Manufacture of New Colouring Matters.
Year: 1892

page_text: Date of Application, 6th Jan., 1892
Complete Specification Left, 5th Oct., 1892-Accepted, 5th Nov., 1892
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE ACTIEN GESELLSCHAFT FÜR ANILIN
FABRIKATION, of Berlin, Germany, Chemical Manufacturers.]
Manufacture of New Colouring Matters.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Chartered Patent Agent, do hereby declare the
nature of this invention to be as follows:-
This invention relates to the production of new azo-dyestuffs, derived from
p-amidobenzene-azo-amido-a naphthaline.
This base, the constitution of which is represented by the formula
p-amidobenzene-azo-amido-a naphthaline.
This base, the constitution of which is represented by the formula
NH,– CHN=NCH – NH,
-
or
8
-
CHN
10 2
NH,
NH,
has been first described by Meldola (Chem. Soc. I. 43, 432) and was prepared by
reducing with ammonium sulphide the nitroazoamido compound obtained from
diazotised para-nitraniline and a naphthylamine. Meldola converted this base
into a tetrazo-compound and combined the same with phenole, resorcine,
a and ẞ naphtole and ẞ naphtolmonosulfo-acid (Schäffer's) the resulting products
which have not been examined in detail, were either insoluble in water or did "not
possess tinctorial power." (Chem. Soc. I. 43. 438.)
The base has up to the present time not been practically used for the preparation
of colouring matters.
a
My foreign correspondents have now discovered, that contrary to the aforesaid
observations of Meldola, the tetrazo compound of p-amidobenzene-azo-amido-
naphthaline yields not only a colouring matter by the combination with Schaffer's
naphtholmonosulphoacid, but that, by the combination of the same with other
sulpho acids or carbo acids of amines phenoles, amidophenoles, and the like,
which have not been tried by Meldola, valuable colouring matters may be
obtained.
All these new colours possess the property of dyeing cotton in an alkaline or salt
bath, and they may also be fixed on wool in a dye bath, containing salt; moreover,
these new dyestuffs stand light and washing fairly well.
The new colouring matters, resulting from the above mentioned base, are
generally of darker shades than the corresponding dyestuffs obtained hitherto from
para-diamines.
para-ulamines.
I. COLOURING MATTERS OBTAINED FROM
ONE MOLECULE OF THE BASE
AND TWO EQUAL MOLECULES OF AN AMINE, A PHENOLE AN AMIDO-
PHENOLE OR THEIR SULPHO ACIDS AND CARBO-ACIDS.

page_text: forms an orange red solution is caused to react upon two molecules of a sulpho acid
of the following products:
naphthols
dioxynaphthalines
naphthylamines
amidonaphthols.
The combination is, according to the nature of these compounds performed either
in alkaline solution or in presence of acetic acid. The shades of the colouring
matters obtained in this way vary from blue to blue-black.
My foreign correspondents have further found, that the aforesaid sulphoacids
may be replaced by two molecules of phenolcarbo-acids, but the products obtained
from the latter are almost entirely insoluble in water.
The products resulting from the combination with two molecules of m-phenylene-
diamine or m-toluylene-diamine are soluble in diluted acids, and may be dyed in an
acid dye bath as well on unmordanted cotton as on cotton mordanted with tannine;
in the first case violet-brown, in the second case blue-black shades are obtained.
The combination products resulting from the tetrazo salt and two molecules of
amines, phenoles, amidophenoles-and which are insoluble in water-may be made
soluble by sulphonation; the latter process is carried out in the usual manner by
means of the well known and suitable sulphonating agents, employed for such
purposes.
II. COLOURING MATTERS OBTAINED FROM ONE MOLECULE OF THE BASE
AND TWO DIFFERENT MOLECULES OF AMINES, PHENOLES, AMIDO-
PHENOLES OR THEIR SULPHO- AND CARBO ACIDS.
Ե
phenole
amidophenol
or their sulpho and carbo acids, an intermediate product, which contains one free
diazo group and may therefore be combined with a second molecule of another of
the aforesaid compounds. In this way mixed azo colours are obtained, the shade of
which varies according as to the compounds employed from blue to brown and blue
black
III. COLOURING MATTERS OBTAINED BY COMBINING ONE MOLECULE OF THE
BASE WITH ONE MOLECULE OF a NAPHTHYLAMINE REDIAZOTISING THE
INTERMEDIATE PRODUCT, AND COMBINING THE LATTER WITH TWO
MOLECULES OF EQUAL OR DIFFERENT SULPHO ACIDS.

page_text: Instead of a naphthylamine-as described under heap III-one molecule of
y-amidonaphthol monosulpho acid may be combined with the tetrazo salt to an
intermediate product, which, after re-diazotising, yields blue black colouring matters,
when combined with two molecules of equal or different compounds as mentioned
herein before.
Such of the aforesaid combination products produced under II, III and IV
which are insoluble in water may be rendered soluble by sulphonation as mentioned
under I.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of New Colouring Matters.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery
Lane, in the County of London, Chartered 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 :-
This invention relates to the production of new azo dyestuffs derived from
p-amidobenzene-azo-amido-a naphthaline.
This base, the constitution of which is represented by the formula
NH, - CH N=NCH – NH,
1
or
-
NH,
C₁HN,
NH,
has been first described by Meldola (Chem. Soc. I. 43, 432) and was prepared by
40 reducing with ammonium sulphide the nitroazoamido compound obtained from
diazotised-para-nitraniline and a naphthylamine. Meldola converted this base into

page_text: a tetrazo compound and combined the same with phenole, resorcine, a and ẞ naphthole
and ẞ naphtholmonosulpho acid (Schäffer's); the resulting products which have not
been examined in detail, were either insoluble in water or did "not possess tinctorial
power (Chem. Soc. I. 43, 438).
The base has up to the present time not been practically used for the preparation
of colouring matters.
My foreign correspondents have now discovered that, contrary to the aforesaid
observations of Meldola, the tetrazo compound of p-amido benzene azo-amido-
n-naphthaline yields, not only a colouring matter by the combination with
Schäffer's ẞ naphthol monosulpho acid, but that, by the combination of the same
with other sulpho-acids or carbo-acids of amines, phenoles, amidophenoles and the
like, which have not been tried by Meldola, valuable colouring matters may be
obtained.
All these new colours possess the property of dyeing cotton in an alkaline or salt
bath, and they may also be fixed on wool in a dye bath containing salt; moreover,
these new dye stuffs stand light and washing fairly well.
The new colouring matters, resulting from the above mentioned base, are
generally of darker shades than the corresponding dyestuffs obtained hitherto from
para diamines.
EXAMPLE.
26.2 kgs. p-amidobenzene azo amido a-naphthaline are dissolved in diluted
hydrochloric acid and converted into the tetrazo compound by the action of a
solution of 14 kgs. of sodium nitrite; the tetrazo salt, which forms an orange red
solution, is caused to react upon a solution of 63 kgs. crystallized sodium naphthionate
in presence of an excess of sodium acetate. After stirring for about 12 hours,
the mixture is gently heated, neutralized with soda, and the colouring matter is
precipitated with salt.
It dyes unmordanted cotton a deep black violet.
Instead of naphthionic acid other suitable sulpho acids of the naphthylamines, the
naphthols, dihydroxynaphthalenes and amidonaphthols may be employed.
The combination is according to the nature of these compounds performed either
in alkaline solution or in presence of acetic acid.
The shades of the colouring matters obtained in this way vary from blue to
blue black.
The phenol carbon acids yield when combined with the aforesaid tetrazo compound,
products which are almost entirely insoluble in water.
The products resulting from the combination with two molecules of m-phenylene
diamine or m-toluylene diamine are soluble in diluted acids, and may be dyed in
an acid dye bath as well on unmordanted cotton as on cotton mordanted with
tannin; in the first case violet brown, in the second case blue black shades are
obtained.
II.
COLOURING MATTERS OBTAINED FROM ONE MOLECULE OF THE BASE
AND TWO DIFFERENT MOLECULES OF AMINES, PHENOLES, AMIDO-
PHENOLES, OR THEIR SULPHO- AND CARBO ACIDS.

page_text: p amidobenzene-azo amido a naphthalene forms with one molecule of an amine,
phenole, amidophenole or their sulpho- and carbo-acids, an intermediate product,
which contains one free diazo group and may therefore be combined with
a second molecule of another of the aforesaid compounds. In this way mixed azo
colours are obtained, the shades of which vary according to the compounds employed,
from blue to brown and blue black.
EXAMPLE.
The tetrazo salt, obtained as described in the example under head I is combined
in an alkaline solution with 24 kgs. of a naphthol a mono sulphonate of sodium; to
O the intermediate product, which is a dark blue precipitate an alkaline solution of
23·9 kg. y-amido-naphthol-monosulpho acid is added.
+3
11
BY COMBINING ONE MOLECULE OF
THE BASE WITH ONE MOLECULE OF a-NAPHTHYLAMINE, REDIAZOTISING
THE INTERMEDIATE PRODUCT, AND COMBINING THE LATTER WITH TWO
MOLECULES OF EQUAL OR DIFFERENT SULPHO ACIDS.
III. COLOURING MATTERS OBTAINED
α
My foreign correspondents have further discovered, that the intermediate
product obtained according to the process mentioned under head II from
one molecule of the tetrazo salt and one molecule of naphthylamine may be
rediazotised, and the rediazotised product may afterwards be combined with two
molecules of a sulpho-acid of the following bodies: naphtholes, dihydroxynaphtha-
lines, naphthylamines, amido-naphtholes.
Moreover, the rediazotised product may first be combined with one molecule of the
aforesaid sulpho acids and afterwards with a second molecule of another of the
compounds above mentioned.
EXAMPLE.
The intermediate product formed by the combination of 26.2 kgs. amido-
benzene-azoamido-a-naphthaline and 14 kgs. of a naphthylamine, which separates
in the shape of a black insoluble precipitate, is rediazotised in an acidulated
solution by the action of 7 kgs. sodium nitrite, and the product obtained in this way
is combined with 69'6 kgs. sodium salt of ẞ naphtholdisulphoacid R. The resulting
combination product is a dark greyish blue dye.
Similar colouring matters of grey blue to black blue shades are obtained when
for the naphtholdisulpho acid R are substituted other sulpho-acids of the
naphthols, the sulpho acids of the naphthylamines, dihydroxynaphthalenes and
amidonaphthols.
Moreover the intermediate product before described may, after the rediazotation
be combined, first with one molecule of one of the aforesaid sulpho acids and after-
wards with one molecule of a sulpho acid different from that combined in the first
stage the mixed azo colors resulting in this way resemble in their properties and
shades those mentioned before.
Generally the products obtained according to the process described under this
head are much darker than those of the corresponding dye-stuffs formed without
insertion of a naphthylamine.

page_text: IV.
THE BASE WITH
COLOURING MATTERS OBTAINED BY COMBINING ONE MOLECULE OF
ONE MOLECULE OF Y-AMIDONAPHTHOL MONOSULPHO
ACID, REDIAZOTISING THE INTERMEDIATE PRODUCT, AND COMBINING
THE LATTER WITH TWO MOLECULES OF EQUAL OR DIFFERENT
COMPOUNDS.
Instead of a naphthylamine as described under head III, one molecule of
y amidonaphtholmonosulphoacid may be combined with the tetrazo salt in an
alkaline solution to form an intermediate product, which, after rediazotising, yields
blue black colouring matters, when combined with two molecules of equal or different
compounds as mentioned above.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, I declare that what I
claim is :-
a
1. The herein described process for the production of azo colouring matters by
combining one molecule of the tetrazo compound of p-amido benzene azo amido
naphthaline with two molecules of an amine, phenole (except carbolic acid,
resorcine and the naphtholes) amido phenole or their carbo or sulpho acids (except
Schaeffer's ẞ naphtholmonosulpho acid).
2. The herein described process for the production of mixed azo colouring
matters by combining one molecule of the tetrazo compound of p-amido benzene
azo amido a naphthaline with one molecule of an amine, phenole, amidophenole
or their sulpho- cr carbo-acids to form an intermediate product and reacting with
the latter upon one molecule of another of the substances which may be combined
with the tetrazo compound to form the intermediate product.
3. The herein described process for the production of colouring matters by com-
bining one molecule of the tetrazo compound of p-amido benzene azo amido
naphthaline with one molecule of a naphthylamine, rediazotising this product
and combining it with two equal or different molecules of amines, phenoles, amido
phenoles or their sulpho- or carbo-acids.
a
D
4. The herein described process for the production of colouring matters by
combining one molecule of the tetrazo compound of p-amido benzene azo amido
naphthaline with one molecule of y amidonaphtholmono sulpho acid, rediazotising
this product and combining it with two equal or different molecules of amines,
phenoles, amido phenoles or their sulpho- or carbo-acids.
5. The azo colouring matters produced by each of the processes referred to in the
preceding claims.
Dated this 5th day of October 1892.
ABEL & IMRAY,
Agents for the Applicant.