Year: 1897

page_text: are formed by causing one molecule of a tetrazotized diamido base to act upon
one molecule of the diazotized sulpho-acid of an amido-napthaline or upon the
diazotized sulpho-acid of amido benzol or its homologues, or upon one molecule of
diazotized nitrated, amidated, or oxylated amine of the benzole and naphthaline
series.
EXAMPLE I.
9'2 kilos. of benzidine are diazotized in the usual way. The resulting solution
of muriatic tetrazodiphenyl is allowed to flow into a solution of diazo-benzol-sulpho-
acid which has been produced in the usual manner from 8.6 kilos. of para-sulphanilic
acid. On neutralizing the free mineral acid by means of acetate of soda the new
tetrazo-azo compound is thrown down in the form of a flaky dark brown pre-
cipitate. This compound, when combined with two molecules of naphthionic acid
in weak acid solution, yields a colouring matter which dyes unmordanted cotton
in an alkaline bath, Turkey red.

page_text: EXAMPLE II.
On substituting for the benzidine mentioned in Example I, 106 kilos. of tolidine,
and for the para-sulphanilic acid, 11'2 kilos. of naphthionic acid then on mixing the
diazotizing mixture with acetate of soda, or even with a solution of soda, the new
substance is obtained in the form of a light brown precipitate.
Instead of benzidine or tolidine there may be employed other para-diamines such
as, for instance, ethoxybenzidine, dianisidine, diamidostilbendisulpho-acid, para-
phenylenediamine, etc. and instead of sulphanilic acid or naphthionic acid there
may be employed any other amidosulpho-acid (which is capable of being diazotized)
of the benzol series or of the naphthalin series. The tetrazo-azo compounds thus
obtained are precipitates which are soluble with difficulty and are in general of a
dark brown colour.
As above mentioned there may be employed in like manner certain other amido
compounds, namely the nitrated, amidated, and oxylated amines of the benzol
series or of the naphthaline series, when diazotized.
By the action of one molecule of a diazotized nitraniline or nitro-toluidine, or
of amido-phenol or amido-cresol or of phenylene-diamine or tolylendiamine or of
diamido-naphthaline, etc. upon one molecule of the tetrazo compound of a diamine,
there are produced new tetrazo compounds which serve equally well as those before
described for the production of new colouring matters.
I may proceed for example as follows:-54 kilos. of metaphenylendiamine are
diazotized by means of 3.5 kilos. of sodium nitrite and the necessary quantity of
hydrochloric acid. Into the diazo solution thus produced there is allowed to flow
a solution of tetrazo-di-phenyl which has been produced in the well known manner
from 9.2 kilos. of benzidine.
After neutralizing the free mineral acid with sodium acetate, or with soda,
the new tetrazo-azo compound is obtained in the form of a red-brown precipitate
which is soluble only with difficulty.
Dated this 8th day of
1 1007
A. M. & WM. CLARK,
Chartered Patent Agents, 53, Chancery Lane, London.
I, ALEXANDER MELVILLE CLARK, of the Firm of A. M. & Wm. Clark, of 53,
Chancery Lane, in the County of Middlesex, Fellow of the Chartered Institute
of Patent Agents, do hereby declare the nature of this invention (a communication
to me by the Firm of Kullmann & Rapp, of Rotterdam, Holland), and in what
manner the same is to be performed to be particularly described and ascertained in
and by the following statement:-
-
The known single and mixed tetrazo.colours shew no considerable differences
in shade if they are produced from benzidine in lieu of tolidin as a base.
It has now been discovered that it is possible to manufacture new single and
mixed trisazo colours which, besides possessing greater fastness against acids,
yield shades which are quite different from those of the analogous tetrazo colours,
by replacing the tetrazo compounds of the paradiamines by a series of new inter-
mediate bodies derived from the former by combining one molecule of these new
products (of which the correct scientific name is tetrazo-azo compounds) with two

page_text: molecules of the same or with one molecule of one and another molecule of a different
amine or phenole or sulpho acid of the same whether in acid neutral or alkaline
solution.
It is a special characteristic, and contrary to all experience, that in particular
the trisazo products derived from tetrazo ditolyl, dye in general yellower and
redder, respectively, than the same trisazo derivatives of tetrazo diphenyl.
The new tetrazo azo compounds which have the general formula:-
-N=N-R-N-N-R¹-N=N-
are formed by causing one molecule of a terazotized diamido base to act upon one
molecule of the diazotized sulpho acid of amido naphthalines or of amido benzole
or of its homologues or upon one molecule of diazotized nitrated, amidated or
oxylated amine of the benzole or naphthaline series.
EXAMPLE I.
9.2 kilos. of benzidine are diazotized in the usual way. The resulting solution
of muriatic tetrazodiphenyl is run into a solution of diazo benzole sulpho acid
which has been produced in the usual manner from 8.6 kilos. of para-sulphanilic
acid. On neutralizing the free mineral acid by means of acetate of soda the new
tetrazo azo compound precipitates in a flaky dark-brown form. This product,
when combined with two molecules of naphthionic acid in a weak acid solution,
yields a colour which dyes in an alkaline bath un-mordanted cotton Turkey red.
EXAMPLE II.
Substituting for the 9.2 kilos. benzidine in Example I, 10'6 kilos. tolidine and for
the para sulphanilic acid, 112 kilos naphthionic acid, another new body is obtained
as a light brown precipitate when the mixture of these two diazotized products is
treated with acetate of soda or carbonate of soda. Combined, as in Example I,
with naphthionic acid this tetrazo azo compound gives a colour which dyes in an
alkaline bath un-mordanted cotton scarlet red.
EXAMPLE III.
9.2 kilos. benzidine are transformed into tetrazodiphenyl and added to a solution
of 54 kilos. metaphenylendiamine previously diazotized with 35 kilos. nitrite of
soda and the necessary quantity of muriatic acid. The free mineral acid is.
neutralized with acetate of soda, the resulting nearly insoluble intermediate
product stirred a short time and then first mixed with a solution of 5'4 kilos. meta-
phenylendiamine in muriatic acid and afterwards with a solution of 13 kilos. of
y-amidonaphthol acid rendered alkaline by carbonate of soda. After stirring for
a while the new colour, which is not easily soluble in cold water, separates in
brown flakes. It dyes un-mordanted cotton in a neutral or alkaline bath a brown
violet shade.
Instead of benzidine or tolidine other para-diamines may be employed as for
instance aethoxybenzidine, dianisidine, diamidostilbensulpho acid, paraphenylen-
diamine, etc., and instead of sulphanilic acid or naphthionic acid or metaphenylen-
diamine every other amido acid of the benzole or naphthalin series which can be-
diazotized may be used and finally metaphenylendiamine can be replaced by every
nitrated, amidated, or oxylated amine previously diazotized.
The new tetrazo azo compounds produced by this method are difficultly soluble
precipitates generally of brown colour.
Having now particularly described and ascertained the nature of the said in-
vention and in what manner the same is to be performed I declare that what I
claim is :-
1. The production of new tetrazo-azo compounds by combining one molecule of
the tetrazo derivatives of the diamines with one molecule of a diazotized sulpho acid

page_text: of the amido naphthalines or amidobenzole or its homologues or with one molecule
of a nitrated, amidated, or oxylated amine previously diazotized.
2. The production of the new single as well as the mixed disazo azo colours,
which are obtained when one molecule of these new tetrazo azo compounds is
combined in alkaline neutral or weak acid solution with two molecules of an
amine or phenole or their sulpho acids.
Dated this Rith law of Ta1000
A. M. & WM. CLARK.
Chartered Patent Agents, 53, Chancery Lane, London.