The Manufacture or Production of New Azo Dye-stuffs.
Year: 1895

page_text: Date of Application, 7th June, 1895
Complete Specification Left, 7th Mar., 1896-Accepted, 11th Apr., 1896
ARIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of New 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:-
"
Azo dye-stuffs containing acidyl amido groups have been but little used hitherto
for dyeing purposes.
My foreign correspondents use the term acidylamido
groups," in the present Specification, for amido groups in which a hydrogen atom
is substituted by the radicle of any organic acid, and in accordance therewith the
use the expression acidylamido compounds for such products as contain amido
groups in which a hydrogen atom of these amido groups is substituted by any
organic acid radicle.
My foreign correspondents have now produced new azo dye-stuffs which contain
such acidyl-amido groups, and which are of great value for dyeing and printing
purposes. The researches of my foreign correspondents have shewn, that those
acidyldiamido compounds, in which one hydrogen atom of the one amido group is
substituted by the radicle of any polybasic acid such as oxalic acid, succinic acid,
phthalic acid, or the like, are of especial value for the said purposes.
In order to produce such dye-stuffs containing acidylamido groups, my foreign
correspondents employ "diamido compounds" of the aromatic series in which a
hydrogen atom of the one amido group is substituted by the radicle of any organic
acid, and they obtain monoazo and disazo dye-stuffs either by diazotising the
"free" amido group contained in the last defined diamido compounds, and coupling
the diazo derivatives thus formed with the usual dye-stuff components, or, inversely,
by acting with diazo. compounds (including diazo derivaties of acidyldamido
compounds) on those, acidyldamido compounds which are capable of combining
with diazo products to form azo dye-stuffs, or by allowing one molecular proportion
of a tetrazo compound to act on two molecular proportions of acidyldiamido
compounds (employing either the same or two different ones), or by combining one
molecular proportion of a tetrazo compound, in any order, with one molecular
proportion of an acidylidiamido compound and one molecular proportion of any
other dye-stuff component.
The production of these monoazo and disazo dye-stuffs is effected in the well
known manner.
My foreign correspondents have further found that the azo dye-stuffs prepared
by coupling acidyldiamines with diazo or tetrazo compounds, especially the mixed
and symmetrical disazo dye-stuffs prepared by coupling one molecular proportion
of an acidyl diamine and one molecular proportion of any other dye-stuff component
with one molecular proportion of a tetrazo compound, or by coupling two molecular
proportions of acidyldiamines with one molecular proportion of a tetrazo compound,
such as a tetrazodiphenyl, tetrazoditolyl, or the like, can be profitably used as
so-called intermediate products for the manufacture of new valuable polyazo dye-
stuffs, viz., the mixed and symmetrical disazo dye stuffs hereinbefore defined, can
be further diazotised, and the diazo or tetrazo compounds thus formed can be
combined with the usual dye-stuff components, the said polyazo dye stuffs being
thus produced.

page_text: Whereas from diazo-, or tetrazo compounds, and aniline or the like monamines of
the benzene series, intermediate products suitable for further diazotisation and
combination are obtained only with great difficulty; diazo amido compounds being
usually, formed, the diazo- and tetrazo compounds readily act on acidyl diamines,
normal amido azo compounds being thus produced, as my foreign correspondents
have ascertained. The dye-stuffs obtained by further diazotising the last named.
amido azo compounds and subsequent combination with dye stuff components, are
generally more soluble, and faster against the action of alkali, and yield darker
shades on fibre, than the analogous dye-stuffs derived from aniline, toluidine, or
the like.
For the production of these new dye-stuffs containing acidyl amido groups, all
acidyl diamines of the benzene or napthalene series may be used which are
capable of being combined with diazo compounds. Such acidyl diamines are, for
instance acetyl meta phenylenediamine, acetyl meta toluylenediamine, met-
amidophenylene oxamic acid, having the formula
(see Klusemann, Berichte der Deutschen chem. Gesellschaft, 7. 1261), metamido-
toluylene oxamic acid and the like compounds, which are prepared in the generally
known manner.
The last-named acidyldiamines, and the analogues thereof which contain free
carboxylic groups, are of especial value, as the dye stuffs derived therefrom yield,
on fibre, shades which (particularly when treated with salts of chromic acid, salts
of copper, or other metallic salts) are very fast against the action of washing and
fulling.
In order to illustrate the process of producing such dye-stuffs, my foreign
correspondents give the following examples, one, two, three, four, five, and six.
The parts are by weight.
VIOLET-BLACK AZO DYE-STUFF OBTAINED FROM EQUAL MOLECULAR
PROPORTIONS OF a-NAPHTHYLAMINE,
METAMIDOPHENYLENE
ACID, AND ALPHA₁ NAPHTHOL ALPHA SULPHONIC ACID.
OXAMIC 3
A diazo solution obtained in the usual manner from 14.3 parts of alpha naphthyl-
amine by means of sodium nitrite in the presence of muriatic acid, is allowed to
flow into a solution prepared by dissolving 18 parts of metamidophenylene
oxamic acid
3
in cold water, and adding a small quantity of caustic soda-lye and an excess of
.sodium acetate. The resulting mixture is stirred during 24 hours, and is then
rendered alkaline at a low temperature. It is heated for a short time at about
50 degrees Centigrade. The amido azo compound thus formed is filtered off and 4

page_text: mixed with a small quantity of water, and 7 parts of nitrite of sodium and a
sufficient quantity of muriatic acid are then added at from about 5 to 10 degrees
Centigrade. After 12 hours, the finished diazo compound is filtered off, and added
to a watery solution containing 14.4 parts of alpha, naphthol-alpha, sulphonic
acid, and rendered alkaline with sodium carbonate. After standing during about
12 hours, the mixture is heated for a short time at about 50 degrees Centigrade.
The finished dye-stuff thus formed is salted out, filtered, pressed, and dried. It
produces, on wool, violet black shades, which become fast against the action of
washing and fulling by a subsequent treatment with bichromate of potassium and
the like.
The dye stuff has the formula:
CH,NN CH¸‹
-
NHCO.CO0Na
as aniline, sulphanilic acids, naphthylamine sulphonic acids, nitranilines, amido-
benzoic acids, amido salicylic acid, or the like, are employed in place of alpha
naphthylamine.
EXAMPLE 2.
GREEN-BLACK AZO DYE-STUFF FROM EQUAL MOLECULAR PROPORTIONS OF
DEHYDROTHIOTOLUIDINE SULPHONIC ACID, METAMIDOPHENYLENE
OXAMIC ACID, AND DIHYDRO OXYNAPHTHALENE SULPHONIC ACID "S.”
(OR a₁ o, DIHYDROXYNAPHTHALENE ALPHA MONOSULPHONIC ACID).
A diazo solution prepared from 34.2 parts of dehydrothiotoluidine sulphonic acid
in the usual manner, is allowed to flow into a solution obtained by dissolving
18 parts of metamidophenylene oxamic acid in cold water, and adding a small
quantity of soda lye and an excess of sodium acetate. After about 12 hours, the
mixture is rendered alkaline and heated to about 50 degrees Centigrade. The
amido azo compound thus formed is filtered off and diluted with a small quantity
of water; 7 parts of sodium nitrite and an excess of muriatic acid are then added at
from 5 to 10 degrees Centigrade.
At the end of 12 hours, the finished diazo compound is filtered off and added to
a solution prepared by dissolving in water 24 parts of alpha, alpha, dihydroxy-
naphthaline alpha monosulphonic acid, and adding an excess of sodium acetate.
The resulting mixture is allowed to stand during 12 hours. It is then heated for
a short time at about 50 degrees Centigrade, and after adding a small quantity of
sodium carbonate, the finished dye-stuff is salted out, filtered off, pressed, and
dried. It dyes unmordanted cotton in green-black shades, which become fast
against the action of washing and fulling by a subsequent treatment of the dyed
goods with potassium bichromate or the like metallic salts.
The dye-stuff has the formula:

page_text: If an equivalent quantity of phenol is used, instead of dihydroxynaphthalene
monosulphonic acid "S" in the foregoing example, a disazo dye-stuff results which,
by further alkylation, is converted into a new valuable colouring matter yielding
on unmordanted cotton chocolate brown shades fast to the action of alkali, acids,
and light.
If the dihydroxyuaphthalene monosulphonic acid "S" is replaced by an
equivalent quantity of alpha, hydroxynaphthalene alpha, monosulphonic acid, a
colouring matter is obtained which dyes unmordanted cotton a grayish-black.
VIOLET-BLACK AZO DYE-STUFF PRODUCED FROM ONE MOLECULAR PROPORTION
OF BENZIDINE, ONE MOLECULAR PROPORTION OF METAMIDOPHENYLENE
OXAMIC ACID, AND TWO MOLECULAR PROPORTIONS OF DIHYDROXY-
NAPHTHALENE SULPHONIC ACID "S" (a₁ α DIHYDROXYNAPHTHALENE
a₂ DISULPHONIC ACID).
18.4 parts of benzidine are diazotised in the usual manner, and the tetrazo
solution is added to a solution in water of 18 parts of metamido phenylene oxamic
acid, mixed with a small quantity of caustic soda lye, or sodium carbonate, and
with an excess of sodium acetate. The mixture is stirred during about 24 hours.
The intermediate product thus formed is diazotised by means of 7 parts of sodium
nitrite, in the presence of a small excess of muriatic acid, and the resulting product
is allowed to stand during 12 hours. The finished diazo compound is poured into
a solution of 48 parts of alpha, alpha, dihydroxynaphthalene alpha monosulphonic
acid, mixed with an excess of sodium acetate. At the end of 12 hours, the mass is
rendered alkaline by means of sodium carbonate, and heated for a short time at
about 50 degrees Centigrade. The finished dye-stuff is then salted out, pressed,
and dried. It yields, on unmordanted cotton, violet-black .shades, which become
deep black and fast against washing and to the action of light by a subsequent
treatment with chromates or salts of copper or the like.
The dye stuff has the formula :-
Equivalent quantities of other aromatic diamines, such as tolidine, dianisidine, or
the like, may be used in place of benzidine, similar dye stuffs being thus obtained.
The aa dihydroxy naphthalene-a-monosulphonic acid may be replaced by
corresponding quantities of other dye-stuff components, such as alpha, naphthol
alpha, or 3 sulphonic acid alpha, alpha, dihydroxynaphthalene beta, betag
disulphonic acid, gamma amidonaphthol sulphonic acid, alpha, alpha, naphthol
sulphonic acid, naphthylamine sulphonic acids, salicylic acid, amidophenylene
oxamic acid, amidototoluylene oxamic acid, or the like. The dye-stuffs thus
produced can also be rendered fast against washing and fulling by treatment on
fibre with chromates and salts of copper or the like.

page_text: BLACK TETRAZO DYE-STUFF OBTAINED FROM EQUAL MOLECULAR PROPORTIONS.
OF BENZIDINE METAMIDO PHENYLENE OXAMIC ACID, a₁ а DIHYDROXY-
NAPHTHALENE a MONOSULPHONIC ACID, AND META PHENYLENE DIAMINE..
The tetrazo diphenyl solution prepared from 18:14 parts of benzidine is mixed'
with a solution in water of 18 parts of metamido phenylene oxamic acid.
The resulting product is again diazotised in the manner described in the fore-
going example, and the tetrazo compound thus formed is introduced into a
watery solution of 24 parts of dihydroxynaphthlene monosulphonic acid, mixed
with a small quantity of sodium carbonate, and with an excess of sodium acetate.
The combination being finished, a solution of 10-8 parts of metaphenylene diamine
in a small quantity of hydrochloric acid is added. The complete dye-stuff has the
following formula:-
NIT
It yields, on unmordanted cotton, black shades which become fast against washing
and the action of light, on being subsequently treated with salts of chromic acid, or
with salts of copper or the like.
Other dye-stuffs result, if, for instance, the diazo derivative of the intermediate.
product from equal molecular proportions of benzidine and metamido phenylene.
oxamic acid, is coupled first with one molecular proportion of meta phenylene
diamine, and then with one molecular proportion of a dihydroxynaphthalene mono-
sulphonic acid, or if tetrazodiphenylchloride is coupled with one molecular
proportion of metamido phenylene oxamic acid, and then with one molecular-
proportion of dihydroxynaphthalene monosulphonic acid, and if the diazo compound.
of the so-formed product is coupled with metaphenylene diamine. By such and the
like modifications, products are obtained which do not materially differ in their
properties from that produced in the example, as all these products have either-
the constitutional formula-

page_text: Similar dye stuffs are produced by using in the above example, instead of
bensidine, other diamido compounds, such as tolidine, dianisidine, or the like
diamines, or by using other analogous compounds instead of dihydroxynaphthalene 5
mono sulphonic acid and metaphenylene diamine.
BLUE-BLACK AZO DYE-STUFF PRODUCED FROM ONE MOLECULAR PROPORTION
OF TOLIDINE, ONE MOLECULAR PROPORTION OF METAMIDOTOLUYLENE
OXAMIC ACID, AND TWO MOLECULAR PROPORTIONS OF as a
DROXYNAPHTHALENE-a-SULPHONIC ACID.
DIHY-
A solution of tetrazo ditolyl prepared from 21.2 parts of tolidine in the usual
manner, is introduced into a solution obtained by dissolving 38.8 parts of metamido
toluvlene oxamic acid-
1
BLUE-BLACK AZO DYE-STUFF PRODUCED FROM ONE MOLECULAR PROPORTION
OF TOLIDINE, ONE MOLECULAR PROPORTION OF METAMIDOTOLUYLENE
OXAMIC ACID, AND TWO MOLECULAR PROPORTIONS OF a a DIHY-
DROXYNAPHTHALENE-a-SULPHONIC ACID.
A solution of tetrazo ditolyl prepared from 21.2 parts of tolidine in the usual
manner, is introduced into a solution obtained by dissolving 38.8 parts of metamido
toluylene oxamic acid-
CH3
CHÁNH,
NH.COCOOH
in a small quantity of caustic soda-lye, and adding an
excess of sodium acetate. After about 24 hours, the mixture is rendered alkaline;
and heated for a short time at about 50 degrees Centigrade. The so-formed amido
azo compound is salted out and filtered off. It is diluted with a small quantity of
water, and diazotised by means of 14 parts of sodium nitrite in the presence of an
excess of muriatic acid, at a temperature of about from 5 to 10 degrees Centigrade.
The formation of the tetrazo compound is complete after about 12 hours. The
tetrazo compound, filtered off, is stirred into a watery solution of 48 parts of
alpha, alpha, dihydroxynaphthalene alpha sulphonic acid "S," and the mixture is
allowed to stand. At the end of 12 hours, the mixture is rendered alkaline with
sodium carbonate, and heated for a short time at about 50 degrees Centigrade:
The thus finished dye-stuff is salted out, filtered off, pressed, and dried.
produces, on unmordanted cotton, bluish-black shades which become fast against
washing and the action of light by subsequent treatment with potassium bichromate
or sulphate of copper or the like.
It

page_text: The tolidine may be replaced in the example be equivalent quantities of
analogous paradiamines, and instead of two molecular proportions of dihydroxy-
naphthalene monosulphonic acid, two molecular proportions of other dye-stuff
components, employing either the same or two different ones, may be used, analogous
dye-stuffs being thus obtained.
VIOLET-BLACK AZO DYESTUFF OBTAINED FROM ONE
PRO-
MOLECULAR
PORTION OF BENZIDINE, ONE MOLECULAR PROPORTION OF METAMIDO-
PHENYLENE OXAMIC ACID, ONE MOLECULAR PROPORTION OF a1 NAPH-
THYLAMINE-ẞ3 SULPHONIC ACID, AND TWO MOLECULAR PROPORTIONS
OF α a DIHYDROXYNAPHTHALENE-a-MONOSULPHONIC ACID.
The intermediate product obtainable as described in the foregoing third example
from 184 parts of benzidine and 18 parts of metamidophenylene oxamic acid, is
stirred into a solution of 33 parts of the sodium salt of alpha, naphthylamine beta,
sulphonic acid. The resulting mixture is allowed to stand during 24 hours, and is
then heated at about 60 degrees Centigrade by means of a water-bath. After
being rendered alkaline, the finished amido azo compound is filtered off, and mixed
with a small quantity of water. 14 parts of sodium nitrite and an excess of
muriatic acid are then added. At the end of 24 hours, the finished tetrazo
compound is introduced into a solution of 53 parts of the sodium salt of
alpha, alpha-dihydroxynaphthalene alpha mono sulphonic acid, and the mass is
allowed to stand during 24 hours. The complete dye-stuff thus formed is isolated
in the usual way.
It produces, on unmordanted cotton, violet-black-shades which
are rendered fast against the action of washing and fulling by a subsequent
treatment on fibre with salts of chromic acid or salts of copper, or other suitable
salts.

page_text: The dye-stuff components used in the preceding sixth example may be replaced
by analogous bodies, similar colouring matters being thus obtained.
Other dyestuffs result if, in the foregoing Examples 1, 2, 3, 4, 6, metamido-
toluylene oxamic acid is used instead of metamidophenylene oxamic acid, or if, in
Example 5, the metamidotoluylene oxamic acid is replaced by the phenylene
compound, or if other "acidylamines.” such as acetylmetaphenylene diamine,
benzoyl metaphenylene diamine, or the like, are used in place of metamidophenylene,
or metamidotoluylene oxamic acid. The colouring matters thus obtained possess
properties similar to those of the dyestuffs described in the foregoing examples.
According to the researches of my foreign correspondents, the above defined
poly-azo dyestuffs may also be produced on fibre; for instance, by dyeing fibres or
materials with amido azo compounds prepared from diazo or tetrazo compounds
and acidyldiamines in the above described manner, by further diazotising these
compounds on fibre, and subsequently coupling with phenols, amines, amidophenols,
or other. dyestuff components. Thus, for instance, the symmetrical colouring
. matter obtained by coupling one molecular proportion of tetrazodiphenyl with two
molecular proportions of metamido phenylene oxamic acid, produces, on cotton,
yellowish-orange shades, and in order to produce the aforesaid polyazo colouring
matters on fibre, the material thus dyed is treated first in a bath containing
sodium nitrite and muriatic acid in the usual manner, and subsequently is placed
in a solution of any dyestuff component, using phenols, amines, amidophenols,
'amidophenolethers, their sulpho or carboxylic acids, or the like. In an analogous
manner, so-called "mixed" dyestuffs, such as that blue-black dyeing product
obtainable from one molecular proportion of tetrazodianisol, one molecular pro-
portion of metamidophenylene oxamic acid, and one molecular proportion of
alpha, alpha, dihydroxynaphthalene. alphasulphonic acid, or the brown dyestuff
obtained from one molecular proportion of tetrazo-diphenyl, one molecular
proportion of metamidophenylene oxamic acid, and one molecular proportion of
gammaamidonaphtholsulphonic acid, can be diazotised and coupled on fibre in the
manner hereinafter defined. The shades thus produced may be rendered more
fast by a subsequent treatment with sodium dichromate or other metallic salts.
As above mentioned, my foreign correspondents have produced other azo
dyestuffs containing acidylamido groups, by coupling diazotised acidylamid
compounds with dye-stuff components, and they have found that amongst these
dyestuffs those are of especial value which are prepared from aromatic diamines

page_text: in which a hydrogen atom of one amido group is substituted by the radicle of a
more basic acid, such as oxalic acid, succinic acid, phthalic acid, and the like.
Such compounds are metamido or paramido phenylene oxamic acid.
metamido or paramidotoluylene oxamic acid, and the like.
My foreign correspondents have found that such compounds are profitably used
for the production of polyazo dye-stuffs. For this purpose, diazotised acidy!
diamines are combined with amido compounds which, when coupled, are capable of
further diazotisation, such as alphanaphthylamine, alpha, amido beta, naphthol-
ethylether, alpha, naphthylamine beta, (or beta) sulphonic acid, amidonaphthols,
amidonaphtholsulphonic acids, alpha, amido beta naphtholethylether beta, (or
beta) sulphonic acid, metamidophenylene oxamic acid and its homologues,
paraxylidine, and the like. The dyestuffs thus obtained are further diazotised,
either in bulk or on fibre, and are then coupled with dyestuff components,-
disazo dyestuffs being produced which yield dark shades very fast against the
action of washing and fulling.
If treated with potassium bichromate or sulphate of copper, or the like, these
shades become still darker, and entirely fast against the action of washing and
fulling; for instance, fibres mordanted with salts of chromic acid and the like may
be dyed with these dyestuffs, the same shades being obtained. My foreign corre-
spondents give the following example, the parts being by weight.
BLACK AZO-DYESTUFF FROM EQUAL MOLECULAR PROPORTIONS OF MET-
AMIDOPHENYLENE OXAMIC ACID, ALPHANAPHTHYLAMINE, AND ALPHAI
ALPHA-DIHYDROXYNAPHTHALENE-a-SULPHONIC ACID "S."
A diazo solution prepared from 18 parts of metamidophenylene oxamic acid in
the usual way, is introduced into a solution of 18 parts of alphanaphthylamine
hydrochloride. The mixture is allowed to stand during 12 hours. At the end of
this time, an excess of acetate of sodium is added, and after about 12 hours, the
mixture is rendered alkaline by means of soda lye, and is then heated for a short
time at about 50 degrees Centigrade. The intermediate product thus formed is
salted out and filtered off. After adding a small quantity of water, it is mixed
with a solution of 7 parts of nitrite of sodium, and then with an excess of muriatic.
acid, care being taken that the temperature does not exceed about from 5 to
10 degrees Centigrade. After 12 hours, the finished diazo compound is filtered off
and stirred into a watery solution prepared from 24 parts of alpha-alpha, dioxy-
naphthalene alphasulphonic acid, and containing an excess of sodium acetate.
the end of 12 hours, the mixture is heated for a short time at about 50 degrees
Centigrade. It is rendered alkaline with carbonate of sodium, and the finished
dyestuff is filtered off, pressed, & dried.
At
It yields, on wool, deep black shades which are rendered fast against washing,
fulling, and the action of light, by a subsequent treatment with salts of chromic
acid, or salts of copper or the like.
The dyestuff has the formula :—

page_text: Similar dyestuffs are obtained if the metamidophenyleneoxamic acid is replaced
by other acidyle-diamines, or if other amido compounds which, when coupled, are
apable of further diazotisation, are used in place of a-naphthylamine, or if the
dihydroxynaphthalenesulphonic acid is replaced by other dyestuff components.
If, for instance, amines or amido-sulphonic acids be employed instead of dihydroxy-
naphthalenesulphonic acids, brown & brown-black dye stuffs are produced.
My foreign correspondents do not limit themselves to the particulars given in
the above examples, as the directions contained therein may be varied. The
present invention relates, in general, to the production in bulk or on fibre of azo
dyestuffs and of polyazo dyestuffs from aromatic diamines in which a hydrogen
atom of one amido group is substituted by the radicle of any organic acid, which
process consists either-
(1.) In diazotising acidyldiamines, and coupling the thus obtained diazo
derivatives with dyestuff components;-or
(2.) In combining diazoderivatives of acidyldiamido compounds with amido
compounds yielding amidoazo compounds, which are capable of being further
diazotised, and in subsequently coupling the so formed diazo products with dyestuff
components in bulk or on fibre ;-or
' (3.) In combining with diazo or tetrazo compounds, acidyldiamines which are
capable of being combined with diazo compounds to form azo dyestuffs. In using
tetrazo compounds, iny foreign correspondents either couple one molecular propor-
tion of these bodies with two molecular proportions of acidyl diamines (employing
either the same or two different ones), or they couple equal molecular proportions
of a tetrazo compound, and, in any order, an acidyl diamine and any other dyestuff
component or
(4.) In further diazotising the last named dyestuffs from diazo or tetrazo
compounds and acidyl diamines, and in coupling the thus formed diazo compounds,
with dyestuff components, likewise in bulk and on fibre.
Dated this 7th day of June 1895.
NEWTON & SON,
Agents for the Applicant.
The Manufacture or Production of New 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 and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :—
"
Azo dye-stuffs containing acidylamido groups have been but little used hitherto
for dyeing purposes. My foreign correspondents apply the term "acidylamido
groups," in the present Specification, to amido groups in which a hydrogen atom is
displaced by the radicle of any organic acid, and in accordance therewith they
apply the expression "acidylamido compounds" to products containing amido
groups in which a hydrogen atom is displaced by any organic acid radicle.
My foreign correspondents have now produced new azo dye-stuffs containing
such acidylamido groups which are of great value for dyeing and printing purposes.
Their researches have shewn that acidyldiamido compounds, in which a hydrogen
atom in one of the amido groups is displaced by the radicle of any polybasic acid,
such as oxalic acid, succinic acid, phthalic acid, or the like, are of special value for
the said purposes.
In order to produce such dye-stuffs containing acidylamido groups, my foreign
correspondents use "diamido compounds
of the aromatic series, in which a
hydrogen atom in one of the amido groups is displaced by the radicle of any organic

page_text: acid, and they obtain monazo- and disazo dye-stuffs, either by diazotising the amido
group in the said diamido compounds, and coupling the diazo acidylamido deriva-
tives thus formed with the usual dye-stuff components; or, inversely, by acting
with diazo compounds (including diazo acidylamido derivatives) on acidyldiamido
compounds capable of combining with diazo derivatives to form azo dye-stuffs; or
by allowing a molecular proportion of a tetrazo compound to act on two molecular
proportions of either a single acidyldiamido compound, or of two such in molecular
proportions, or by combining a molecular proportion of a tetrazo compound, in any
order, with a molecular proportion of an acidyldiamido compound and a molecular
proportion of any other dye-stuff component.
The production of these monazo and disazo dye-stuffs is effected in the well-
known manner.
My foreign correspondents have further found that the azo dye-stuffs prepared
by coupling acidyldiamine with diazo or tetrazo compounds, especially the mixed
and symmetrical disazo dye-stuffs prepared by coupling a molecular proportion of
an acidyldiamine and a molecular proportion of any other dye-stuff component,
with a molecular proportion of a tetrazo compound, or by coupling two molecular
proportions of acidyldiamines with one molecular proportion of a tetrazo compound,
such as tetrazodiphenyl, tetrazo ditolyl, or the like, can be profitably used as
so-called intermediate products for the manufacture of new valuable polyazo
dye-stuffs, that is to say, the mixed and symmetrical disazo dye-stuffs herein before
defined can be further diazotised, and the diazo or tetrazo compounds thus formed
can be combined with the usual dye-stuff components, thereby producing the said
polyazo dye-stuffs.
But whereas diazo or tetrazo compounds and aniline, or the like monamines of
the benzene series, afford intermediate products suitable for further diazotisation
and combination only with great difficulty, diazo amido compounds being usually
formed, diazo- and tetrazo compounds readily act on acidyl diamines, normal amido-
azo compounds being produced according to the experiments of my foreign
correspondents. The dye-stuffs obtained by further diazotising the last-named
amido-azo compounds, and subsequently combining the diazo-derivatives with
dye-stuff components, are generally more soluble, and withstand the action of
alkali better, and also yield darker shades on-fibres, than the analogous dye-stuffs
derived from aniline, toluidine, or the like.
In producing these new dye-stuffs containing acidyl amido groups, all acidyl
diamines of the benzene or naphthalene series may be used which can be combined
with diazo compounds. Such acidyldiamines are, for instance, acetyl metaphenylene
diamine, acetyl meta toluylene diamine, the metamidophenylene oxamic acid
represented by the formula:-
(see Klusemann, Berichte der Deutschen Chem. Gesellschaft 7, 1261), metamido
toluylene oxamic acid, and similar compounds, which are prepared in a well-known
manner.
The last named acidyldiamines, and the analogues thereof containing free
carboxylic groups, are of special value, as the dye-stuffs derived therefrom yield
shades which (particularly when treated with salts of chromic acid, salts of copper,
or other metallic salts) withstand washing and fulling particularly well.

page_text: In order to illustrate the process of producing such dye-stuffs, my foreign
correspondents give the following six examples. The parts are by weight :-
VIOLET-BLACK AZO DYE-STUFF OBTAINED FROM MOLECULAR PROPORTIONS
OF α-NAPHTHYLAMINE, METAMIDOPHENYLENE OXAMIC ACID, AND ALPHA₁
NAPHTHOL ALPHA SULPHONIC ACID.
A diazo solution obtained in the usual manner from 14.3 parts of alpha-
naphthylamine, by means of sodium nitrite and muriatic acid, is allowed to flow
into a solution of 18 parts of metamidophenylene oxamic acid-
in cold water, to which a small quantity of caustic soda-lye, and an excess of
sodium acetate, have been added. The mixture is stirred during 24 hours, and
after having been rendered alkaline at a low temperature, is heated for a short
time at about 50 degrees Centigrade. The amido azo compound thus formed
having then been filtered off and mixed with a small quantity of water, 7 parts of
nitrite of sodium, and a sufficient quantity of muriatic acid, are added, at from
about 5 to 10 degrees Centigrade. After 12 hours, the finished diazo compound is
filtered off, and added to a solution of 22.4 parts of alpha, naphthol alpha, sulphonic
acid, rendered alkaline with sodium carbonate. After standing during about
12 hours, the mixture is heated for a short time at about 50 degrees Centigrade.
The finished dye-stuff thus formed is salted out, filtered, pressed, and dried. It
produces violet-black shades on wool, which withstand washing and fulling after
treatment with bichromate of potassium and the like.
The dye-stuff is represented by the formula :-
Instead of the above prescribed alpha, naphthol alpha, sulphonic acid, other
naphtholsulphonic acids, or dihydroxynaphthalene sulphonic acids, or naphthyl-
amine sulphonic acids, may be used, from blue-black to grayish-black dye-stuffs
being thus produced. Similar products are obtained, if other amines, or substituted
amines, such as aniline, sulphanilic acids, naphthylamine sulphonic acids, nitranilines,
amido-benzoic acids, amidosalicylic acid, or the like, are used instead of alpha
naphthylamine.

page_text: GREEN-BLACK AZO DYE-STUFF FROM MOLECULAR PROPORTIONS OF DEHYDRO-
THIOTOLUIDINE SULPHONIC ACID, METAMIDOPHENYLENE OXAMIC ACID,.
DIHYDROXYNAPHTHALENE SULPHONIC ACID "S" (
AND
-
ALPHAL
ALPHA DIHYDROXYNAPHTHALENE ALPHA, MONO-SULPHONIC ACID).
A diazo solution prepared from 34.2 parts of dehydrothiotoluidine sulphonic acid,
in the usual manner, is allowed to flow into a solution obtained by dissolving 18 parts
of metamidophenylene oxamic acid in cold water, together with a small quantity of
soda-lye, and an excess of sodium acetate. After about 12 hours, the mixture is.
rendered alkaline, and heated to about 50 degrees Centigrade. The amido-azo.
compound which is thus formed having been filtered off, and then mixed with a
small quantity of water, 7 parts of sodium nitrite, and an excess of muriatic acid,.
are added at from 5 to 10 degrees Centigrade.
After 12 hours, the diazo compound is filtered off, and added to a solution of
24 parts of alpha₁ alpha dihydroxynaphthalene alpha monosulphonic acid
containing an excess of sodium acetate. The mixture is allowed to stand during
12 hours. It is then heated for a short time, at about 50 degrees Centigrade, and
after adding a small quantity of sodium carbonate, the dye-stuff is salted out,.
filtered off, pressed, and dried.
•
It dyes unmordanted cotton green-black shades, which are rendered fast, both
on washing and fulling, by a subsequent treatment of the dyed goods with potassium.
bichromate or similar metallic salts.
The dye-stuff is represented by the formula :—
5 If an equivalent quantity of phenol is used, instead of dihydroxynaphthalene-
monosulphonic acid "S," in carrying out the foregoing example, a disazo dyestuff
is formed, which may be converted, by further alkylation, into a new valuable
colouring matter, yielding, on unmordanted cotton, chocolate-brown shades which.
withstand the action of alkali, acids, and light.
- VIOLET-BLACK AZO DYE-stuff prodUCED FROM ONE MOLECULAR PROPORtion
OF BENZIDINE, ONE MOLECULAR PROPORTION, OF METAMIDOPHENYLENE-
OXAMIC ACID, AND TWO MOLECULAR PROPORTIONS OF DIHYDROXY-
NAPHTHALENESULPHONIC ACID "S" (ALPHA ALPHA-DIHYDROXYNAPH-
THALENE-ALPHA, SULPHONIC ACID).
18-4 parts of benzidine are diazotised in the usual manner, and the tetrazo
solution is added to a solution of 18 parts of metamido-phenyleneoxamic acid,
mixed with a small quantity of caustic soda-lye or sodium carbonate, and an excess of

page_text: sodium acetate. The mixture is stirred during about 24 hours. The intermediate
product thus formed is diazotised by means of 7 parts of sodium nitrite and a
small excess of muriatic acid, and the product is allowed to stand during 12 hours.
The diazo compound is then poured into a solution of 48 parts of alpha, alpha-
dihydroxynaphthalene alpha-monosulphonic acid, containing an excess of sodium
acetate. At the end of 12 hours, the mass is rendered alkaline by means of sodium
carbonate, and heated for a short time at about 50 degrees Centigrade. The dye-stuff
is then salted out pressed and dried. It produces on unmordauted cotton violet-black
shades which may be rendered deep-black and capable of withstanding washing and
the action of light by a subsequent treatment with chromates or salts of copper, or
the like.
The dye stuff is represented by the formula :-
Equivalent quantities of other aromatic diamines, such as tolidine, dianisidine, or
the like, may be substituted for benzidine, similar dyestuffs being thus obtained.
Instead of alpha₁ alpha dihydroxynaphthalene-alpha monosulphonic acid,
corresponding quantities of other dye-stuff components may be used, such as
alpha, naphthol alpha, or 3 sulphonic acid, alpha, alpha dihydroxynaphthalene
beta beta disulphonic acid, gamma-amidonaphtholsulphonic acid, alpha,
alpha, naphtholsulphonic acid, naphthylaminesulphonic acids, salicylic acid,
amidophenylene oxamic acid, amidotoluylene oxamic acid, or the like.
dye-stuff's thus produced can also be rendered fast, on washing and fulling, by
treatment on the fibre with chromates or salts of copper or the like.
The
}
METAMIDOPHENYLENE
BLACK TETRAZO DYE-STUFF OBTAINED FROM MOLECULAR PROPORTIONS OF
BENZIDINE,
OXAMIC ACID, ALPHA! ALPHA
ALPHA-MONOSULPHONIC ACID, AND. META-
DIHYDROXYNAPHTHALENE
PHENYLENE DIAMINE.
The tetrazodiphenyl solution prepared from 18.4 parts of benzidine is mixed
with a solution of 18 parts of metamidophenylene oxamic acid, to which has
been added 20 parts of a 20 per cent. caustic soda-lye, and an excess of sodium
acetate.
The product is again diazotised in the manner described in the foregoing
I example, and the tetrazo compound thus formed is introduced into a solution of

page_text: 24 parts of dihydroxynaphthalenemonosulphonic acid, containing an excess of
sodium acetate. When the combination is effected, a solution of 10.8 parts
of metaphenylenediamine, in a small quantity of hydrochloric acid, is added. The
dye-stuff is represented by the following formula:-
It produces black shades on unmordanted cotton, which may be made to
withstand washing and the action of light by treatment with salts of chromic acid,
or with salts of copper or the like.
Similar dye stuffs are formed if, for instance, the diazoderivatives of the
intermediate product from molecular proportions of benzidine and metamido-
phenylene oxamic acid is coupled, first, with a molecular proportion of metaphenyl-
enediamine, and then with molecular proportion of a dihydroxynaphthalenemono-
sulphonic acid, or if tetrazodiphenylchloride is coupled with a molecular proportion
of metamidophenylene oxamic acid, and then with a molecular proportion of
dihydroxynaphthalenemono sulphonic acid, and if the diazo compound of the
product is coupled with metaphenylenediamine. By such and the like modifica-
tions, products are obtained which do not materially differ in their properties from
that produced by following the example, as all these products are represented
either by the formula :-

page_text: BLUE BLACK AZO DIE-STUFF PRODUCED FROM ONE MOLECULAR PROPORTION
OF TOLIDINE, TWO MOLECULAR PROPORTIONS OF METAMIDOTOLUYLENE-
OXAMIC ACID, AND TWO MOLECULAR PROPORTIONS OF ALPHA ALPHA
DIHYDROXYNAPHTHALENE-ALPHA SULPHONIC ACID "S."
A solution of tetrazoditolyl, prepared from 21.2 parts of tolidine in the usual
manner, is introduced into a solution of 38.8 parts of metamidotoluyleneoxamic
acid-
CH3
CoHg-NH,
NH.CO. COOH.
After
in a small quantity of soda lye, together with an excess of sodium acetate.
about 24 hours, the mixture is rendered alkaline, and heated for a short time at
about 50 degrees Centigrade. The amidoazo compound having been salted out
and filtered off, is rinsed with a small quantity of water, and diazotised by means
of 14 parts of sodium nitrite and an excess of muriatic acid, at a temperature of
about 5 to 10 degrees Centigrade. The formation of the tetrazo compound is
complete after about 12 hours. The tetrazo compound having been filtered off, is
stirred into a solution of 48 parts of alpha, alpha, dihydroxynaphthalene alpha-
sulphonic acid "S," and the mixture is allowed to stand. At the end of 12 hours,
the mixture is rendered alkaline with sodium carbonate, and heated for a short
time at about 50 degrees Centigrade. The dye-stuff is salted out, filtered off,
pressed, and dried. It produces, on unmordanted cotton, bluish-black shades,
which may be made to withstand washing and the action of light by subsequent
treatment with potassium bichromate or sulphate of copper, or the like.

page_text: Equivalent quantities of analogous paradiamines may be substituted for tolidine,
and instead of two molecular proportions of dihydroxynaphthalenemonosulphonic
acid, two molecular proportions of either a single or two other dye-stuff components
may be used, analogous dye-stuffs being thus obtained.
VIOLET-BLACK AZO DYESTUFF OBTAINED FROM ONE MOLECULAR PROPORTION
OF BENZIDINE, ONE MOLECULAR PROPORTION OF METAMIDO PHENYLENE
OXAMIC ACID, ONE MOLECULAR PROPORTION OF ALPHA, NAPHTHYLAMINE-
BETA-SULPHONIC ACID, AND TWO MOLECULAR PROPORTIONS OF ALPHA]
ALPHA-DIHYDROXYNAPHTHALENE, ALPHA-MONOSULPHONIC ACID.
The intermediate product obtainable as described in the foregoing third example,
from 184 parts of benzidine and 18 parts of metamidophenylene oxamic acid, is
stirred into a solution of 24.6 parts of the sodium salt of alpha, naphthylamine
beta, sulphonic acid. The mixture is allowed to stand during 24 hours, it is then
heated at about 60 degrees Centigrade. After being rendered alkaline, the
finished amido azo compound is filtered off, and mixed with a small quantity of
water. 14 parts of sodium nitrite, and an excess of muriatic acid, are then added.
At the end of 24 hours, the tetrazo compound is filtered off, and introduced into a
solution of 526 parts of the sodium salt of alpha, alpha, dihydroxynaphthalene
alpha monosulphonic acid, containing a suitable quantity of sodium acetate, and
the mass is allowed to stand during 24 hours. The dye-stuff thus formed is
isolated in the usual way. It produces violet-black shades on unmordanted cotton,
which are rendered fast, on washing and fulling, by a subsequent treatment on the
fibre with salts of chromic acid, or salts of copper or other suitable salts.

page_text: The coloring matter is represented by the formula-
Instead of the dye-stuff components used in the preceding sixth example,
analogous compounds may be used, similar coloring matters being thus obtained.
Other dye-stuffs are formed if, in the foregoing examples 1, 2, 3, 4, 6, metamido-
toluylene oxamic acid is used instead of metamidophenylene oxamic acid, or by
substituting, in Example 5, for the metamidotoluylene oxamic acid, the corresponding
phenylene compound, or if other acidyldiamines, such as acetyl metaphenylene
diamine, benzoyl meta phenylene diamine, or the like, are used instead of
metamidophenylene, or metamidotoluylene oxamic acid. The coloring matters
thus obtained possess properties similar to those of the dye-stuffs described in the
foregoing examples.
According to the researches of my foreign correspondents, the above defined
poly-azo dye-stuffs may also be produced on fibres, for instance, by dyeing fibres or
materials with amido-azo compounds prepared from diazo or tetrazo compounds, and
acidyl diamines, in the above described manner, then diazotising these compounds
on the fibre, and subsequently coupling with phenols, amines, amidophenols, or
other dye-stuff components. Thus, for instance, the symmetrical coloring matter
obtained by coupling a molecular proportion of tetrazodiphenyl with two molecular
proportions of metamido phenylene oxamic acid, produces yellowish-orange shades
on cotton, and in order to produce the aforesaid polyazo coloring matters on the
fibre, the material thus dyed is first diazotised in a bath containing sodium nitrite
and muriatic acid, in the usual manner, and is subsequently placed in a solution of
any dye-stuff component, using phenols, amines, amidophenols, amidophenolethers,
their sulpho or carboxylic acids, or the like. In an analogous manner, so-called
mixed dyestuffs, such as the blue-black dyeing product obtainable from a molecular
proportion of tetrazo dianisol, a molecular proportion of metamidophenylene oxamic
acid, and a molecular proportion of alpha, alpha, dihydroxynaphthalene alpha
sulphonic acid, or the brown dye-stuff obtained from a molecular proportion of
tetrazo-diphenyl, a molecular proportion of metamidophenylene oxamic acid, and
a molecular proportion of gamma amido naphtholsulphonic acid, can be diazotised,
and coupled, while on the fibre, in the manner hereinbefore defined. The shades
thus produced may be rendered more fast by a subsequent treatment with sodium
dichromate, or other metallic salts.
As above mentioned, my foreign correspondents have produced other azo dye-
stuffs containing acidylamido groups, by coupling diazotised acidylamido compounds
with dye-stuff components, and they have found that amongst these dye-stuffs,
those are of special value which are prepared from aromatic diamines in which a
hydrogen atom of one of the amido groups is displaced by the radicle of a

page_text: poly-basic acid, such as oxalic acid, succinic acid, phthalic acid, and the like. Such
compounds are metamido or paramido phenylene oxamic acid,
metamidotoluylene oxamic acid, and the like.
My foreign correspondents have found that such compounds are profitably used
for the production of poly-azo dye-stuffs. For this purpose, diazotised acidyl-.
diamines are combined with amido compounds which, when coupled with them,
afford compounds capable of being further diazotised, such as alpha-naphthylamine,
alpha, amido beta, naphtholethylether, alpha, naphthylamine beta, (or beta)
sulphonic acid, amidonaphthols, amidonaphtholsulphonic acids, alpha, amido beta,
naphtholethylether beta, (or beta) sulphonic acid, metamidophenylene oxamic
acid, and its homolgues, paraxylidine, and the like. The dye-stuffs thus obtained
are further diazotised, either as such, or on the fibre, and are then coupled with
dye-stuff components, disazo dye-stuffs being produced which yield dark shades
very fast both on washing and fulling.
If treated with potassium bichromate or sulphate of copper or the like, these
shades become still darker, and entirely fast, on washing and fulling. Of course,
fibres mordanted with salts of chromic acid and the like may be dyed with these
dye-stuffs, the same shades being obtained. My foreign correspondents give the
following example, the parts being by weight:
BLACK DISAZO DYE-STUFF FROM MOLECULAR PROPORTIONS OF METAMIDO-
PHENYLENE OXAMIC ACID, ALPHA NAPHTHYLAMINE, AND AMIDO-
NAPHTHOLMONOSULPHONIC ACID G.
A diazo solution prepared from 18 parts of metamido phenylene oxamic acid in
the usual manner, is introduced into a solution of 18 parts of alphanaphthylamine
hydrochloride. The mixture is allowed to stand during 12 hours. At the end of
this time, an excess of acetate of sodium is added, and after about 24 hours, the
mixture is rendered alkaline by means of soda-lye. The intermediate product thus
formed is salted out and filtered off. After adding a small quantity of water, it is
mixed with a solution of 7 parts of nitrite of sodium, and then with an excess of
muriatic acid, care being taken that the temperature does not exceed about
from 5 to 10 degrees Centigrade. After 12 hours, the diazo compound is filtered
off, and stirred into a watery solution of 23.9 parts of amidonaphtholmonosulphonic
acid G, containing an excess of sodium carbonate. At the end of 12 hours, the
mixture is heated for a short time at about 50 degrees Centigrade, and the dye-
stuff is then filtered off, pressed, and dried.
It produces black shades on cotton. On further diazotising the dye-stuff, and
coupling it with dye-stuff components on the fibre, deep black shades are obtained,
which are distinguished by their great fastness on washing and fulling, and in
light.
The dve stuff is represented by the formula…….

page_text: Similar dye-stuffs are obtained by substituting, for the metamidophenylene
oxamic acid, other acidyldiamines, or if other amido compounds yielding products,
which can be further diazotised are used in place of alphanaphthylamine, or by
substituting for the amidonaphthol sulphonic acid G, other dye stuff components.
If, for instance, amines or amido sulphonic acids be employed instead amido-
naphtholsulphonic acid G, brown and brown-black dye-stuffs are produced.
My foreign correspondents do not limit themselves however, to the particulars
given in the above examples, as the directions contained therein may be varied.
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 manufacture or production of monazo dye-stuffs by combining the diazo
derivatives of the amido phenylene oxamic acids, or of its homologues and
analogues, with the usual dye-stuff components.
2. The production of dis-azo dye-stuffs by combining the dis-azo derivatives of
the amidophenylene oxamic acids, and of their homologues and analogues, with
amido compounds which yield amido-azo compounds capable of being further
diazotised, by further diazotising the so-formed intermediate products, and by
coupling the diazo-azo compounds thus obtained with dye-stuff components, either
in bulk or on fibres.
3. The production of azo dye-stuffs (a) by combining any diazo derivative of
the benzene or naphthalene series, with metamidophenylene oxamic acid, or other
so-called acidyldiamido compounds of the aromatic series, which are capable of
being coupled with diazo derivatives; (b) by combining one molecular proportion
of any tetrazo derivative of the aromatic series, such as tetrazo-diphenyl or the
like, with two molecular proportions of metamidophenylene oxamic acid, or of
other so-called acidyldiamido compounds of the aromatic series, capable of being
combined with diazo compounds, using either one or two different compounds, or,
in any order, with one molecular proportion of an acidyl diamine, and with one
molecular proportion of any other dye-stuff component.
4. The use of metacidyldiamines of the aromatic series in the process illustrated
by the foregoing Claim Three.
5. The production of polyazo dye-stuffs by further diazotising the amido-azo
compounds obtained by the processes described in Claim 3, and in coupling the
so-formed diazo-azo products with suitable dye-stuff components, either in bulk or
on fibres.
6. The use of metacidyl diamines of the aromatic series, for the production of
polyazo dye-stuffs in the manner defined in the foregoing Claim 5.
7. As new products of manufacture-(a) the new coloring matters produced by
means of the processes herein before defined, or by any other means producing the
same result; (b) the fibres or materials dyed, printed, or treated in the manner
hereinbefore defined, or in any other way affording the same result.
Dated this 5th day of March 1896.
NEWTON & SON,
Agents for the Applicant.