The Manufacture of Chemical Compounds, suitable for the Production of Colouring Matters in Búlk or on Fibre.
Year: 1895

page_text: Date of Application, 17th June, 1895
Complete Specification Left, 16th Mar., 1896-Accepted, 18th Apr., 1896
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture of Chemical Compounds, suitable for the
Production of Colouring Matters in Búlk or on Fibre.
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:-
My foreign correspondents discovered some time ago that betanaphthol-
trisulphonic acid, or salts thereof, when added to solutions of tetrazo .compounds,
yield salts of the tetrazo compounds used, which dissolve with difficulty in water,
and therefore are precipitated from the resulting solutions. Such salts possess
great stability, and can be used for the production of azo dye stuffs in bulk or on
fibre, as they yield real dye stuffs, when allowed to act on dye stuff components,
the betanaphtholtrisulphonic acids being displaced during the formation of the
dyestuffs. My foreign correspondents hereinafter use the term "tetrazo salts"
for such salts of tetrazo compounds.
My foreign correspondents have now found, that "tetrazo,salts" are produced
which possess the same properties as those obtained by means of betanaphthol-
trisulphonic acids and tetrazo, compounds, by acting on tetrazo compounds, such as
tetrazo diphenylchloride, tetrazodimethoxy diphenylchloride, and the like, with
beta, naphthol alpha, monosulphonic acid, or salts thereof, and the researches
of my foreign correspondents have further shewn, that not only tetrazo
compounds are capable to yield salts soluble with difficulty in water, when
acted on with betanaphtholtrisulphonic acids, or with beta, naphthol alpha
sulphonic acid, but that also from diazo compounds, such salts (for which my
foreign correspondents hereinafter use the expression "diazo salts") can be
produced. For instance, such "diazo salts may be produced from nitramido
compounds, such as nitraniline and the like, by diazotising such bodies, and by
acting on the thus obtained diazo solutions with the above mentioned beta
naphthol alpha, sulphonic acid, or with naphtholtrisulphonic acids or salts thereof,
diazo salts being produced which dissolve with difficulty in water, and which are
distinguished by their stability, and can be used in place of theusual diazo
compounds of uitramines, which are readily decomposed.
"
In order to illustrate the method of producing the "tetrazo salts" and the
"diazo salts" hereinbefore defined, my foreign correspondents give the following
Examples One and Two, the parts being by weight.
PRODUCTION OF A TETRAZO SALT FROM TETRAZO DIMETHOXYDIPHENYL-
CHLORIDE AND BETA, NAPHTHOLALPHA, SULPHONATE OF SODIUM.
÷
A solution of 24.6 parts of beta, naphthol alpha, sulphonate of sodium is allowed
to flow into a concentrated solution of tetrazo dimethoxydiphenylchloride prepared
in the usual manner from 12.3 parts of dianisidine and 7 parts of sodium nitrite,
in the presence of hydrochloric acid. The so-formed tetrazo salt immediately
CO
021

page_text: begins to separate, and the precipitation is profitably hastened by the addition of
common salt. The finished precipitate is filtered off and pressed.
The tetrazo salt thus obtained has the following formula:
PRODUCTION OF A DIAZO SALT FROM NITRODIAZO BENZENECHLORIDE AND
BETA NAPHTHOL ALPHA, SULPHONATE OF SODIUM.
The
A solution of 24-6 parts of beta, naphthol alpha, sulphonate of sodium is allowed
to flow into a diazo solution prepared in the usual manner from 13.8 parts of para-
nitraniline and 7 parts of sodium nitrite in the presence of hydrochloric acid.
so-produced diazo salt, forming a yellow orange precipitate, begins immediately to
separate. The separation being completed, the precipitate is filtered off and
pressed.
The diazo salt has the constitutional formula :
It possesses great stability, and may be used in the production of dye-stuffs in
bulk or on fibre, in place of nitro diazo benzene chloride or the like.
The process proceeds in an analogous manner if either corresponding quantities
of other nitramito compounds, or of other suitable amido compounds, be employed
in place of nitraniline used in the preceding Example II; or it, instead of beta
naphthol alpha, sulphonate of sodium, equivalent quantities of betanaphtholtri-
sulphonic acids, or salts thereof, be employed, such as beta, naphthol betaz beta..
alpha, trisulphonic acid, or other betanaphthol trisulphonic acids, or mixtures of
alpha and betanaphthotrisulphonic acids, for instance, the mixture resulting from
the fusion with alkalies of naphthalene tetrasulphonic acid or the like. In this
case, the diazo compounds combine with the betanaphtholtrisulphonic acids to form
almost insoluble diazo salts, which can be easily separated from the diazo salts
produced from the said diazo compounds with the alphanaphthol trisulphonic acids,
as these diazo salts dissolve with readiness.
My foreign correspondents do not limit themselves to the particulars given in
the foregoing examples, as these may be varied without altering thereby the nature
of this invention, which in general relates to the production of almost insoluble

page_text: tetrazo salts by acting on tetrazo compounds with beta, naphthol alpha, sulphonic
acid, or salts thereof, and to the production of almost insoluble diazo salts by
adding beta, naphthol alpha, sulphonic acid, or betanaphthol trisulphonic acids, or
salts thereof, to diazo solutions prepared from amido compounds, or substituted
amido compounds, which tetrazo salts and diazo salts are to be used in the
production of dye-stuffs, either in bulk or on fibre, in place of the usual tetrazo
and diazo compounds.
Dated this 17th day of June 1895
The Manufacture of Chemical Compounds, suitable for the
Production of Colouring Matters in Bulk or on Fibre.
1 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 :-
My foreign correspondents discovered some time ago that, on adding certain
salts of betanaphtholtrisulphonic acid to solutions of tetrazo compounds, beta-
naphtholtrisulphonates of the tetrazo compounds are produced, which separate
from the solution, as they are not easily soluble in water.
Such salts are very
stable, and can be used for the production of azo dye-stuffs, as such, or on fibres as
they yield true dye-stuffs when allowed to act on dye-stuff components, the beta-
naphtholtrisulphonic acids becoming displaced during the formation of the dye-stuffs.
My foreign correspondents hereinafter use the term "tetrazo salts" for such salts
of tetrazo compounds.
My foreign correspondents have now found that "tetrazo salts" are produced
possessing the same properties as those obtained by means of beta-naphtholtrisul-
phonic acids, and tetrazo compounds, by acting on tetrazo compounds, such as.
tetrazo diphenylchloride, tetrazoditolylchloride, tetrazo dimethoxydiphenylchloride,.
and the like, with beta, naphthol alpha, monosulphonic acid, or salts thereof, and
the researches of my foreign correspondents have further shown, that not only are
tetrazo compounds capable of yielding salts which dissolve with difficulty in water,
when acted on with betanaphtholtrisulphonic acids, or with beta, naphthol alpha₁
sulphonic acid, but that such salts (for which my foreign correspondents hereinafter
use the expression "diazo salts") can also be produced from diazo compounds
thus "diazo salts" may be produced from nitramido compounds, such as nitraniline
and the like, by diazotising them, and adding to the diazo solutions thus obtained,
the above-mentioned beta, naphthol alpha, sulphonic acid, or betanaphtholtrisul-
phonic acids, or salts thereof, stable, difficultly soluble "diazo salts being thus
produced, which can be used instead of the usual diazo compounds of nitramines,
which are readily decomposed.
"
In order to illustrate a method of producing the above-defined "tetrazo salts"
and "diazo salts," my foreign correspondents give the following Examples One and
Two, the parts being by weight.
:
66
"
PRODUCTION OF A TETRAZO SALT FROM TETRAZO DIMETHOXYDIPHENYL-
CHLORIDE AND SODIUM BETA, NAPHTHOL ALPHA SULPHONATE.
A solution of 24.6 parts of sodium beta, naphthol alpha, sulphonate is allowed
to flow into as concentrated a solution as possible of tetrazodimethoxydiphenyl-

page_text: chloride, prepared in the usual manner from 12.3 parts of dianisidine and 7 parts of
sodium nitrite in the presence of muriatic acid. The "tetrazo salt" immediately
begins to separate, but the precipitation is, with advantage, hastened by adding
common salt. The finished precipitate is filtered off and pressed.
The "tetrazo salt" thus obtained is probably 'that represented by the following
formula:-
It possesses great stability, and may be used in the production of dye-stuffs, as
such, or on fibres, instead of nitro-diazo-benzene-chloride or the like.
The process proceeds in an analogous manner, if either corresponding quantities
of other nitramido compounds, or of other suitable amido compounds, be used in
place of the nitraniline prescribed in the preceding Example II, or if, instead of
sodium beta, naphthol alpha, sulphonate, equivalent quantities of betanaphthol-
trisulphonic acids, or salts thereof, be taken, such as beta, naphthol beta, beta.
alpha trisulphonic acid, or other betanaphtholtrisulphonic acids, or mixtures of
alpha and beta naphtholtrisulphonic acids, for instance, the mixture formed on
fusing naphthalenetetrasulphonic acid, or the like, with alkalies. In this case, the
diazo compounds combine with the betanaphtholtrisulphonic acids to form almost
insoluble diazo salts," which can easily be separated from the "diazo salts
produced from the said diazo compounds and the alpha naphtholtrisulphonic acids,
as these latter diazo salts are readily soluble.
"
My foreign correspondents do not limit themselves to the particulars given in
the foregoing examples, as these may be varied, without thereby altering the
nature of this invention, which, speaking generally, relates to the production of

page_text: almost insoluble "tetrazo salts" from tetrazo compounds and beta, naphthol alpha,
sulphonic acid, or salts thereof, and to the production of almost insoluble "diazo
salts" from beta, naphthol alpha, sulphonic acid, or betanaphtholtrisulphonic acids,
or salts thereof, and diazo solutions prepared from nitramido compounds, or
substituted nitramido compounds, the which "tetrazo salts" and "diazo salts are
to be used in the production of dye-stuffs, either in bulk or on fibres, in place of
the usual tetrazo and diazó compounds.
"
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), 1 declare that what I claim is :-
1. The production of beta; naphthol alpha, monosulphonic tetrazo salts from
beta, naphthol alpha, monosulphonic acid, or salts thereof, and tetrazo derivatives
of para-diamido compounds prepared with the aid of mineral acids.
"
2. The process for producing stable beta, naphthol alpha, sulphonic tetrazo
salts," which process consists in allowing two molecular proportions of an alkaline
salt of beta naphthol alpha, sulphonic acid to act, in an acid or neutral solution,
on a single molecular proportion of the tetrazo derivative of a paradiamido
compound, and subsequently isolating, in a suitable manner, the beta naphthol
alpha, sulphonic "tetrazo salts" thus produced.
3. The production of beta, naphthol alpha, monosulphonic and of beta naphthol-
trisulphonic "nitro diazo salts" from beta, naphthol alpha, monosulphonic acid, or
from certain beta naphtholtrisulphonic acids, or salts thereof, and diazo derivatives
of nitramido compounds prepared with the aid of a mineral acid.
4. The process of producing stable beta, naphthol alpha, sulphonic " nitro diazo
salts," or beta naphtholtrisulphonic "nitro diazo salts," which process consists in
acting on a molecular proportion of the diazo derivative of a nitramido compound
of the benzene or naphthalene series, with a molecular proportion of an alkaline
salt of beta, naphthol alpha, sulphonic acid, or of beta, naphthol beta, beta, alpha
trisulphonic acid (or of the betanaphtholtrisulphonic acid which is formed together
with an alphanaphthol trisulphonic acid, on sulphurating naphthalene beta, beta3
disulphonic acid, and subsequently fusing the so-formed naphthalene tetrasulphonic
acid with alkalies), either in acid or neutral solution, and in subsequently isolating,
in a suitable manner, the "nitro-diazo salt
so formed.
"
5. The use of diazo derivatives of uitraniline, nitrotoluidines, nitronaphthylamines,
and the like nitramines or substituted nitramines, in the process illustrated by the.
foregoing Claim 4.
6. The use of the beta, naphthol alpha, monosulphonic "tetrazo salts," and of
the beta, naphthol alpha, monosulphonic or betanaphtholtrisulphonic "nitrodiazo
salts" for the production of azo dye-stuffs, as such, or on fibres.
7. The production of azo dye-stuffs, as such, or on fibres, from the beta, naphthol
alpha monosulphonic "tetrazo salts," and from the beta, naphthol alpha, mono-
sulphonic or betanaphtholtrisulphonic "nitrodiazo salts herein before defined;
which process consists either in allowing a molecular proportion of the said
"tetrazo salts" to act on two molecular proportions of the usual dye-stuff coin-
ponents, or in acting with a molecular proportion of the said "uitrodiazo salts" on
a molecular proportion of any dye-stuff component.
8. As new products, the new beta, naphthol alpha, sulphonic "tetrazo salts," the
beta, naphthol alpha, sulphonic "nitro-diazo salts," and the betanaphtholtrisulphonic
"nitro-diazo salts "produced by the processes hereinbefore defined, or in any other
manner affording the same result.
Dated this 14th day of March 1896.
NEWTON & SON,
Agents for the Applicant.