The Manufacture or Production of Azo Colouring Matters, and Materials therefor.
Year: 1894

page_text: Date of Application, 12th Mar., 1894
Complete Specification Left, 12th Dec., 1894-Accepted, 12th Jan., 1895
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
.
The Manufacture or Production of Azo Colouring Matters, and
Materials therefor.
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:-
Of ẞ, amido-a-naphtholmonosulphonic acids, only one has become known up to
the present time, vz., the so-called B₁ amido a, naphthol ẞ, monosulphonic acid G,
which can be obtained by melting with alkalies the 3 naphthylaminedisulphonic
acid G.
My foreign correspondents have now found that two new B₁-amido a naphthol-
monosulpho acids differing from the said ẞ, amido a naphthol ẞ, monosulphonic
acid G, are produced by sulphonating B₁ amido a naphthol. My foreign
correspondents prepare the last-named B₁ amido a naphthol, by melting with
alkalies the B, naphthylamine a sulphonic acid, or salts thereof, at from 260 to
270 degrees Centigrade. The resulting amidonaphthol dissolves readily in hot
water, but with difficulty in cold water, and crystallises in scales possessing silver-
like lustre, and melting at 158 degrees Centigrade.
In order to illustrate the method of transforming B₁ amido a naphthol into two
isomeric B, amido a naphtholmonosulphonic acids, the following example is given.
The parts are by weight,
PRODUCTION OF TWO ISOMERIC B₁ AMIDO a1
NAPHTHOLMONOSULPHONIC ACIDS
FROM AMIDO
a↓
NAPHTHOL.
10 parts of B₁ a, amidonaphthol (ẞi amido a naphthol) are dissolved in 50 parts
of concentrated sulphuric acid (at 66 degrees Baumé) at from about 20 to
30 degrees Centigrade. As soon
as the amido naphthol has dissolved, the
sulphonation is finished. The two isomeric acids separate as a white crystalline
mass of pap-like consistence, on pouring the sulphonated mixture into 200 parts of
water. In order to separate the two isomeric ẞ, amido a naphtholmonosulphonic
acids one from the other, the mixture of the two acids (filtered off from the
sulphuric liquid) is converted into the calcium salts, and the solution of the calcium
salts (which is about 400 litres if the parts are kilos. by weight) is mixed with
muriatic acid in excess. One of the two acids, viz., the so-called B₁ amido
a naphtholmonosulphonic acid V, separates in white flakes, which are filtered off,
whilst the other isomeric acid, that is to say, the so-called ẞ₁ amido ས naphthol-
monosulphonic acid Sch. is precipitated by adding common salt to the resulting
filtrate.
In order to produce the two isomeric ß₁ amido a naphthol monosulphonic acids,
my foreign correspondents do not limit themselves to the directions given in the

page_text: above example, for these can be varied. For instance, the sulphuric acid (at
66 degrees Baumé) can be replaced by a stronger sulphuric acid or a weaker
sulphuric acid (such as 60 degrees Baumé); in the latter case, the mixture must
be heated at about 60 degrees in order to effect the sulphonation. The separation
of the two acids can also be carried out in a manner other than that described in
the above first example, riz., by means of all those methods which can be used
where two substances are to be separated, one of which dissolves more readily than
the other.
On following the directions given in the above first example, nearly equal
proportions of the two isomeric. B₁ amido a naphtholmonosulphonic acids are
obtained.
The resulting two ẞ, amido a naphthol monosulphonic acids V and Sch. differ
by their properties from the aforesaid ẞ, amido a naphthol ẞ, monosulphonic
acid.
The researches of my foreign correspondents have shown, that, of the above
two new ẞ, amido a naphtholmonosulphonic acids V and Sch., the latter, viz., the
Bamido a naphtholmonosulphonic acid Sch., which differs by its higher degree of
solubility from the B₁ amido a naphtholmonosulphonic acid V, possesses great
technical value as a dye-stuff component, as it yields, when combined with the
tetrazo compounds of diamines, so-called "symmetrical" and "mixed" disazo dye-
stuffs, which produce, on unmordanted cotton, chiefly pure black and very intense
shades.
"
The method of producing these "symmetrical" and "mixed disazo dye-stuffs
from the B, anido a naphiholmonosulphonic acid Sch., in general consists either in
combining two molecular porportions of the said acid with one molecular proportion
of the tetrazo derivatives of "benzidine, its analogues or homologues," or in
coupling first one molecular proportion of the said acid with one molecular
proportion of a tetrazo compound derived from "benzidine, its analogues or
homologues," and in subsequently combining the resulting intermediate products
with one molecular proportion of another dye-stuff component (riz., amine, diamine,
phenol, amidophenol, amidophenolether of the benzene or naphthalene series, a
sulphonic or carboxylic acid thereof). In the latter case, so-called "mixed
disazo dye-stuffs are formed, which can also be produced by coupling one molecular
proportion of the tetrazo compounds derived from "benzidine, its analogues or
honologues," first with one molecular proportion of the said dye-stuff components,
and subsequently with one molecular proportion of ẞ, amido a naphtholmono
sulphonic acid Sch.
66
"
The combination of the ẞ₁ amido a naphtholmonosulphonic acid Sch., or salts
thereof, with the tetrazo compounds, or the intermediate products containing a
free diazo group, is most advantageously effected in alkaline solutions.
My foreign correspondents mean by the above expression, benzidine its
analogues or homologues," for instance, the following diamido compounds, viz.,
Benzidine, tolidine. diamidophenyltolyl, diamidodiphenolether, dianidoalkyl-
bydroxydiphenyl, diamidoalkylbydroxyphenyltolyl, diamidoazobenzene, diamido-
azotoluene, diamidoazoxylene, diamidoazoxybenzene, diamidoazoxytoluene, diamido
stilbene, diamidofluorene, dianidonaphthalene, diamidocarbazol, diamidod:-
phenyleneoxide, diamidoditoluyleneoxide, paraphenylenediamine, paratoluylene-
diamine, benzidinesulphone, tolidinesulphone, diamidophenyltolylsulphone,
..diamidodiphenoxyacetic acid, diamidodiphenyleneketoxine, diamidophenylbenz-
imidazol, diamidodiphenylamine, amidobenzeneazo a naphthylamine, amidotoluene-
azo a naphthylamine, amidoxyleneazo a naphthylamine, amidobenzeneazopara-
xylidine, amidotolueneazoparaxylidine, amidoxyleneazoparaxylidine,
benzeneazometaamidoparacresolether, amidotolueneazometaamidoparacresolether,
amidoxyleneazumetaamidoparacresolether, amidobenzeneazoorthoamidoparacresol-
amidotolueneazoorthoamidoparacresolether, amidoxyleneazoorthoamido-
paracresolether, amidobenzeneazo ethoxy a naphthylamine, amidotolueneazo
ẞ ethoxy a naphthylamine, amidoxyleneazo ẞ ethoxy a naphthylamine, sulphonic
ether,
amido-

page_text: acids, carboxylic acids or sulphocarboxylic acids thereof. My foreign corre-
spondents, however, do not limit themselves to the employment of the diamido
compounds hereinbefore enumerated, as all those diamines and sulphonic,
carboxylic, or sulphocarboxylic derivatives thereof, can be used which can be
converted into tetrazo compounds, either directly, or by means of the corresponding
monoacetodiamines. In place of the latter monoacetodiamido compounds, the
corresponding mononitroamines, sulphonic acids, or other derivatives thereof, can
be used, in the latter case, the intermediate mononitroazo compounds are first to
be reduced before redinzotising and coupling,-this reduction being effected at the
same time when the acetyl group contained in the first-formed intermediate mono-
acetoazo products (in case monoacetodiamines be used) is displaced.
'
One method of producing the above "symmetrical" disazo dye-stuffs from
B amido a naphthol monosulphonic acid Sch., is illustrated by the following
example: The parts are by weight.
COLORING
MATTER OBTAINED FROM ONE MOLECULAR
PROPORTION OF
BENZIDINE AND TWO MOLECULAR PROPORTIONS OF B₁ AMIDO
NAPHTHOLMONOSULPHONIC ACID SCH.
а1
18.4 parts of benzidine, or the corresponding quantity of a salt thereof, are
converted in the well known manner, in watery solution, into tetrazodiphenyl salt,
and the resulting tetrazo solution is then allowed to run into an icy-cold alkaline
solution, in water, of 50 parts (two molecules) of the sodium salt of ẞ₁ amido
a, naphtholmonosulphonic acid Sch. obtainable as described in the foregoing first
example. The formation of the "symmetrical" disazo dye-stuff commences
immediately, and is completed in about 24 hours. The complete coloring matter
is isolated in the usual manner, viz.: by salting out, filtering off, pressing, and
drying. It produces intense black shades on unmordanted cotton, and possesses
the following formula ·
SO,Na
Other dye stuffs result in an analogous manner, if the benzidine used in the above
example is replaced by the corresponding quantities of other diamines. The
so-formed coloring matters likewise yield very intense and dark shades on
unmordanted cotton.
.
These "symmetrical" disazo dye-stuffs possess the valuable property of being
further diazotisable when fixed on the fibre, and of being then capable of combining
with phenols, amines, diamines, amidophenols, amidophenolethers of the benzene
or naphthalene series, sulphonic or carboxylic acids thereof,-still deeper black shades
being thus produced, which are distinguished for their fastuess against washing and
fulling.
As above mentioned, the ẞ₁ amido a naphtholmonosulphonic acid Sch. is capable
of combining with the equimolecular proportion of a tetrazo compound, so-called
intermediate products being formed which contain a free diazo group, and therefore

page_text: can be coupled with one molecular proportion of another dye stuff component,
(phenol, amine, diamine, amidophenol, amidophenolether of the benzene or naph-
thalene series, a sulphonic or carboxylic derivative thereof). So-called "mixed"
disazo dye-stuffs are thus produced.
Of the dye stuff components, amidonaphtholsulphonic acids can be used, for
instance, amidonaphtholmonosulphonic acid G., a amido a naphthol a mono-
Fulphonic acid, a, amido a naphthol a, monosulphonic acid, a, a, amido naphthol
BB disulphonic acid, B₁ amido ß, naphthol ẞ, ẞa disulphonic acid, ẞ, amido
a, naphthol ẞ, monosulphonic acid, ß, amido as naphthol a, 13, disulphonic acid, or
the like.
The "mixed" disazo dye stuffs obtainable by means of the last named amido-
naphthol sulphonic acids can also be produced by coupling first one molecular
proportion of one of these amidonaphthol sulphonic acids with one molecular
proportion of a tetrazo compound, and subsequently combining the so-formed
intermediate products with one molecular proportion of B₁ amido a naphthol-
monosulphonic acid Sch. These "mixed" disazo dye-stuffs yield, on unmordanted
cotton, very intense, from bluish-black to black shades, and also possess the
valuable property of being further diazotisable when fixed on the fibre, and also of
combining with phenols amines, diamines, amidophenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic derivatives thereof, or other
suitable so-called developers, shades being thus produced which are distinguished
for their depth and intensity, and also for their fastness against washing and fulling.
The shades thus obtainable are in general black.
In order to illustrate one method of producing the above "mixed" disazo dye-stuffs,
the following example is given. The parts are by weight.
DYE-STUFF OBTAINED FROM EQUIMOLECULAR PROPORTIONS OF, BENZIDINE
B₁-AMIDO-a, NAPHTHOLMONOSULPHONIC ACID SCH. AND AMIDONAPHTHOL
MONOSULPHONIC ACID G.
The tetrazo solution resulting in the well-known manner from 184 parts of
benzidine is allowed to flow into an icy-cold solution prepared by dissolving
25 parts of the ẞ, amido-a-naphthol monosulphonate of sodium and a sufficient
quantity of sodium carbonate to keep the mixture alkaline.
When the formation of the intermediate product is completed, a well-cooled
✓ solution prepared by dissolving 25 parts of the sodium salt of amidonaphthol-
monosulphonic acid G., and rendered alkaline by means of sodium carbonate, is
added.
The formation of the "mixed "disazo dye-stuff at once begins, and is accelerated
advantageously by heating. The complete colouring matter is isolated in the usual
way, riz., by salting out, filtering off, pressing, and drying. It produces deep-black
shades on unmordanted cotton, and possesses the following formula :-

page_text: The same colouring-matter results, if tetrazo diphenyl-chloride is first coupled
with one molecular proportion of amidonaphtholmonosulphonic acid G., and
subsequently with one molecular proportion of B₁-amido-a-naphtholmonosulphonic
acid Sch.
The other "mixed "disazo dye-stuffs are obtained in an analogous manner, viz.,
on using, in place of amidonaphthol monosulphonic acid G employed in the
foregoing third example, the equivalent quantity of another amidonaphthol
sulphonic acid or another dye-stuff component (amine, phenol, amidophenol,
amidophenolether, diamine of the benzene or naphthalene series, sulphonic or
carboxylic derivatives thereof), or on replacing benzidine by the corresponding
quantity of another diamine..
It is to be understood that the "mixed" disazo dye-stuff can also be obtained
inversely, viz., on combining one molecular proportion of a tetrazo compound first
with one molecular proportion of any dye-stuff component (such as amine, phenol,
diamine, amidophenol, amidophenolether of the benzene or naphthalene series, or a
sulphonic or carboxylic derivative thereof), and subsequently with one molecular
proportion of B-amido-a-naphtholmonosulphonic acid Sch., or an alkaline salt
thereof.
The "symmetrical" and "mixed" colouring-matters hereinbefore defined, can, by
a further diazotisation and subsequent combination with dye-stuff components, be
converted into new polyazo dye-stuffs, which likewise yield valuable intense dark
shades on unmordanted cotton.
The production of these polyazo dye-stuffs is effected in the well-known manner.
As above mentioned, the last-named process can also be carried out on the fibre,-
shades being thus produced which are distinguished for their great intensity and
fastness.
1 1001
NEWTON & SON,
Agents for the Applicant.
COMPLETE SPECIFICATION,
The Manufacture or Production of Azo Colouring Matters, and
Materials therefor.
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:-
Only one beta, amido alpha, naphthol monosulphonic acid has been known up to
the present time, viz. :-the so-called amidonaphthol sulphonic acid G (beta,
amido alpha, naphthol bęta, monosulphonic acid), which can be obtained by fusing
the beta naphthylaminedisulphonic acid G with alkalies.
My foreign correspondents have now found that two new beta, amido alpha
naphtholmonosulphonic acids, differing from the said beta, amilo alpha, naphthol
beta, monosulphonic acid, are produced by sulphonating beta, amido alpha, naphthol.
My foreign correspondents prepare the last named beta, amido alpha naphthol
by fusing beta, naphthylamine alpha, sulphonic acid, or salts thereof, with alkalies,
at from 260 to 270 degrees Centigrade. The amidonaphthol readily dissolves in
hot water, but with difficulty in cold water, and crystallises in silvery lustrous scales
melting at 158 degrees Centigrade.
In order to illustrate the method of converting beta, amido alpha, naphthol into
two isomeric beta, amido alpha, naphthol monosulphonic acids, the following example
is given. The parts are by weight.

page_text: PRODUCTION OF TWO ISOMERIC BETA1 AMIDO ALPHA NAPHTHOL MONO-
SULPHONIC ACIDS FROM BETA1 AMIDO ALPHA NAPHTHOL.
10 parts of heta, alpha amidonaphthol (beta amido alpho̟ naphthol) are dissolved
in 50 parts of concentrated sulphuric acid (66 degrees Baumé) at from about 20 to
30 degrees C. The sulphonation is finished as soon as the amidonaphthol is
dissolved. The two isomeric acids separate as a white cystalline mass of pap-like
consistency, on pouring the sulphonated mixture into 200 parts of water. In order
to separate the two isomeric beta, amido alpha, naphthol monosulphonic acids, the
mixture of the two acids (filtered off from the sulphuric liquid) is converted
into calcium salts, and the solution of the calcium salts (amounting to about
400 litres, if the parts are kilos. by weight) is mixed with muriatic acid in excess.
One of the acids, viz., beta, amido alpha, naphtholmonosulphonic acid V, separates
in white flakes, which are filtered off, whilst the other isomeric acid, viz., beta,
amido alpha, naphthol monosulphonic acid Sch., is precipitated by adding common
salt to the filtrate.
In order to produce the two isomeric beta, amido alpha, naphtholmonosulphonic
acids, my foreign correspondents do not limit themselves to the directions given in
the above example, as these can be varied. For instance, in place of sulphuric
acid at 66 degrees Baumé, a stronger or a weaker acid (such as one of 60 degrees
Baumé) can be used; in the latter case, the mixture must
be heated at
about 60 degrees, in order to effect the sulphonation. The separation of the two
acids can also be carried out in a manner other than that described in the above
Example A, viz., by means of any method which can be used when two substances
are to be separated, of which one dissolves more readily than the other.
On following the directions given in the above Example A, nearly equal
proportions of the two isomeric beta, amido alpha, naphtholmonosulphonic acids
are obtained.
As above mentioned, the said two beta₁ amido alpha, naphtholmonosulphonic
acids V, and Sch., differ in properties from beta, amido alpha, naphthol beta, mono-
sulphonic acid. In order to illustrate more fully the difference existing between
the three acids, the following table is given, showing some of the characteristic
properties of these acids, or derivatives thereof.

page_text: The researches of my foreign correspondents have shown that of the above two
new beta, amido alpha, naphtholmonosulphonic acids V and Sch., the latter,
viz., the beta, amido alpha, naphtholmonosulphonic acid Sch., which differs by its
greater solubility from the beta, amido alpha, naphthol monosulphonic acid V., , is
of great technical value as a dye-stuff component, as, when combined with the
tetrazo compounds of diamines, it yields so-called "symmetrical" and "mixed"
disazo dye-stuffs, which produce on unmordanted cotton very intense shades,
distinguished for their fastness.
"
The method of producing these "symmetrical" and "mixed disazo dye stuffs
from the beta, amido alpha, uaphtholmonosulphonic acid Sch., in general consists
either in combining two molecular proportions of the said acid with one molecular
proportion of the tetrazo derivatives of "benzidine, its analogues or homologues,"
or in coupling first one molecular proportion of the said acid with one molecular
proportion of a tetrazo compound derived from "benzidine, its analogues or
homologues," and in subsequently combining the intermediate products with one
molecular proportion of another dye-stuff component (viz., amine, diamine, phenol,
dihydroxy compound, amidophenol, amidophenolether of the benzene or naphthalene
series, a sulphonic or carboxylic acid thereof). In the latter case, so-called
"mixed" disazo dye-stuffs are formed, the greater number of which can, also be
produced by coupling one molecular proportion of the tetrazo compounds derived
fron "benzidine, its analogues or homologues," first with one molecular proportion
of the said dye stuff components, and subsequently with one molecular proportion
of beta amido alpha, naphtholmonosulphonic acid Sch.
The combination of the beta, amido alpha, naphtholmonosulphonic acid Sch., or
salts thereof, with the tetrazo compounds, or the intermediate products containing
a free diazo group, is most advantageously effected in alkaline solutions, or in
solutions acidulated with acetic acid. According to the researches of my foreign
correspondents, the dye-stuffs produced by combining beta, amido alpha, naphthol-
sulphonic acid Sch. in alkaline solution, in general differ from those obtained by
coupling the said acid in acetic acid solution.
My foreign correspondents mean by the above expression, "benzidine its
analogues or homologues," for instance, the following diamido compounds, viz.:
Benzidine, tolidine, diamidophenyltolyl, diamido diphenolether, diamido alkyl-
hydroxydiphenyl, diamido alkylhydroxyphenyltolyl, diamido azobenzene, diamido
azotoluene, diamido azoxylene, diamido azoxybenzene, diamido azoxytoluene
diamido stilbene, diamido fluorene, diamido naphthalene, diamido carbazol, diamido-
diphenyleneoxide, diamido ditoluylene oxide, paraphenylene diamine, paratoluylene
diamine, benzidine sulphone, tolidine sulphone, diamidophenyltolylsulphone,
diamidodiphenoxyacetic acid, diamido diphenylene ketoxine, diamidophenyl-
benzimidazol, diamidodiphenylamine, amidobenzene azoalphanaphthylamine,
amidotoluene azoalphanaphthylamine, amidoxylene az alphanaphthylamine,
amidobenzene. azoparaxylidine, amidotoluene azoparaxylidine, amidoxylene
azoparaxylidine, amidobenzene azometaamidoparacresolether, amidotoluene azo-
metaamidoparacresolether, amidoxylene azometaamidoparacresolether, amido-
benzene azoorthoamidoparacresolether, amidotoluene azoorthoamidoparacresolether,
amidexylene azoorthoamidoparacresolether, amidobenzene azobetaethoxyalpha-
naphthylamine, amidotoluenea zobetaethoxyalphanaphthylamine, amidoxylene azo-
betaethoxyalphanaphthylamine, sulphonic acids, carboxylic acids, or sulpho
carboxylic acids thereof. My foreign correspondents, however, do
limit themselves to the use of the diamido compounds hereinbefore enumerated,
as all the diamines and sulphonic, carboxylic, or sulpho carboxylic derivatives
thereof, can be used which are convertible into tetrazo compounds, either
directly, or by means of the corresponding monacetyl diamines.
In place
of the latter monacetyldiamido compounds, the corresponding mononitroamines,
sulphonic acids, or other derivatives thereof, can be used; in the latter case, the
mononitrazo compounds must be reduced, and again diazotised and combined with
dye-stuff components, whilst on using monoacetylated diamines, the monoacetyl
not

page_text: amido azo derivatives first produced must be suitably treated, in order
the acetyl group, and again diazotised, and combined with the respective dye-stuff
components.
One method of producing the said "symmetrical" disazo dye-stuffs from beta,
amido alpha, naphtholmonosulphonic acid Sch., is illustrated by the following
oromnle. The parts are by weight.
:
COLORING MATTER OBTAINED
PROPORTION
BETA, AMIDO
FROM ONE MOLECULAR
OF
PROPORTIONS
AND TWO
BENZIDINE
MOLECULAR
ALPHA NAPHTHOLMONOSULPHONIC ACID SCH.
184 parts of benzidine, or the corresponding quantity of a salt thereof, are
converted in the well-known manner into a tetrazodiphenyl salt, and the tetrazo
solution is then allowed to run into an icy-cold aqueous solution, rendered and
kept alkaline by means of sodium carbonate of 52-2 parts (two molecules) of the
sodium salt of beta, amido alpha, naphthol monosulphonic acid Sch., obtainable as
described in the foregoing Example A. The formation of the symmetrical disażo
dye-stuff immediately commences, and is completed in about 24 hours.
coloring matter is isolated in the usual manner, riz. :-by salting out, filtering off,
pressing, and drying. It produces intense black shades on unmordanted cotton,
and is represented by the following formula:
-
'The
The corresponding dye-stuff produced by combining one molecular proportion
of tetrazodiphenylchloride with two molecular proportions of beta, amido alpha
naphtholmonosulphonic acid Sch. in acetic acid solution, yields violet shades of
great fastness on exposure to-the action of light.
Other dye-stuffs are formed in an analogous manner, if, instead of the benzidine
of the above example, the corresponding quantities of other diamines be used.
The coloring matters thus formed also yield very intense and fast shades on
unmordanted cotton.
These "symmetrical" disazo dye-stuffs possess the valuable property of
being further diazotisable when fixed on the fibre, and are then capable of
combining with phenols, amines, diamines, dihydroxy compounds, amidophenols
amidophenolethers of the benzene or naphthalene series, sulphonic or carboxylic
acids thereof, still deeper shades being thus produced, distinguished for their
fastness on washing and fulling.
As above mentioned, the beta, amido alpha, naphtholmonosulphonic acid Sch. is
capable of combining with a molecular proportion of a tetrazo compound, so-called
intermediate products being formed containing a free diazo group, and which
therefore can be further coupled with one molecular proportion of another dye-stuff
component (phenol, amine, diamine, dihydroxy compound, amidophenol, amido-
H

page_text: phenolether of the benzene or naphthalene series, a sulphonic or carboxylic
derivative thereof). So-called "mixed "disazo dye-stuffs are thus produced.
According to the researches of my foreign correspondents, those mixed disazo
dye-stuff in particular are of considerable value which are formed on combining
the said intermediate products with certain amidonaphtholsulphonic acids, using,
for instance, amido naphtholmonosulphonic acid G, alpha-amido alpha, naphthol
alpha, monosulphonic acid; alpha, amido alpha, naphthol alpha, monosulphonic acid,
alpha, alpha, amidonaphthol beta, betas disulphonic acid, beta₁ amido beta
naphthol beta, beta, disulphonic acid, beta, amido alpha, naphthol beta, monosulphonic
acid, beta, amido alpha, naphthol alpha, beta, disulphonic acid, or the like.
The "mixed "disazo dye-stuffs obtainable by means of the last named amido-
naphtholsulphonic acids, can also be produced by coupling first one molecular
proportion of one of these amidonaphtholsulphonic acids with one molecular propor-
tion of a tetrazo compound, and subsequently combining the intermediate product
so formed, with one molecular proportion of beta, amido alpha naphthol mono-
sulphonic acid Sch.
75.
These "mixed" disa zo dye-stuffs yield, on unmordanted cotton, very intense from
bluish-black to black shades, and also possesses the valuable property of being
further diazotisable when fixed on the fibre, and of then combining with phenols,
amines, diamines, dihydroxy compound, amido phenols, amidophenolethers of the
benzene or naphthalene series, sulphonic or carboxylic derivatives thereof, or other
suitable so-called developers, shades being thus produced which are distinguished
for their depth and intensity, and also for their fastness on washing and fulling.
The shades thus obtainable are generally black.
In order to illustrate one method of producing such "mixed" disazo dye-stuffs,
the following example is given. The parts are by weight.
DYE-STUFF OBTAINED FROM MOLECULAR PROPORTIONS OF BENZIDINE, BETAL
AMIDO ALPHA NAPHTHOLMONOSULPHONIC ACID SCH., AND AMIDO-
NAPHTHOLMONOSULPHONIC ACID G.
The tetrazo solution formed, in the well known manner, from 184 parts of
benzidine, is allowed to How into an icy-cold solution prepared by dissolving
25 parts of beta, amido alpha, naphtholinonosulphonate of sodium, together with a
sufficient quantity of sodium carbonate to keep the mixture alkaline. When the
formation of the intermediate product is completed, a well cooled solution, prepared
by dissolving 26.1 parts of the sodium salt of amidonaphthol monosulphonic acid G,
and rendered alkaline by means of sodium carbonate is added. The formation of
the "mixed" disazo dye-stuff at once begins, and is advantageously accelerated by
beating. The coloring matter is isolated in the usual way, viz., by salting out,
filtering off, pressing, and drying. It produces deep black shades on unmordanted
cotton and is represented by the following formula :—

page_text: The same coloring matter is formed if tetrazodiphenylchloride is coupled in a
solution rendered alkaline by means of sodium carbonate, first with one molecular
proportion of amidonaphthol monosulphonic acid G., and subsequently with one
molecular proportion of beta, amido alpha, naphthol monosulphonic acid Sch.
The corresponding dye-stuff obtained by coupling one molecular proportion of
tetrazo diphenyl chloride, in acetic acid solution, with one molecular proportion of
beta, amido alpha, naphtholmonosulphonic acid Sch., and with one molecular pro-
portion of amidonaphtholmonosulphonic acid G., produces, on unmordanted cotton,
violet shades which withstand in a high degree the action of light.
The other "mixed" disazo dye-stuffs are obtained in an analogous manner, viz.:-
on using, in place of amidonaphtholmonosulphonic acid G. used in the foregoing
Example C, the equivalent quantity of another amidonaphtholsulphonic acid, or
another dye stuff component (an amine, phenol, amidophenol, amidophenolether,
diamine, or dihydroxy compound of the benzene or naphthalene series, sulphonic
or carboxylic derivatives thereof), or on using the corresponding quantity of another
diamine in place of benzidine.
It is to be understood that most of the "mixed" disazo dye-stuffs can also be
obtained by an inverse method, riz., by combining one molecular proportion of a
tetrazo compound, first with one molecular proportion of any dye-stuff component
(such as an amine, phenol, diamine, dihydroxy compound, amido phenol, amido
phenolether of the benzene or naphthalene series, or a sulphonic or carboxylic
derivative thereof), and subsequently with one molecular proportion of beta, amido
alpha, naphtholmonosulphonic acid Sch., or an alkaline salt thereof.
For instance, a "mixed" disazo dye-stuff, producing blue shades, is formed on
combining one molecular proportion of tetrazodiphenylchloride, in alkaline
solution, with one molecular proportion of alpha, amido alpha, naphthol beta, beta,.
disulphonic acid, and with one molecular proportion of beta, amido alpha, naphthol-
monosulphonic acid Sch., whilst a "mixed "disazo coloring matter, yielding black
shades, is formed on combining one molecular proportion of the tetrazo derivative
of paradiamidodiphenylamine, in alkaline solution, with one molecular proportion
of beta, amido alpha, naphtholmonosulphonic acid Sch., and, in moderately acid
solution, with one molecular proportion of meta phenylene diamine.
The "symmetrical" and "mixed" coloring matters herein before defined, can be
converted by further diazotisation and subsequent combination, with dye-stuff
components, into new polyazo dye-stuffs, which also yield valuable intense dark
shades and unmordanted cotton. The production of these polyazo dye-stuffs is
effected in the well known manner. As above mentioned, the last-named process
can also be carried out on the fibre, shades being thus produced which are
distinguished for their great intensity and fastness.
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 production of two new beta, amido, naphtholmonosulphonic acids by
sulphonating beta, amido alpha naphthol.
2. The process for producing beta, amido alpha, naphthol monosulphonic acid Sch.,
and beta, amido alpha, naphtholmonosulphonic acid V., hereinbefore referred to,
which process consists in treating beta, amido alpha, naphthol, or salts thereof, at
low temperatures, with concentrated or moderately fuming sulphuric acid, and
subsequently separating the one acid from the other in a suitable mauner, viz., by
means of their different degrees of solubility.
3. The production of "symmetrical" and "mixed "disazo dye-stuffs from beta₁
amido alpha, naphtholmonosulphonic acid Sch., or salts thereof, and tetrazo com-
pounds of benzidine, its analogues or homologues.
4. The process for producing "symmetrical" disazo dye-stuffs, which process
consists in combining one molecular proportion of the tetrazo derivatives of

page_text: "benzidine, its analogues or homologues," with two molecular proportions of betat
amido alpha, naphtholmonosulphonic acid Sch., or alkaline salts thereof.
"
5. The manufacture of "mixed" disazo dye-stuffs, by combining one molecular
proportion of the tetrazo derivatives of "
benzidine, its analogues or homologues
(in any order) with one molecular proportion of beta, amido alpha, naphtholmono-
sulphonic acid Sch., or an alkaline salt thereof, and with one molecular proportion
of an amine, a diamine, phenol, dihydroxy compound, amidophenol, amidophenol-
ether of the benzene or naphthalene series, a sulphonic or carboxylic acid thereof,
including amido naphtholsulphonic acids other than beta, amido alpha, naphthol-
monosulphonic acid Sch.
6. The conversion of the "symmetrical" and "mixed " disazo dye-stuffs herein-
before defined (in substance, or when on the fibre) into polyazo dye-stuffs
by a further diazotisation, and subsequent combination with suitable dye stuff
components.
7. As new products of manufacturé,
a) beta, amido alpha, naphtholmonosulphonic acid Sch. ;
b) beta, amido alpha, naphtholmonosulphonic acid V ; and
c) the new dye-stuffs,
NEWTON & SON,
Agents for the Applicant.