Improvements in the Manufacture and Production of Direct-dyeing Yellow Colouring Matters.
Year: 1889

page_text: Date of Apulication, 16th Nov., 1889
Complete Specification Left, 25th Aug., 1890-Accepted, 27th Sept., 1890
PROVISIONAL SPECIFICATION.
[Communicated from abroad by FARBENFABRIKEN VORMALS FRIEDRICH BAYER
AND Co., of Elberfeld, in the Empire of Germany, Manufacturers.]
Improvements in the Manufacture and Production of Direct-dyeing
Yellow Colouring Matters.
I, BENJAMIN WILLCOX, of 47 Lincolns Inn Fields in the County of Middlesex
Gentleman, do hereby declare the nature of this invention, which invention has
been communicated to me from abroad by The Farbenfabriken vormals Friedrich
Bayer and Company of Elberfeld in the Empire of Germany, to be as follows:-
My foreign correspondents have discovered that the colouring matter known as
primuline and the sulpho-acids of dehydro thio para toluidine can be readily alkylised
by treatment with alkyl haloids, such as methyl, ethyl, amyl or benzyl haloids in
closed or open vessels as hereinafter described. Products are thus obtained which
dye much more beautifully than the aforesaid primuline.
The colour acquires a greener tinge in proportion to the increase in the molecular
weight of the alkyl haloid employed so that the most pure greenish yellow shades are
obtained by the employment of benzyl haloids.
The following may be taken as examples of the manufacture :-
First Example. About 17 kilos. of commercial primuline are heated with about
5.1 kilos. of bromethyl, 44 kilos. of bicarbonate of soda and 100 litres of water in a
closed vessel, at the temperature of a water bath, for from about 5 to 8 hours. From
this solution which is of a deep red colour, the alkylised primuline is precipitated in
brown flakes on the addition of common salt.
Second Example.-About 10 parts of a soda salt of the dehydro thio para toluidine
sulpho-acid, are heated with 6.6 parts of bromethyl, 5 parts of bicarbonate of soda
and 100 litres of water in a closed vessel at the temperature of a water bath for
from about 6 to 7 hours. The product of the alkylising separates as a resinous mass
and is purified by re-dissolving and salting out.
My foreign correspondents have further discovered that beautiful greenish yellow
direct dyeing colouring matters can also be obtained from the various sulphurous or
sulphurised derivatives or derivatives containing sulphur, produced by the action of
sulphur upon para toluidine, meta xylidine and pseudo cumidine, the said colouring
matters being obtained by causing the diazo compounds of the above mentioned
derivatives or the diazo compounds of their sulpho-acids to act upon the sulpho-acids
of the said derivatives or by causing the diazo compounds of their sulpho-acids to act
upon the sulphurous or sulphurised base itself, of the said para toluidine meta xylidine
and pseudo cumidine.
The process for the production of this group of new coloring matters is described
in general terms as follows:
The diazo compound of the sulphurous base or of its sulpho-acid is poured into an
acetic acid solution of the sulpho acid of the sulphurous base, or, when a diazo
compound of the sulpho acid of the sulphurous base is employed, into an acetic
acid solution of the base itself, being allowed to stand for several days at a temperature
of from about 20 to 30 degrees Centigrade gradually raised to from about 60 to
80 degrees being maintained at this temperature until a sample boiled in soda dissolves
with a yellow colour. The solution is then boiled and neutralised with soda and the
colouring matter is separated in the usual way.
Example Colouring matter from thio para toluidine, melting point 191 degrees
Centigrade and the sulpho acid thereof.
About 31 kilos. of thio para toluidine whose melting point is 191 degrees Centigrade
are diazotised in the form of its sulphuric acid salt with about 10 kilos. of nitrite at

page_text: from 30 to 40 degrees. The diazo compound obtained is introduced into an acetic
acid solution of about 25 kilos. of thio para toluidine sulpho acid (produced by
sulphurising the thio para toluidine, melting at 191 degrees, with fuming acid). A
dirty looking greyish black deposit results at first, whilst stirring continually, the
temperature is raised to from about 20 to 30 degrees Centigrade and then after two 5
days to from about 60 to 70 degrees.
The dirty black colour of the deposit gradually changes to a pure orange.
When a sample after boiling with soda dissolves with a yellow colour the whole
mass is beated to boiling and neutralised with soda and the colouring matter is
separated by salting out in the usual way.
This product dyes unmordanted cotton a beautiful greenish yellow.
It cannot be diazotised on the fibre.
With the various derivatives containing sulphur derived from para toluidine the
most beautiful greenish yellow direct dyeing colouring matters can be produced.
Redder dyes are obtained with the employment of sulphurous derivatives of meta 1
xylidine and pseudo cumidine.
Dated 16th day of November 1880
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture and Production of Direct-dyeing
Yellow Colouring Matters.
I BENJAMIN WILLCOX of 47 Lincolns Inn Fields in the County of Middlesex
Patent Agent do hereby declare the nature of this invention which has been
communicated to me from abroad by Farbenfabriken vormals Friedrich Bayer and Co.
of Elberfeld in the Empire of Germany 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 discovered that beautiful yellow direct dyeing
colouring matters can be obtained from the various derivatives containing sulphur
(thio-bases) produced by the action of sulphur upon para-toluidine, meta-xylidine or
pseudo-cumidine the said colouring matters being obtained by causing diazo compounds
of the above mentioned derivatives or the diazo compounds of their sulpho-acids to
act upon the sulpho acids of the said derivatives or by causing the diazo compounds
of their sulpho-acids to act upon the thio-bases of the said para-toluidine, meta
xylidine and pseudo-cumidine.
The process for the production of this group of new colouring matters is described
in general terms as follows:-
The diazo compound of the base or of its sulpho-acid for example of dehydro-
theotoluidine-sulpho acid or of the so called primuline sulpho-acid is poured into an
acetic acid solution of the sulpho-acid of another or of the same thio-base or when a
diazo-compound of the sulpho acid of the thio base is employed into an acetic acid
solution of the base itself the mixture being allowed to stand for a time usually for
several days at a temperature of from about 20 to 30 degrees Centigrade and being
then gradually raised to from about 60 to 80 degrees and maintained at this
temperature until a sample when boiled in an alkaline solution (one of soda for
instance) dissolves with a yellow colour. The solution is then boiled and neutralized
with an alkaline solution (one of soda for instance) and the colouring matter is
separated in the usual way. The dyestuff forms more rapidly if instead of an acetic
acid solution a solution of an alkali such as soda is employed in forming the
dyestuff.
Example Colouring inatter from thio-para-toluidine melting at 191 degrees
Centigrade and the sulpho acid thereof.
About 31 kilos. of the thio-para-toluidine whose melting point is 191 degrees

page_text: Centigrade in the form of sulphate is diazotized with about 10 kilos. of nitrite at
from 30 to 40 degrees Centigrade. The resulting diazo compound is introduced into
an acetic acid solution of about 25 kilos. of thio-para-toluidine-sulpho-acid (produced
by sulphonating with fuming acid the thio-para-toluidine melting at 191 degrees-
A dirty greyish-black deposit is at first formed. Whilst stirring continually the
temperature is now raised to from about 20 to 30 degrees Centigrade and after the
mixture has been kept at this temperature for about two days the temperature is
raised to from about 50 to 60 degrees Centigrade. The dirty black colour of the
deposit gradually changes to a pure orange. When a sample on boiling with soda
dissolves with a yellow colour the whole mass is heated to boiling and neutralized
with soda and the colouring matter is then separated by salting out in the usual
way. This product dyes unmordanted cotton a beautiful yellow having a greenish
tinge.
Instead of the thio-para-toluidine melting at 191 degrees the so called primuline
base or the sulpho acids of these bases may be employed with like results.
From the various derivatives containing sulphur derived from para-toluidine the
most beautiful yellow direct dyeing colouring matters with a greenish tinge can be
produced. Redder yellow dyes are obtained when thio derivatives of meta-xylidine
and pseudo-cumidine are employed.
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 :-
First. The production of colouring matters by combining the diazo compounds of
thio-bases (which can be formed by the action of sulphur on para-toluidine; meta-
xylidine, or pseudo-cumidine) or of their sulpho-acids with sulpho-acids of the same
or other thio-bases or by combining sulpho-acids of the diazo compounds of the said
thio bases with the same or other thio bases.
Second. As new articles of manufacture the colouring matters hereinbefore
described.
Dated this 25th day of Angust. 1890
J. H. JOHNSON & Co.,
47, Lincoln's Inn Fields, W.C., Agents.