The Manufacture or Production of New Colouring Matters.
Year: 1893

page_text: Date of Application, 31st Oct., 1893
Complete Specification Left, 30th July, 1894-Accepted, 1st Sept.,
1894.
PROVISIONAL SPECIFICATION,
[Communicated from abroad by THE FARBENFABRIKEN vormals FRIEDRICH
BAYER & Co., of Elberfeld, in the Empire of Germany.]
The Manufacture or Production of New Colouring Matters.
I, HENRY EDWARD NEWTON of The Office for Patents, Bream's Buildings
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
α
My foreign correspondents have found that the a₁ amido a naphthol a, ẞs
disulpho acid, which can be obtained from naphthalene a₁ B2 as trisulpho acid, by
nitrating, reducing, and subsequently melting with alkalies, is specially suited for
combination with the tetrazoderivatives of "benzidine, its analogues or homologues,"
so-called "symmetrical" and "mixed" dyestuffs being thus produced. These
colouring matters chiefly yield, on unmordanted cotton, from greenish blue, blue, to
violet or brown shades, possessing great purity, and are distinguished by the
property that, when fixed on the fibre, they can be diazotised, and coupled with
phenols, amines, or the like, shades being thus obtained which in a high degree
withstand washing and fulling.
My foreign correspondents mean by the above expression "benzidine, its
analogues or homologues," the following diamines, viz.:-Benzidine, tolidine, diamido-
phenytolyl, diamidodiphenolether, diamidoalkyloxydiphenyl, diamidoalkyloxy-
phenyltolyl, diamidoazobenzene, diamidoazotoluene, diamidoazoxylene, diamido-
azoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene, diamido-
naphthalene, diamidocarbazol, diamidodiphenylene oxide, diamidoditoluylene oxide,
paraphenylene diamine, para toluylene diamine, benzidine sulphone, tolidine
sulphone, diamidophenyltolyl sulphone, diamidodiphenoxy acetic acid, diamidodi-
phenylene ketoxime, diamidophenylbenzimideazol, amido benzene azo-a-naphthyl-
amine, amidotoluene-azo-a-naphthylamine, amidoxylene-azo-a-naphthylamine,
amidobenzene azo-para-xylidine, amidotoluene-azo-paraxylidine, amidoxylene-azo-
paraxylidine, amidobenzene-azo-meta or ortho-amido paracresolether, amidotoluene-
azo-meta or ortho amido paracresolether, amidoxylene-azo-meta or ortho-amido-
paracresolether, amido-benzene-azo-ß-ethoxy-a-naphthylamine, amidotoluene-azo-
B-ethoxy a naphthylamine, amidoxylene-azo-ß-ethoxy-a-naphthylamine, sulpho or
carboxylic acids of the said diamines.
Similar diamines or diamine sulpho acids, which can be converted into tetrazo
compounds, either directly, or by means of the monoacetylderivatives, can likewise
be employed in this process. In place of the monoacetyldiamines or monoacetyl
diamine sulpho acids, the corresponding mononitroamines, or mononitroamine sulpho
acids, can be used, but in this case the first formed mononitro-azo products must be
treated in a suitable manner, in order to reduce the nitro group, this reduction
being carried out at the same time, if, in the corresponding monoacetylamidoazo
compounds, the acetyl group is split off, before further diazotisation and
combination.
The method of producing the "symetrical" dye stuffs resulting from para-
diamines and a₁ amido a-naphthol a, ẞ, disulpho acid, is illustrated by the following
the norte haine by weight

page_text: COLOURING MATTER FROM ONE MOLECULAR PROPORTION OF DIANIBIDINE
AND TWO MOLECULAR PROPORTIONS OF. a₁-AMIDO-a -NAPHTHOL a₂ B₂
DISULPHO ACID.
24.4 parts of dianisidine are converted into the tetrazo compound in the well 5
known manner, and the so-formed tetrazo solution (whilst being cooled) is allowed
to flow into a solution prepared by dissolving 68·2 parts of the acid sodium salt of
a-amido-a-naphthol a, ẞ, disulpho acid, and rendered alkaline by means of sodium
carbonate. The formation of the dyestuff begins at once, and is complete after
about 24 hours. The complete colouring matter is isolated by salting out, filtering 10
off, and pressing. It yields on unmordanted cotton, clear blue shades, and possesses
the following formula :-
The researches of my foreign correspondents have also shewn, that one molecular
proportion of the above amidonaphtholdisulpho acid can be combined with one
molecular proportion of the tetrazoderivatives of "benzidine, its analogues or
homologues," intermediate products being thus formed which contain one free
diazo group, and therefore can be coupled with a further molecular proportion of
an amine, a diamine, phenol, amidophenol, amidophenolether of the benzene or
naphthalene series, a sulpho or carboxylic acid thereof. So-called "mixed" dye-
stuffs are obtained in this manner.
The same "mixed" colouring matters can also be produced by coupling one
molecular proportion of the tetrazo derivatives of "benzidine, its analogues or
homologues" at first with oue molecular proportion of an amine, a diamine, phenol,
amidophenol, amidophenolether of the benzene or naphthalene series, a sulpho or
carboxylic acid thereof, and subsequently with one molecular proportion of the
above amido a naphthol a, ẞ, disulpho acid.
a1
These "mixed" dye-stuffs also possess the ability of dyeing unmordanted cotton,
and in chief yield violet blue or brown shades.
The production of the "mixed" colouring matters derived from the above a₁ amido-
a, naphthol a, ẞ3 disulpho acid, is illustrated by the following example. The parts
are by weight.

page_text: DYE STUFF FROM EQUAL MOLECULAR PROPORTIONS OF BENZIDINE, a₁ NAPИ
THOL a₂ MONOSULPHO ACID, AND a₁ AMIDO a NAPHTHOL a2 ẞ3 DISULPHO
ACID.
1
The solution of tetrazodiphenylchloride, obtained in the known manner from
184 parts of benzidine, is allowed to flow into an ice-cold solution prepared by
dissolving 24'6 parts of the a₁ naphthol a, mono-sulphonate of sodium and 30 parts
of sodium acetate. When the formation of the intermediate product is finished,
an ice-cold solution of 34-1 parts of the acid sodium salt of the amido naphthol
a2 33 disulpho acid is added. The formation of the mixed dyestuff begins at once,
and preferably is completed by heating. The complete colouring matter is isolated
by salting out, filtering off, pressing, and drying. It produces reddish blue shades
on unmordanted cotton, and possesses the following formula :-
απ
Analogous colouring matters result if, in the above examples, dianisidine and
benzidine are replaced by the corresponding quantities of other diamines, or if, in
the above second example, a₁ naphthol a, monosulpho acid is replaced by the
corresponding quantity of another dyestuff component (amine, diamine, phenol,
amidophenol, amidophenolether of the benzene or naphthalene series, or sulpho or
carboxylic acids thereof).
As above mentioned, the aforesaid "symmetrical" and "mixed" dye-stuffs, when
fixed on the fibre, can be diazotised again, and coupled with the known dye-stuff
components (phenols, amines, and the like), shades being, thus obtained which are
distinguished by their intensity and fastness.
My foreign correspondents do not limit themselves, in the production of the
above defined "symmetrical" and "mixed" dye-stuffs, to the directions given in
the above two examples, as the latter can be varied in many respects, without altering
thereby the nature of this invention, which in general relates to the production of
symmetrical and " mixed " tetrazo dye-stuffs derived from a₁-amido-
a-naphthol a, ẞ, disulpho acid, or salts thereof.
66
"
Dated this 31st day of October 1893.
NEWTON & SON,
Agents for the Applicant.

page_text: The Manufacture or Production of New Colouring Matters.
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 :--
My foreign correspondents have found that the alpha, amido alpha, naphthol
alpha, beta, disulphonic acid which can be obtained from naphthalene alpha, beta,
alpha, trisulphonic acid, by nitrating, reducing, and subsequently fusing with
alkalies, is specially suited for combination with the tetrazo derivatives of
"benzidine, its analogues or homologues," so-called "symmetrical" and "mixed
dye-stuffs being thus produced. These coloring matters produce on unmordanted
cotton, shades varying chiefly from greenish-blue or blue, to violet or brown, of
great purity, and they are distinguished by the property that they can be diazotised
when fixed on fibres, and then coupled with phenols, amines, or the like,-shades
being thus obtained which in a high degree withstand washing and fulling.
My foreign correspondents mean by the above expression-" benzidine its
analogues or homologues," the following diamines, viz., Benzidine, tolidine, diamido-
phenyltolyl, diamidodiphenolether, diamidoalkyloxydiphenyl, diamidoalkyloxy-
phenyltolyl, diamidoazobenzene, diamidoazotoluene, diamidoazoxylene, diamido-
azoxybenzene, diamidoazoxytoluene, diamidostilbene, diamidofluorene, diamido-
naphthalene, diamidocarbazol, diamidodiphenylene oxide, diamidoditoluylene oxide,
paraphenylenediamine, paratoluylenediamine, benzidine sulphone, tolidine sulphone,
diamidophenyltolyl sulphone, diamidodiphenoxy acetic acid, diamidodiphenylene-
ketoxine, diamidophenylbenzimidazol, amidobenzeneazoalphanaphthylamine,
amidotolueneazoalphanaphthylamine, amidoxyleneazoalphanaphthylamine, amido-
benzeneazoparaxylidine, amidotolueneazoparaxylidine, amidoxyleneazoparaxylidine,
amidobenzeneazometa or orthoamidoparacresolether, amidotolueneazometa or ortho
amidoparacresolether, amidoxyleneazometa or ortho amidoparacresolether, amido-
benzeneazobetaethoxyalphanaphthylamine, amidotolueneazobetaethoxyalphanaph-
thylamine, amidoxyleneazobetaethoxyalphanaphthylamine, sulphonic or carboxylic
acids of the said diamines.
Similar diamines, or diamine-sulphonic acids of the benzene or naphthalene
series, which are convertible into tetrazo compounds, either directly, or by means
of their monoacetyl derivatives, can however also be used. The corresponding
mononitramines, or mononitramine sulphonic acids, can be used in place of the
monacetylated diamines, or monacetylated diamine sulphonic acids, in which case
the mononitroazo compounds which are first formed, must be reduced, and the
amidoazo compounds again diazotised, while the monacetylamidoazo compounds
which are formed on using monacetylated diamines, are treated in a suitable
manner, in order to split off the acetyl group, and the amidoazo compounds so
produced are again diazotised, and further combined with dye-stuff components.
The method of producing the "symmetrical" dye-stuffs from paradiamines and
alpha, amido alpha, naphthol alpha, beta, disulphonic acid, in general consists in
allowing one molecular proportion of the tetrazo derivative of a diamine, to act
on two molecular proportions of alpha, amido alpha, naphthol alpha, betas
disulphonic acid, or alkaline salts thereof, in solutions rendered alkaline, for
instance, by means of sodium carbonate. This method is illustrated by the
following example. The parts are by weight.

page_text: COLORING MATTER OBTAINED FROM ONE MOLECULAR PROPORTION OF
DIANISIDINE AND TWO MOLECULAR PROPORTIONS OF ALPHA AMIDO
ALPHA NAPHTHOL ALPHA, BETA, DISULPHONIC ACID.
24.4 parts of dianisidine are converted into the tetrazo compound in the well-
known manner, and the cooled tetrazo solution is allowed to flow into a solution
prepared by dissolving 68-2 parts of the acid sodium salt of alpha, amido alpha
naphthol alpha, beta, disulphonic acid, and rendered alkaline with sodium carbonate.
The formation of the dye-stuff begins at once, and is complete after about 24 hours.
The finished coloring matter is isolated by salting out, filtering off, and pressing.
It produces on unmordanted cotton, clear blue shades. It is represented by the
following formula :-
The researches of my foreign correspondents have also shown, that one molecular
proportion of the above defined alpha, amido alpha, naphthol alpha, beta, disulphonic
acid, or an alkaline salt thereof, can be combined with one molecular proportion of
the tetrazo derivatives of "benzidine, its analogues or homologues," preferably in a
solution which is either alkaline, or moderately acidulated with acetic acid. In the
latter case, intermediate products are formed containing one free diazo group, and
which therefore can be further combined with a molecular proportion of an amine,
a diamine, a phenol, an amidophenol, an amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic acid thereof. This latter combination
may be effected in alkaline or acidulated solutions, according to the nature of the
dye-stuff component used. So-called "mixed dye-stuffs are obtained in this
manner.
"
The same "mixed " coloring matters can also be produced inversely, viz., by
coupling one molecular proportion of the tetrazo derivatives of "benzidine, its
analogues or homologues," in an acid or alkaline solution (as the nature of the
dye-stuff components may require), first with one molecular proportion of an amine,
a diamine, a phenol, an amidophenol, an amidophenolether of the benzene or
naphthalene series, a sulphonic or carboxylic acid thereof, and subsequently,
preferably in an alkaline solution, with a molecular proportion of the above alpha,
amido alpha, naphthol alpha, beta, disulphonic acid, or an alkaline salt thereof.
The "mixed dye-stuffs produced by these process, also dye unmordantel
cotton, shades being thus obtained which are chiedy violet, blue, or brown.

page_text: A method of producing these mixed coloring matters derived from the above
alpha, amido alpha, naphthol alpha, betas disulphonic acid, is illustrated by the
following example. The parts are by weight.
DYE-STUFF
OBTAINED FROM MOLECULAR PROPORTIONS OF BENZIDINE,
ALPHA NAPHTHOL ALPHA, MONOSULPHONIC ACID, AND ALPHAL AMIDO
ALPHA NAPHTHOL ALPHA, BETA3 DISULPHONIC ACID.
The solution of tetrazo diphenylchloride, obtained in the known manner. from
18-4 parts of benzidine; is allowed to flow into an ice cold solution prepared by
dissolving 24-6 parts of the alpha, naphthol alpha, monosulphonate of sodium, and
30 parts of sodium acetate. When the formation of the intermediate product is
complete, an ice-cold solution in water prepared from 34°1 parts of the acid sodium
salt of alpha, amido alpha, naphthol alpha, beta, disulphonic acid, and 30 parts of
sodium carbonate, is added. The formation of the mixed dye-stuff begins at once,
and is with advantage completed by heating. The finished coloring matter is
isolated by salting out, filtering off, pressing, and drying. It produces violet-blue
shades on unmordanted cotton. This dye-stuff is represented by the following
formula:-
Analogous coloring matters are obtained if, in the foregoing Examples A and B,
instead of dianisidine and benzidine, the corresponding quantities of the other
diamines above referred to, are used, or if, in the above Example B, instead of the
alpha, naphthol alpha, monosulphonate of sodium, the corresponding quantity of
another dye-stuff component (amine, diamine, phenol, amidophenol, amidophenol-
ether of the benzene or naphthalene series, or sulphonic or carboxylic acids
thereof) is used.
As above mentioned, the aforesaid "symmetrical" and "mixed" dye-stuffs can
be again diazotised when fixed on fibres, and coupled with the known dye-stuff
components (phenols, amines, and the like),-shades being thus obtained which are
distinguished by their intensity and fastness.
In order to illustrate the variety of coloring matters obtainable from the above
named alpha, amido alpha, naphthol alpha, beta, disulphonic acid, and the shades
produced by these dye-stuffs on unmordanted cotton, the following table is given.
In the first column of this table, the different components of some of the coloring
matters hereinbefore defined are indicated, the shades obtainable by means of the
corresponding dye-stuffs being indicated in the second column :--

page_text: lianisidine + 1 molecular proportion of alpha, amido
alpha naphthol alpha, beta, disulphonic acid
+1 molecular proportion of alpha naphthylamine
-
benzidine + 1 molecular proportion of alpha, amido alpha,
naphthol alpha, beta, disulphonic acid + 1 molecular
proportion of alpha, naphthol alpha, monosulphonic
acid
benzidine + molecular proportion of alpha, amido
alpha naphthol alpha, beta, disulphonic acid
+1 molecular proportion of alpha, naphthol alpha,
monosulphonic acid

page_text: dianisidine 1 molecular proportion of alpha, amido
alpha naphthol alpha, beta, disulphonic acid
+1 molecular proportion of alpha, naphthol alpha.
monosulphonic acid
benzidine 1 molecular proportion of alpha, amido
alpha naphthol alpha, beta, disulphonic acid
+1 molecular proportion of beta, beta, dihydroxy-
naphthalene
tolidine 1 molecular proportion of alpha, naphthyl-
amine beta monosulphonic acid (Clève's B-acid)
+1 molecular proportion of alpha, amido alpha
naphthol alpha, betas disulphonic acid-

page_text: In the foregoing Examples A and B, my foreign correspondents have described
distinct methods by means of which the new dye-stuffs can be prepared, but they
do not limit themselves to the directions given in the said examples. The methods
described can also be varied, and all the methods in use for the production of
analogous dye-stuffs can be employed. Naturally, such variations or modifications
do not alter the nature of this invention, which in general relates to the production
of symmetrical and mixed tetrazo dye-stuffs derived from alpha, amido alpha
naphthol alpha, beta, disulphonic acid.
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 "symmetrical dye-stuffs by combining one molecular
proportion of the tetrazo salts of benzidine, its analogues, or homologues, with two
molecular proportions of alpha, amido alpha, naphthol alpha, beta, disulphonic
acid, or an alkaline salt thereof.
2. The process for producing "mixed "dye-stuffs, which process consists either
in combining one molecular proportion of the tetrazo salts of benzidine, its
analogues or homologues, with one molecular proportion of alpha, amido alpha..
naphthol alpha, beta, disulphonic acid, or an alkaline salt thereof, and one molecular
proportion of another dye-stuff component, or in coupling one molecular pro-
portion of the tetrazo salts of benzidine, its analogues or homologues, first with one
molecular proportion of a dye-stuff component, and then with one molecular
proportion of alpha, amido alpha, naphthol alpha, beta, disulphonic acid, or an
alkaline salt thereof.
3. As new products of manufacture, the new dye-stuffs produced by the processes
hereinbefore defined, or in any other way affording the same result.
Dated this 23rd day of July 1894.
NEWTON & SON,
Agents for the Applicant.