a naphthylamine, amidotoluene
azo a naphthylamine, amidoxylene azo a naphthylamine, amidobenzene azopara-
xylidine, amidotoluene azoparaxylidine, amidoxyleneazoparaxylidine, amidobenzene
azometaamidoparacresolether, amidotoluene azometaamidoparacresolether, amido-
xylene azometa amidoparacresolether, amidobenzene, azoortho amidoparacresol-
ether, amidotoluene azo orthoamidoparacresolether, amidoxylene azo orthoamido-
paracres lether, amidobenzene azo ẞ ethoxy a naphthylamine, amidotoluene azo
Bethoxy a naphthylamine, amidoxylene azo Bethoxy a naphthylamine, or
sulphonic or carboxylic derivatives, or other derivatives thereof.
It is, however, understood that other diamines, or substituted diamines, which
can be converted into tetrazo compounds, either directly or by means of the mono
areto compounds thereof, can also be used. In place of the monoaceto diamines,
the corresponding mononitro amido compounds can be used; in the latter case, the
nitro zo compounds first formed are to be reduced, this reduction being effected at
the appropriate time, when, in the corresponding intermediate aceto amido azo
products, the acetyl group is displaced.
a4
My foreign correspondents inean by the above expression, "amido compounds
which, when coupled, are rediazotisable," all amido products of the benzene or
naphthalene series, which, when combined with a diazo or tetrazo compound, yield
real amido azo products further diazotisable, for instance, the following amido
products, riz., a naphthylamine, a naphthylamine B, monosulphonic acid, a naph-
thylamine B monosulphonic acid, a amido B, naphtholether 3 monosulphonic
acid, a, amido B, naphtholether ẞ monosulphonic acid, amidonaphtholmono-
sulphonic acid G, 01 amido a4 naphthol
a2 monosulphonic acid, amido
a1
naphthol
a monosulphonic acid, a amido a naphthol B, B, disulphonic acid, B₁ amido
B. naphthol B, ẞ, disulphonic acid, B₁ amido a naphthol B, monosulphonic acid,
Bamido a naphthol a ẞ, disulphonic acid, a amido ẞ, naphthoxyacetic acid,
a amido naphthoxyacetic sulphonic acid, a₁ a amidonaphthol, a a
naphthol, a amido B, naphthol obtainable by melting with alkalies a naphthyl-
amine--monosulphonic acid, a₁ amido ß naphthol, ß₁ amido ẞ naphthol, amido-
naphtholether, or the like, paraxylidine, o amido-p-cresolether, m amido p cresol-
ether. It is, however, understood that other amido compounds which, when
coupled are capable of further diazotisation, can be used. My foreign corre-
spondents hereinafter term these amido products "amido compounds further
diazotisable."
amido-
The aforesaid process for producing polyazo dye-stuffs can also be modified,
inasmuch as the hereinbefore defined intermediate products resulting from the
combination of one molecular proportion of a tetrazo compound with one molecular
proportion of an "amido compound further diazotisable," are, after diazo-
tisation, coupled with one molecular proportion of the one of the amidonaphthol-
sulphonic acids above defined, and with one molecular proportion of another of
these amidonaphthol sulphonic acids, or, in any order, with one molecular
proportion of such an amidonaphtholsulphonic acid and one molecular proportion
of an amine, a diamine, phenol, amidophenol, amidophenolether of the benzene or
naphthalene series, or a sulphonic or carboxylic derivative thereof. The polyazo
dye-stuffs thus obtainable, yield shades varying from red, brown, to blue, and can
be rediazotised (in substance, and when fixed on the fibre), and combined with
amines, phenols, and so on, respectively, dye-stuffs and shades being thus obtained
which are distinguished for their great intensity and fastness.

page_text: COLORING MATTER OBTAINED FROM ONE MOLECULAR PROPORTION
OF
AND
TOLIDINE, ONE MOLECULAR PROPORTION OF a-NAPHTHYLAMINE,
TWO MOLECULAR PROPORTIONS OF ẞ₁ AMIDO az NAPHTHOL a₁ ẞ DISUL-
PHONIC ACID.
21.2 parts of tolidine are diazotised in the usual manner, and the tetrazo solution
so formed is added to a cold watery solution of 18 parts of a naphthylamine hydro-
chloride. After stirring during several hours, sodium acetate is profitably added,
to accelerate the reaction. The mixture cooled by means of ice is allowed to stand
during 12 hours. 7 parts of sodium nitrite, and subsequently a sufficient quantity
of muriatic acid is added until the liquid shows an acid reaction. On continual
stirring, the mixture is allowed to stand during 12 hours, and when the diazotisation
is completed, the liquid mixture is introduced into a solution rendered alkaline by
means of potassium or sodium carbonate, and containing 63-8 parts of 3₁ amido
a, naphthol a ẞ, disulphonic acid. After standing during 12 hours, the mixture is
beated at about 90 degrees Centigrade, and the dye-stuff is isolated by salting out,
filtering off, pressing, and drying. It produces on unmordanted cotton blue
shades fast against the action of alkalies and acids, and possesses the following
formula:-
Other dye-stuffs result in an analogous manner, if either the tolidine used in the
above example is replaced by the corresponding quantity of another paradiamine,
or if, in place of a naphthylamine, another "amido compound further diazotisable"
is used, or if, in place of using B₁ amido a naphthol a₁ 3. disulphonic acid, two
molecular proportions of ẞ₁ amido as naphthol ẞ, monosulphonic acid, or another
amidonaphtholsulphonic acid containing the hydroxylic group and a sulphonic
group in the relative position OH: SO,H 13, or if, in any order, one molecular
proportion of these amidonaphtholsulphonic acids, and one molecular proportion of
another dye-stuff component, are coupled, with the tetrazo compounds resulting
from diazotising the intermediate products obtained on coupling one molecular
=

page_text: proportion of a tetrazo compound with one molecular proportion of an "amido
compound further diazotisable."
The researches of my foreign correspondents have also shown, that in place of
the aforesaid intermediate products resulting from the combination of one mole-
cular proportion of a tetrazo compound with one molecular proportion of an
"amido compound further diazotisable," those intermediate products can also be
used which are obtained on coupling one molecular proportion of a tetrazo com-
pound derived from the diamines above defined, with two molecular proportions of
the said "amido compounds further diazotisable" (employing either the same or
two different compounds), or, in any order, with one molecular proportion of an
"amido compound further diazotisable," and one molecular proportion of another
dye stuff component (amine, diamine, phenol, amidophenol, amidophenolether of
the benzene or naphthalene series, a sulphonic or carboxylic derivative thereof).
The last defined intermediate products, after being diazotised, can be combined
respectively with one molecular proportion of the said amidonaphtholsulphonic
acids, or with two molecular proportions of these amidonaphtholsulphonic acids
(employing either the same or two different acids), or, in any order, with one
molecular proportion of these amidonaphtholsulphonic acids and one molecular
proportion of another dye-stuff component (amine, diamine, phenol, amidophenol,
amidophenolether of the benzene or naphthalene series, a sulphonic or carboxylic
acid thereof). The colouring matters thus obtainable chiefly yield shades varying
from green, brown, to blue, and distinguished for their great fastness against the
action of alkalies and acids. These polyazo dyestuffs also possess the valuable
property of being further diazotisable (in substance or when fixed on the fibre),
and also of combining with dye-stuff components (amines, diamines, phenols,
admidophenols, amidophenolethers of the benzene or, naphthalene series, sulphonic
or carboxylic derivatives thereof). Dyestuffs or shades are respectively thus
obtained which are distinguished for greater intensity than the dye stuffs not
further diazotised possess.
Two methods of producing the last-named polyazo dyestuffs are illustrated by
the following two examples. The parts are by weight.
DYE-STUFF OBTAINED FROM ONE MOLECULAR PROPORTION OF BENZIDINE,
TWO MOLECULAR PROPORTIONS OF a₁-NAPHTHYLAMINE ẞ, MONOSUL-
PHONIC ACID, AND TWO MOLECULAR PROPORTIONS OF B₁-AMIDO-
a₁-NAPHTHOL a₁ B.-DISULPHONIC ACID.
18.4 parts of benzidine are diazotised, and the resulting tetrazo solution is added
to a solution, in water, of 49 parts of the sodium salt of a-naphthylamine B-mono-
sulphonic acid (Cleve's B-acid). After adding sodium acetate, the mixture is
allowed to stand during 12 hours. It is then heated at about 80 degrees
Centigrade, and after rendering alkaline, the intermediate product is salted out
and filtered off. The product so formed is mixed with water, and after adding
13-8 parts of sodium nitrite, the mixture is acidulated by means of muriatic acid.
At the end of 12 hours, the diazotised intermediate product is filtered off. It is
mixed with water, and then introduced into a solution rendered alkaline by means
of sodium or potassium carbonate, and containing 63-8 parts of B₁-amido-az-naph-
thol-a-disulphonic acid.. After standing during 12 hours, the liquid mixture is
heated at 90 degrees Centigrade. The dye-stuff is subsequently. isolated in the
usual manner by salting out, filtering off, pressing, and drying. It yields on

page_text: unmordanted cotton very dark shades, which withstand alkalies, acids, and light.
"The colouring-matter so formed possesses the following formula :-
Other colouring-matters result in an analogous manner, if the components used
5 in the foregoing second example are replaced by the corresponding quantities of
the analogous components hereinbefore defined.
The following example describes a method of producing a colouring matter
which contains in the last place two different components. The parts, are by
weight.
COLOURING MATTER FROM EQUIMOLECULAR PROPORTIONS OF BENZIDINE,
SALICYLIC ACID, B₁-AMIDO-a,-NAPHTHOL-a₁ B. DISULPHONIC ACID, AND
BAMIDO-as-NAPHTHOL-B-MONOSULPHONIC ACID.
The tetrazo solution obtained in the usual manner from 18-4 parts of benzidine,
is introduced into an icy-cold solution, which is rendered alkaline by means of
sodium carbonate, and contains 13.8 parts of salicylic acid. After standing during
about 4 hours, a solution prepared by dissolving 31.9 parts of ẞ-amido-az-naphthol-
a B-disulphonic acid, and rendered alkaline by means of sodium or potassium
carbonate, is allowed to flow into the above liquid mixture. At the end of
12 hours, the mixture is heated at 90 degrees Centigrade, and the intermediate
product so formed is salted out, filtered off, mixed with 6.9 parts of sodium nitrite,
and muriatic acid in a moderate excess is added. While cooling by means of ice,
the mixture is allowed to stand during 12 hours. The diazo product so formed is
then introduced into a solution rendered alkaline by means of sodium carbonate,
and containing 23.9 parts of ẞ-amido-as-naphthol-ẞ, mono sulphouic acid. At the
end of 12 hours, the mixture is heated, and the complete dye-stuff is isolated by

page_text: salting out, filtering off, pressing, and drying. It produces on unmordanted cotton.
very fast dark-brown shades, and possesses the following formula :-
.
Other mixed polyazo dyestuffs can be obtained in a manner analogous to that
described in the last example, if either the benzidine used therein is replaced by
the equivalent quantity of another diamine, or if another hydroxy carboxylic acid,
or a phenol, an amine, a diamine, amidophenol, amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic derivative thereof, is used in place of
salicylic acid, or if the 3-amido a, naphthol a B-disulphonic acid is replaced by
the corresponding quantity of another amido compound, further diazotisable,
belonging to the benzene or naphthalene series, or if the ẞ₁ amido-a,-naphthol-
B. monosulphonic acid as last component, is replaced by the corresponding quantity
of another amidonaphtholsulphonic acid containing the hydroxylic and a sulphonic
group in the relative position OH: SO,H = 1: 3.
As above mentioned, the polyazo dye-stuffs obtained by means of the processes
herein before defined, can be converted into new polyazo dye-stuffs by diazotising
and combining with phenols, amines, diamines, amidophenols, amidophenolethers of
the benzene or naphthalene series, sulphonic or carboxylic derivatives thereof.
The last-named colouring matters are distinguished for their fastness and intensity.
If the last-mentioned process, (viz., diazotisation and combination with dye-stuff
components) is carried out on the fibre, fast and intense shades are likewise
obtained.
Dated 16th day of March 1894.
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION.
The Manufacture or Production of Poly-azo Dyestuffs.
I, HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane, in the County of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
The present invention relates to the production of polyazo dyestuffs from such
. amidonaphtholsulphonic acids as contain the hydroxylic group and a sulphonic
group relatively in the meta position (OH: SO,H=1:3).
The researches of my foreign correspondents have shewn that the polyazo
dyestuffs formed from such amidonaphtholsulphonic acids, give shades of great
fastness.

page_text: Of the said amidonaphtholsulphonic acids, the following are used, viz., beta
amido-alpha,-naphthol-beta, monosulphonic acid and beta-amido-alpha, naphthol
alpha beta, disulphonic acid.
The above-mentioned beta, amido-alpha, naphthol beta-monosulphonic acid can
be obtained, for example, by fusing beta-amido-alpha, beta-disulphonic acid, or
salts thereof, with alkalies, and the said beta, amido-alpha, naphthol alpha, beta-
disulphonic acid can be produced, for example, by heating beta-naphthylamine
alpha-sulphonic acid, or beta, naphthylamine alpha, beta-disulphonic acid, or
beta, naphthylamine alpha, alpha, disulphonic acid, with fuming sulphuric acid,
and subsequently fusing the beta, naphthylamine-alpha, alpha, beta, trisulphonic
acid so formed, with alkalies.
These two amidonaphtholsulphonic acids, containing the hydroxylic group and a
sulphonic group relatively in the meta position (OH: SO,H=1:3), can be
profitably used in producing valuable polyazo dye stuffs, and my foreign
correspondents believe that the valuable properties of these polyazo dyestuffs are
due to the meta position of the hydroxylic, relatively to the sulphonic group.
For instance, from blue to bluish-black dyestuffs, distinguished for their intensity
and fastness on exposure to the action of alkalies, acids, and light, are obtained, if
one molecular proportion of the tetrazo compound of a paradiamine is combined
with one molecular proportion of "amido compounds affording rediazotisable
products," and if the intermediate products so formed be diazotised, and allowed to
act on two molecular proportions of either the aforementioned beta, amido alpha,
naphthol beta, monosulphonic acid, or the beta, amido-alpha, naphthol-alpha,-beta-
disulphonic acid. These and the analogous polyazo dye-stuffs also possess the
valuable property of being further diazotisable (both in substance and when fixed
on the fibre), and of then combining with phenols, amines, diamines, dihydroxy
compounds, amido phenols, amido phenolethers of the benzene or naphthalene
series, sulphonic or carboxylic or other derivatives thereof, new dye stuffs or
shades being thus obtained which are distinguished by great intensity and
fastness.
My foreign correspondents use the tetrazo compounds of diamines, which may be
formed, for instance, from the following diamido compounds, viz. :-Benzidine,
tolidine, diamidophenyltolyl, diamidodiphenolether, diamidoalkylhydroxydiphenyl,
diamidoalkylhydroxyphenyltolyl, diamidodiazobenzene, diamidoazotoluene, diamido-
azoxylene, diamidoazoxybenzene, diamidoazoxytoluene, diamidostilbene, diamido-
fluorene, diamidonaphthalene, diamidocarbazol, diamidodiphenylene
oxide,
diamidoditoluylene oxide, diamidodiphenylamine, paraphenylenediamine, para-
toluylenediamine, benzidene sulphone, tolidinesulphone, diamidophenyltolylsulphone,
diamidodiphenoxyacetic acid, amidobenzene-azo-alpha-naphthylamine, amido-
toluene-azo-alpha-naphthylamine, amidoxylene-azo-alpha-naphthylamine, amido-
benzene-azo-para-xylidine, amidotoluene-azo-para-xylidine, amidoxylene-azo-para-
xylidine, amidobenzene-azo-meta-amido-para-cresolether, amidotoluene-azo-meta-
amido-paracresolether, amidoxylene-azo-meta-amido-para-cresolether, amido-
benzene-azo-ortho-amido-para-cresolether, amido-toluene-azo-ortho-amido-para-
cresolether, amidoxylene-azo-ortho-amido-para-cresolether, amidobenzene-azo-beta-
ethoxy-alpha-naphthylamine, amidotoluene azo beta ethoxy alpha naphthylamine,
amidoxylene-azo-beta-ethoxy-alpha-naphthylamine, or sulphonic or carboxylic
derivatives, or other derivatives thereof.
Other diamines, or substituted diamines, which can be converted into tetrazo
compounds, either directly, or after conversion into monacetyl derivatives, can, as
a matter of course, also be used. In place of the monacetylated diamines, the
corresponding mononitroamidocompounds can be used; in the latter case, the
nitroazocompounds which are first formed must be reduced, whilst the corresponding
acetylated intermediate products must be treated in a suitable manner, in order to
separate the acetyl group..
૭
My foreign correspondents mean by the above expression "amido compounds
which, when coupled, afford rediazotizable products," all amido compounds of the

page_text: benzene or naphthalene series which, when combined with a diazo- or tetrazo
compound, yield true amido compounds which can be further diazotised, for
instance. the following amido compounds, viz. :-Alphanaphthylamine, alpha,
naphthylamine-beta-monosulphonic acid, alpha-naphthylamine-beta-monosulphonic
acid, alpha-amido-beta,-naphtholether-beta-monosulphonic acid, alpha-amido-
beta-naphtholether-beta-monosulphonic acid, amidonaphtholmonosulphonic acid G,
alpha amido-alpha-naphthol-alpha, mono-sulphonic acid, alpha-amido-alpha,
naphthol-alpha-monosulphonic acid, alpha-amido-alpha, naphthol-beta, beta-
disulphonic acid, beta-amido-beta-naphthol-beta, beta-disulphonic acid, betai
amido-alpha, naphthol beta, monosulphonic acid, beta, amido-alpha-naphthol-
alpha, beta, disulphonic acid, alpha-amido-beta-naphthoxyacetic acid, alpha-amido-
beta-naphthoxyaceticsulphonic acid, alpha-alpha, amidonaphthol, alpha, alpha-
amidonaphthol, alpha-amido-beta-naphthol obtainable by melting with alkalies
alpha, naphthylamine-beta-monosulphonic acid, alpha,-amido-beta-naphthol, beta₁-
amido-beta-naphthol, amidonaphthether, or the like, paraxylidine, ortho-amido-
para-cresolether, meta-amido-para-cresolether. It is, however, to be understood,
that other amido compounds which, when coupled, afford products capable of
further diazotisation can be used.
The aforesaid process for producing polyazo dye stuffs can also be modified,
inasmuch as the hereinbefore defined intermediate products formed by combining
one molecular proportion of a tetrazo compound with one molecular proportion of
an "amido compound affording a diazotisable product," are, after diazotisation,
coupled with a molecular proportion of the one, and with a molecular proportion of
the other, of the amidonaphtholsulphonic acids above defined, or, in any order, with
a molecular proportion of such an amidonaphtholsulphonic acid, and a molecular
proportion of an amine, diamine, phenol, amidophenol, amidophenolether of the
benzene or naphthalene series, or a sulphonic or carboxylic derivative thereof.
The polyazo dye stuffs thus obtainable yield shades varying from red, brown, to
blue, and can be rediazotised (in substance, and when fixed, on the fibre), and
combined with amines, phenols, and so on, dyestuffs and shades being thus obtained
which are distinguished by their great intensity and fastness.
In order to illustrate the method of producing the polyazo dye-stuffs hereinbefore
defined, the following example is given, the parts being by weight.
COLOURING MATTER
OBTAINED FROM ONE
MOLECULAR
PROPORTION OF
TOLIDINE, ONE MOLECULAR PROPORTION OF ALPHA-NAPHTHYLAMINE,
AND TWO MOLECULAR PROPORTIONS OF BETA-AMIDO-ALPHA-NAPHTHOL-
ALPHA BETA DISULPHONIC ACID.
21-2 parts of tolidine are diazotised in the usual manner, and the tetrazo solution
is added to a cold, watery solution of 18 parts of alpha-naphthylamine hydro-
chloride; after stirring during several hours, sodium acetate is, with advantage,
added, to accelerate the action, and the mixture is then allowed to stand during
12 hours, being kept ice-cold; 7 parts of sodium nitrite are next added, and
subsequently a sufficient quantity of muriatic acid, to render the liquid acid. The
mixture is then continually stirred, and after about 12 hours, when the diazotisation
is complete, the whole is introduced into a solution rendered alkaline by means of
potassium or sodium carbonate, and containing 63-8 parts of beta-amido-alpha,-
naphthol-alpha, beta, disulphonic acid. After standing during 12 hours, the
mixture is heated to about 90 degrees Centigrade, and the dye-stuff is then isolated
by salting out, filtering off, pressing, and drying. On unmordanted cotton, it

page_text: produces blue shades which resist the action of alkalies and acids. It is represented
by the following formula :-
Other dye-stuffs are prepared in an analogous manner, either by using, in place
of the tolidine of the Example A, the corresponding quantity of another
paradiamine, or if, in place of alpha naphthylamine, another "amido compound
affording a diazotisable product" is used, or if, in place of using beta-amid.1-
alpha, naphthol-alpha, beta, -disulphonic acid, two molecular proportions of beta₁
amido-alpha,-naphthol-beta-mono-sulphonic acid, or if (in any order) a molecular
proportion of the one and a molecular proportion of the other acid are used, or if,
in any order, a molecular proportion of either of these amido-naphtholsulphonic
acids, and a molecular proportion of another dye-stuff component, are coupled with
the tetrazo compounds formed by diazotising the intermediate products obtained on
coupling a molecular proportion of a tetrazo compound with a molecular proportion
of an "atnido compound affording a diazotisable product."
The researches of my foreign correspondents have also shewn, that in place of
the aforesaid intermediate products formed by combining a molecular proportion of
a tetrazo compound with a molecular proportion of an "amido compound affording
a diazotisable product," the intermediate products can also be used which are
obtained on coupling a molecular proportion of a tetrazo compound derived from
the diamines above defined, with two molecular proportions of the said "amido
compounds affording diazotisable products" (using either the same or two different
compounds) or, in any order, with a molecular proportion of an "amido compound
affording a diazotisable product" and a molecular proportion of another dyestuff
component (an amine, diamine, phenol, dibydroxy-compound, amidophenol, amido-
phenol-ether of the benzene or naphthalene series, or a sulphonic or carboxylic
derivative thereof). The last defined intermediate products, after being diazotised,
can be combined respectively with a molecular proportion of the said amidonaph-
tholsulphonic acids, or with two molecular proportions of these amidonaphthol-
sulphonic acids (using either the one or two different acids), or, in any order, with
a molecular proportion of these amidonaphtholsulphonic acids, and a molecular
proportion of another dyestuff component (amine, diamine, phenol, dihydroxy
compound, amidophenol, amidophenolether of the benzene or naphthalene series,
or a sulphonic or carboxylic acid thereof). The colouring matters thus obtainable
chiefly yield shades varying from green, brown, red, to blue, and distinguished for
their great fastness on exposure to the action of alkalies and acids. These polyazo
dyestuffs also have the valuable property of being further diazotisable (in substance,
or when fixed on the fibre), and also of combining with dyestuff components (amines,
B

page_text: diamines, phenols, dihydroxy compounds, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic derivatives thereof).
Dyestuffs or shades are respectively thus obtained of greater intensity than the
dyestuffs which have not been further diazotised.
Two methods of producing the last named polyazo dyestuffs are illustrated by
the following two examples. The parts are by weight.
DYESTUFF OBTAINED
FROM ONE MOLECULAR PROPORTION OF BENZIDINE,
MOLECULAR PROPORTIONS OF ALPHA-NAPHTHYLAMINE-BETA₁-
MONOSULPHONIC ACID, AND TWO MOLECULAR PROPORTIONS OF BETA1-
TWO
AMIDO-ALPHA, NAPHTHOL-ALPHA BETAL DISULPHONIC ACID.
184 parts of benzidine are diazotised and the tetrazo solution is added to a
solution in water of 49 parts of the sodium salt of alpha-naphthylamine-beta,
monosulphonic acid (Clève's B-acid). Sodium acetate having been added, and the
mixture having stood during 12 hours, it is heated to about 80 degrees Centigrade;
it is then rendered alkaline, and the intermediate product is salted out and filtered
off. This product is mixed with water, and 13.8 parts of sodium nitrite, and the
mixture is then acidulated with muriatic acid. At the end of 12 hours, the
dia zotised intermediate product is filtered off. It is then mixed with water, and
introduced into a solution rendered alkaline by meaus of sodium or potassium
carbonate, and containing 63-8 parts of beta-amido-alpha, naphthol-alpha, beta-
disulphonic acid. After standing during 12 hours, the liquid mixture is heated to
90 degrees Centigrade. The dye-stuff is subsequently isolated in the usual manner
by salting out, filtering off, pressing, and drying. It produces, on unmordanted
cotton, intense blue shades which withstand the action of alkalies acids and light.
The colouring-matter so formed is represented by the following formula :-
Other colouring-matters are formed in an analogous manner, if, instead of the
components used in the foregoing Example B, the corresponding quantities of the
analogous components hereinbefore defined are taken.
3

page_text: The following example describes a method of producing a colouring matter
containing ultimately two different components. The parts are by weight.
SALICYLIC ACID, BETA-AMIDO-ALPHA; NAPHTHOL-ALPHA BETA-DISUL-
PHONIC ACID, AND BETA-AMIDO-ALPHA-NAPHTHOL-BETA MONOSULPHONIC
ACID.
The tetrazo solution obtained, in the usual manner, from 18-4 parts of benzidine,
is introduced into an icy-cold solution, which is rendered alkaline by means of
sodium carbonate, and contains 13-8 parts of salicylic acid. After standing during
about 4 hours, a solution prepared by dissolving 31.9 parts of beta-amido-alpha,-
naphthol-alpha, beta-disulphonic acid, and rendered alkaline by means of sodium
or potassium carbonate, is allowed to flow into the above liquid mixture. At the
end of 12 hours, the mixture is heated to 90 degrees Centigrade. The intermediate
product having been salted out and filtered off, is mixed with 6.9 parts of sodium
nitrite, and a slight excess of muriatic acid is added. The mixture is cooled by
means of ice, and allowed to stand during 12 hours. The diazo product so formed
is filtered off and introduced into a solution rendered alkaline by means of sodium
carbonate, and containing 23.9 parts of beta-amido-alpha-naphthol-beta-mono-
sulphonic acid. At the end of 12 hours, the mixture is heated, and the dyestuff is
isolated by salting out, filtering off, pressing, and drying. It produces, on
unmordanted cotton, very fast bluish red shades, & is represented by the following
formula:-
Other mixed polyazo dye stuffs can be obtained in a manner analogous to that
described in the last example, if either instead of the benzidine used therein, the
equivalent quantity of another diamine be used, or if another hydroxcarboxylic
acid, or a phenol, an amine, a diamine, dihydroxy compound, amidophenol, amido-
phenolether of the benzene or naphthalene series, a sulphonic or carboxylic
derivative thereof, be used in place of salcylic acid, or if, in place of beta-amido-
alpha, naphthol-alpha, beta, disulphonic acid, the corresponding quantity of another
"amido-compound affording a diazotisable product" belonging to the benzene or
naphthalene series, be taken, or if the beta-amido-alpha, napthol beta, mono-
sulphonic acid used as last component have its place taken by the corresponding
quantity of beta, amido-alpha, naphthol-alpha, beta-disulphonic acid.

page_text: As above mentioned, the polyazo dyestuffs obtained by means of the processes
hereinbefore defined, can be converted into new polyazo dyestuffs by diazotising
them, and combining the product with phenols, amines, diamines, dihydroxy
compounds, amidophenols, amidophenolethers of the benzene or naphthalene series,
or sulphonic or carboxylic derivatives thereof, including beta, amido alpha, naphthol-
beta, monosulphonic acid and beta, amido alpha, naphthol-alpha, beta4-disulphonic
acid. The last-named coloring-matters are distinguished by their fastness and
intensity. If the last mentioned process (viz., diazotisation and combination with
dye stuff components) is carried out on the fibre, fast and intense shades are also
obtained. The last named processes, riz., conversion of the polyazo dyestuff's
herein before defined (either in substance, or when on the fibre), by further diazo-
tisation and combination with suitable dyestuff components, is effected in the manner
generally known and in use for analogous purposes.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed (as communicated to
me from abroad), I declare that what I claim is
1. The production of polyazo dyestuffs from beta, amido-alpha, naphthol beta-
monosulphonic acid, beta, amido-alpha-naphthol-alpha, beta-disulphonic acid, or
salts thereof, which process consists in combining a molecular proportion of the
tetrazo derivatives of "benzidine, its analogues or homologues," with a molecular
proportion of the herein before defined "amido compounds affording rediazotisable
products," rediazotising the intermediate products so formed, and subsequently
combining the tetrazo compounds thus formed, either with two molecular proportions
of beta, amido-alpha-naphthol-beta, sulphonic acid, or beta, amido-alpha-naphthol-
alpha, beta, disulphonic acid, or (in any order) with a molecular proportion of
beta, amido-alpha, naphthol beta, sulphonic acid, and with a molecular proportion
of beta, amido-alpha, naphthol-alpha, beta-disulphonic acid, or (in any order) with
a molecular proportion of one of the last named beta, amido-alpha, naphthol-
sulphonic acids, and with a molecular proportion of an amine, diamine, phenol,
dihydroxy compound, amidophenol, amidophenolether of the benzene or naph-
thalene series, or a sulphonic or carboxylic acid thereof.
2. The process for producing polyazo dyestuffs from beta-amido-alpha-naphthol-
beta-monosulphonic acid, or beta-amido-alpha-naphthol-alpha, beta,-disulphonic
acid, or salts thereof, which process consists in combining a molecular proportion
of the tetrazo derivatives of "benzidine, its analogues or homologues," either with
two molecular proportions of the bereinbefore defined "amido compounds affording
rediazotisable products" (using either oue or two different compounds), or (in auy
order) with a molecular proportion of the herein before defined "amido compounds,"
and with a molecular proportion of a phenol, amine, diamine, dihydroxy compound,
amidophenol, amidophenolether of the benzene or naphthalene series, or a sulphonic
or carboxylic acid thereof; subsequently diazotising the intermediate products so
formed, and finally coupling the diazo or tetrazo compounds, as the case may be,
either with a molecular proportion of beta-amido-alpha-naphthol-beta-sulphonic
acid, or of beta-amido-alpha-naphthol-alpha, beta-disulphonic acid, or with two
molecular proportions of these beta-amido-alpha-naphthol-sulphonic acids (using
either one or two different acids), or (in any order) with a molecular proportion of
either of these beta-amido-alpha-naphtholsulphonic acids, and with a molecular
proportion of an amine, a diamine, phenol, dihydroxy compound, amidophenol,
amidophenolether of the benzene or naphthalene series, or a sulphonic or carboxylic
acid thereof.
3. The conversion of the polyazo colouring-matters produced by the processes
claimed in the preceding first and second claims (either in substance, or when on
the fibre), into new dyestuffs, by a subsequent diazotisation and combination with
the known dyestuff components, including the said beta-amido-alpha-naphthol-
sulphonic acids.

page_text: 4. As new products of manufacture, the new polyazo colouring-matters
produced by the processes herein before defined, or by any other process affording
the same result.
Dated this 1nt d
1004
NEWTON & SON,
Agents for the Applicant.