Year: 1888

page_text: Date of Application. 28th Nov., 1888
Complete Specification Left, 20th Aug., 1889-Accepted. 2nd Nov., 1889

page_text: The azo-dye-stuff which is obtained by this process dyes cotton direct from a soap-
bath in a red shade. The color withstands very well the influence of acids, soap and
light.
If, in the above described example a-naphtylamine-sulphonic acid of Piria is used
instead of a naphthole-disulphonic acid, a dye stuff is obtained which dyes cotton an
orange shade. By combining the ẞ naphthole sulphonic acid of Bayer and the
B-naphthole disulphonic acid G with the above diazo-combination a red dye-stuff is
obtained, whereas ẞ naphthole-disulphonic acid R forms a bluish red dye. Phenole
and phenole-sulphonic acids yield yellow dye-stuffs and resorcine yields orange dye-
stuffs.
If diamido-dimethyle-stilbene-sulphide or diamido-tetramethyle-stilbene-sulphide are
used instead of diamido-stilbene-sulphide, and if they are diazotized and the diazo-
combinations thus obtained again combined with the above-described combinations,
dye-stuffs are obtained which also dye cotton direct in shades very similar to those of
the dye-stuffs derived from diamido-stilbene-sulphide.
Some of the combinations thus obtained are only soluble with great difficulty and,
consequently, not well adapted for dyeing purposes. It is in such cases preferable to
convert the bases which are in the above description named diamido-dimethyle-
stilbene-sulphide and diamido-tetramethyle-stilbene-sulphide into their sulphonic
acids by means of sulphuric acid. These sulphonic acids are then converted into
diazo-combinations by means of nitrous acid, and afterwards combined with the above
mentioned phenoles bases or their sulphonic or carbonic acids.
For instance the sulphonic acid of diamido dimethyle-stilbene-sulphide yields,
according to the above described process in combination with Bismarck brown, a
brown dye-stuff which dyes cotton direct a brown shade.
Dated this 28th day of November 1888.
ABEL & IMKAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
A New Manufacture of Dye-stuffs.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane, in
the County of London, Consulting Engineer and 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:-
By heating two molecules each of m-Xylidine, or pseudo-Cumidine with two
molecules of sulphur, sulphurated bases are formed with liberation of sulphurated
hydrogen.
By the action of nitrous acid upon these bases they are converted into diazo-
compounds, which can be combined to form dye stuffs with phenole and its homo-
logues, resorcine, resorcine ethers, orcine, naphtole, dioxy-naphthaline, phenyleu-
diamine, toluylen-diamine, chrysoidines, Bismarck-brown, naphthylamine, and its
alkyle-derivates, or with their sulphonic or carbonic acids.
I. PRODUCTION OF THE SULPHURATED BASES.
The following description of the production of base from m-xylidine and sulphur
may serve as an example for the production of the sulphurated bases.
This base is obtained by heating 40 Kg. of m-xylidine with 10 Kg. of sulphur, as
long as sulphurated hydrogen is given off. After allowing the product of this
reaction to cool down a little, it is entered into sulphuric acid previously diluted with
an equal quantity of water. The solution of the new base which is thus obtained is
then poured into water, whereby the sulphate of the base separates' in yellow flakes,
while same unconverted xylidine remains in solution as sulphate. The sulphate of
the new base is isolated by filtration of the precipitate. The sulphate of the new
base forms a yellow compound which is not soluble in water, but soluble in alcohol.

page_text: II. PRODUCTION OF DYE-STUFFS FROM THE SULPHURATED BASES.
In order to produce dye stuffs from the sulphurated bases, these latter are first
converted into their diazo-combinations in a strongly acidulated solution by means of
nitrous acid, and these combinations are then combined with the above named
substances.
Example: Dye-stuff from the sulphurated base from m-xylidine and a-naphtole-
disulphonic-acid.
20 Kg. of the sulphate of the sulphurated base from m-xylidine are dissolved in
125 Kg. of hydrochloric acid (12° B) and poured into 1,000 liters of water, and
afterwards a solution of 14 Kg. of nitrite of soda in 50 liters of water is gradually
entered into it. The diazo-combination thus obtained, is then poured into an alkaline
solution of a-naphtole, disulphonic acid, whereby the azo-dye-stuff is formed. This
latter is obtained by boiling the solution, precipitating with common salt, and filtering
the precipitate.
The azo-dye stuff which is obtained by this process dyes cotton direct from a soap-
bath in a red shade. The color withstands very well the influence of acids, soap, and
light.
If in the above described example, a-naphthylamine-sulphonic acid of Piria is used
instead of a-naphtole-disulphonic acid, a dye stuff is obtained which dye cotton
an orange shade. By combining the B-naphthole-sulphonic acid of Bayer and the
B-naphthole-disulphonic acid G with the above diazo-combination, a red dye stuff is
obtained, whereas ẞ-naphthole disulphonic acid R forms a bluish red dye. Phenole
and phenole-sulphonic acids yield yellow, and resorcin orange dye-stuffs.
If the sulphurated base from pseudo Cumidine is used instead of sulphurated base
from mi-xylidine and if the former is diazotized and the diazo compound thus obtained
be again combined with the above mentioned substances, dye stuffs are obtained which
also dye cotton direct in shades very similar to those of the dye stuffs derived from
the xylidine-base.
Some of the combinations thus obtained are scarcely soluble in water and conse-
quently not well adapted for dyeing purposes. It is in such cases preferable to
convert the bases above described into their sulphonic acids by means of sulphuric
acid. These sulphonic acids are then converted into diazo-combinations by means of
nitrous acid, and afterwards combined with the above mentioned phenoles, amines or
their sulphonic or carbonic acids.
For instance, the sulphonic acid of the sulphurated m-xylidine base yields according
to the above described process in combination with Bismarck brown, a brown dye-
stuff which dyes a brown shade on cotton without a mordant.
This dye stuff is produced in the following manner. 31.7 Kilo of thio-m-xylidine
sulphate are mixed with 126.8 Kilo of fuming sulphuric acid, the temperature being
maintained at 30° or 40° C. The sulphuration is known to be complete when a
sample of the mixture dissolves in alkali without clouding. The darkly coloured melt
is poured on ice and the free sulphonic acid of the thio-bases appears as an orange
yellow powder. This is filtered washed in water and pressed. 34.8 Kilo of this
compressed cake are then dissolved in 12 Kilo of crude 30 % soda lye and mixed
with 7.2 Kilo of 96 % nitrite of soda. The solution thus obtained is poured into a
mixture of 50 Kilo crude hydrochloric acid with 500 Kilo of ice applied to cool it.
The diazo solution thus obtained is then poured into an aqueous solution of 79 Kilo
Bismarck brown and 75 Kilo soda and the whole is well stirred. After standing for
about 24 hours, the solution is filtered and the colouring matter is separated by means
of salt.
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 :-
1 Was the manuff the nuniluation of aulnhurated hases by heating

page_text: m-xylidine or pseudo-Cumidine with sulphur substantially in the manner described
above.
2. The production of azo dye stuffs from the sulphurated bases mentioned in the
first claim by the reaction of nitrous acid upon the sulphurated bases and by the
combination of the diazo-compounds thus obtained with phenole, its homologues,
resorcine, resorcine ethers, orcine naphthole, dioxynaphthaline, phenylen-diamine,
toluylen-diamine, chrysoidines, Bismarck-Brown naphthylamine and its alkyle deri-
vates, or with their sulphonic or carbonic acids.
3. For the production of azo dye stuffs the conversion of the sulphurated bases
mentioned in the first claim into their sulphonic acids, the reaction of nitrous acid
upon these acids, and the combination of the diazo-compounds, thus obtained with the
substances mentioned in the second claim.
4. As a new manufacture the orange, yellow brown and red dye stuffs produced as
herein described.
Dated this 20th day of Anant 1880
ABEL & IMRAY,
Agents for the Applicant.