Manufacture of Direct Dyeing Colouring Matters.
Year: 1895

page_text: Date of Application, 22nd Apr., 1895
Complete Specification Left, 13th Jan., 1896-Accepted, 15th Feb., 1896
PROVISIONAL SPECIFICATION.
FÜR
[Communicated from abroad by THE ACTIEN GESELLSCHAFT
ANILIN FABRIKATION, of Berlin, in the Empire of Germany, Chemical
Manufacturers.]
Manufacture of Direct Dyeing Colouring Matters.
I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Consulting Engineer and Chartered Patent Agent, do
hereby declare the nature of this invention to be as follows:-
The invention relates to the production of direct dyeing colouring matters in
connection with the invention described in the Specification No. 4018 of 1895.
In this Specification my foreign correspondents have described a process for
the production of substantive dyes which are prepared by means of the following
tetrazo compound :
Their further studies about this kind of colouring matters have led them to the
observation that the process described in the said Specification may be applied to
a series of tetrazo compounds, which possess an analogous constitution.
The typical constitution of all these tetrazo compounds may be expressed by
the following general formula:
in which X and Y signify amido or hydroxyl groups.
It is to be observed that the relative position of these groups in the naphthaline
necleus may vary.
But such positions of X and Y in the naphthaline nucleus as
by themselves or together with the sulpho group would prevent the introduction
of two azo groups are necessarily left out of consideration.
In the Specification No. 4018 of 1895 above referred to the groups X and Y
for instance the positions a and but they may also stand in the
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page_text: Into one or into both of the benzene nuclei carrying the two azo groups other
constituents may enter such as for instance the methyl group, the sulpho group and
the like.
The tetrazo compounds serving as primary materials for the production of the
colours are prepared in the same manner as indicated in the Specification No. 4018
of 1895, by means of para-nitrodiazobenzene or acetyl-para-phenylenediamine and
the respective naphthaline derivatives.
T

page_text: I, CHARLES DENTON ABEL, of No. 28 Southampton Buildings, Chancery Lane,
in the County of London, Consulting Engineer and 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 :-
The invention relates to the production of direct dyeing colouring matters in
connection with the invention described in the Specification No. 4018 of 1895.
In this Specification my foreign correspondents have described a process for the
production of substantive dyes which are prepared by means of the following
tetrazo compound
20 Their further studies about this kind of colouring matters have led them to the
observation that the process described in the said Specification may be applied to
a series of tetrazo compounds, which possess an analogous constitution.

page_text: The typical constitution of all these tetrazo compounds may be expressed by the
following general formula:
in which X and Y signify amido or hydroxyl groups.
It is to be observed that the relative position of these groups in the naphthaline
nucleus may vary. But such positions of X and Y in the naphthaline nucleus as
by themselves or together with the sulpho group could prevent the introduction of
two azo groups are necessarily left out of consideration."
In the Specification No. 4018 of 1895 above referred to the groups X and Y
occupy for instance the positions a and a
but they may also stand in the
positions ₁ and ẞ, etc.
Into one or into both of the benzene nuclei carrying the two azo groups other
constituents may enter, such as for instance, the methyl group, the sulpho group
and the like.
The tetrazo compounds serving as primary materials for the production of the
colours are prepared in the same manner as indicated in the Specification No. 4018
of 1895, by means of para-nitrodiazobenzene or acetyl-para-phenylene-diamine and
the respective naphthaline derivatives.
obtained after reduction, or saponification respectively, are converted into tetrazo
compounds by the action of two molecules of nitrous acid in acid solution.
If the terazo compounds be caused to react upon two molecules (like or
different) of components suitable for the production of colouring matters (such
as phenole, amine, diamine etc.) the new azo dye stuffs are formed, which
generally are characterised by their intensity, their fastness, and their dark tint.

page_text: EXAMPLE 1.
14 kilos. of the tetrazo compound possessing the following constitution.
formula:
[a,OH
aOH
B₁N
=
-
N – CH.NH,
C10H,
BNN
-
CH¸NH,
ẞ,SO,H
L.SO,H
are tetrazotised in the usual manner by addition of 3.5 kilos. of nitrite of soda
and the blue black solution of the tetrazo compound thus formed is allowed
to flow into a solution, which is rendered and kept alkaline, of 6.1 kilos. of
toluylenediamine.
The combination takes place readily and the colouring matter separates as a
blue-black precipitate.
It readily dissolves in water with a blue violet colour and produces on
unmordanted cotton from a salt or soap bath greenish black shades, distinguished
by their intensity and remarkable fastness.
If in the above example the equivalent quantity of ẞ-naphthol be substituted.
for the toluylenediamine a colouring matter is obtained dyeing cotton dark green-
black shades.

page_text: cotton from a salt or soap bath deep black shades, distinguished by their intensity
and fastness.
If in this example the equivalent quantity of B-naphthol be substituted for the
toluylenediamine, a colouring matter dyeing blue black shades is obtained.
EXAMPLE 3.
16 kilos. of the product of the following constitution-formula:
BÌNH,
OH
B₂
NH,
N = N
-
CHB
a1
\SO₂H
CoHa
-SO₂H
a,NN CH¸
NH
SO,H
Вз
are tetrazotised by means of 3.5 kilos. of nitrite of soda and the solution of the
tetrazo-compound thus obtained is slowly added to a solution, which is rendered
and kept alkaline, of 6.1 kilos. of meta-toluylenediamine. The combination-
product, when completely formed is mostly precipitated and is filtered off, the last
traces being salted out from the mother liquors by addition of common salt. The
colouring matter forms, in a dry state, a dark powder possessing a bright metallic
lustre. It is insoluble in alcohol, sparingly soluble in cold water, readily soluble
in hot water with a blackish-blue colour and it dissolves in concentrated sulphuric
acid with a greenish-blue colour, which on addition of water becomes blue. On
addition of alkalies, the colouring matter is partly precipitated from its aqueous
solution without change of colour; mineral acids precipitate the free acid of the
dye-stuff in the form of blue-black flakes. The dyestuff dyes unmordanted cotton,
from a soap or salt-bath blueish-black shades distinguished by their intensity and
fastness.

page_text: into a solution which is rendered and kept alkaline, of 6.1 kilos. of toluylene-
diamine.
After
The new colouring matter is readily formed and partly separates out.
stirring some time the whole is heated, and the dye-stuff is salted out by means of
common salt. The colouring matter, forming in a dry state a dark powder with a
metallic lustre, is insoluble in cold water, but soluble in hot water with a blue-black
colour; from its aqueous solution it is partly precipitated on addition of alkalies
without change of colour; mineral acids effect its complete precipitation in the
form of brown flakes. The colouring matter is insoluble in alcohol, but soluble in
concentrated sulphuric acid with a blackish violet colour, which on addition of
water, becomes violet. The dyestuff dyes unmordanted cotton from a soap or salt
bath black shades of great fastness.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, 1 declare that what I
claim is :-
1. The manufacture of direct dyeing azo-colouring-matters by combining amines
or phenoles with tetrazotized compounds, having the typical constitution indicated
by the following general formula :`