Improvements in the Manufacture of Mordant Dyeing Azo Colouring Matters of the Triphenylmethane Group.
Year: 1890

page_text: Date of Application, 4th Mar., 1890
.Complete Specification Left, 4th Dec., 1890-Accepted, 10th Jan., 1891
PROVISIONAL SPECIFICATION.
Improvements in the Manufacture of Mordant Dyeing Azo Colouring
Matters of the Triphenylmethane Group.
I, BENJAMIN WILLCOX, of 47 Lincoln's Inn Fields, in the County of Middlesex,
Patent Agent, do hereby declare the nature of this invention, which has been com-
municated to me, from abroad by The Farbenfabriken vormals Friedrich Bayer & Co.,
of Elberfeld, in the Empire of Germany, to be as follows:-
My foreign correspondents have discovered that the meta and para amido tetra
substituted diamido triphenyl methanes can be diazotised with ease and the resulting
diazo compound combined with dyestuff components to form new azo bodies which by
oxidation lead to a new group of triphenyl methane colouring matters termed azo
triphenylmethane dyes.
By these means green or blue. to deep blue black colouring matters are obtained
according as the meta or para amido compounds are employed.
The dyestuff components such as amides phenols and the like exert in themselves
little influence on the colour which depends chiefly on the position of the amido group
to be diazotised. On the other hand the selection of the dyestuff component has great
influence on the fastness of the new product.
As far as has been ascertained at present they do not all lead to practically useful
results.
Good results are obtained in particular with the employment of the carbon acids of
phenols and with certain dioxynaphthalenes that is to say in a general way with such
components as lead to azo colouring matter forming lakes.
Products are thus obtained which dye with beautiful and fast colours on metallic
mordants chrome in particular and which are especially well suited for printing
purposes and also for dyeing wool previously mordanted with chrome mordants.
Out of the triamido triphenyl methane derivatives (diamido triphenyl methane
being hereinafter represented for the sake of brevity by the letter D) all the tetra
substituted such as the
substituted such as the
meta and para amido tetra methyl D
meta amido dimethyl diethyl D
meta amido tetra ethyl D
meta amido diethyl dibenzyl D
found suitable namely-
salicylic acid
-
cresol carbon acids
alpha and beta naphthol carbon acids
alpha-beta-dioxynaphthalene (beta hydro naphtho quinone) 1-8 dioxynaphthalene.
The colouring matters of the meta group with salicylic acid and cresol carbon acid
dye wool previously mordanted with chrome a yellowish green with the naphthol
carbon acids a dark olive green,.those of the para group with salicylic acid and cresol
carbon acid dye greenish blue to black, with alpha and beta naphthol carbon acid,
18 dioxynaphthalene and alpha-beta-dioxynaphthalene on the other hand dye blue.
All these colouring matters are more or less soluble in water and consequently are
most conveniently employed in the form of a fine paste.
The following are given as examples of the manufacture of these new colouring
matters.

page_text: EXAMPLE I.
34.5 kilos. of meta amido tetra methyl diamido triphenyl methan are dissolved with
33 kilos. of hydrochloric acid (at 33 per cent.) in 200 litres of water, cooled to
0 degree Centigrade and slowly added with stirring to a solution of 7 kilos. of
nitrite.
The resulting diazo compound is slowly and whilst stirring introduced into a
solution (cooled down to 0 degree Centigrade) of 14 kilos. of salicylic acid in
120 kilos. of soda lye (at 33 per cent.) and 100 litres of water and the mixture is
allowed to stand for say 24 hours at a temperature of from 0 to 4 degrees
Centigrade.
The temperature of the materials is then gently raised and the separated yellow azo
triphenyl methane leuco base may either be separated by filtration dried and oxidised
in an acetic acid or hydrochloric acid solution with the calculated quantity of
peroxide of lead or preferably the mixture directly obtained is supersaturated with
200 kilos. of hydrochloric acid after being diluted with water whereupon the azo leuco
base readily goes into solution the materials then being filtered if necessary and
84 kilos. of a peroxide of lead paste (at 28 per cent.) is introduced with stirring at a
temperature of 30 degrees Centigrade.
The temperature of the liquid is then raised to about 80 degrees Centigrade the
colouring matter separating out in brown flakes is filtered off hot and washed out with
heated brine. The filtrate then contains in solution the lead chloride the excess of
salicylic acid and a certain amount of triphenyl methane base still remaining
uncoupled.
The colouring matter thus produced is dried and finely ground or preferably
employed directly as a paste. It is soluble with great difficulty in cold water but
dissolves more readily in hot water especially with the addition of acetic acid. Glacial
acetic acid dissolves it easily. On wool previously mordanted with chrome it produces
a beautiful clear yellowish green colour fast to fulling.
EXAMPLE II.
34.5 kilos. of para amido tetra methyl diamido triphenyl methane are diazotised in
exactly the same way as in the preceding example and the diazo solution is introduced
into a solution of 20 kilos. of oxynaphthoic acid in 120 kilos. of 33 per cent. soda lye.
The brown deposit is filtered off after a few hours dried, dissolved in 200 litres of
strong acetic acid and 84 kilos. of peroxide of lead (at 28 per cent.) are added the
materials are then gently heated and the lead precipitated with 20 kilos. of sulphuric
acid at 50 per cent. and filtered.
On diluting the filtrate with water the colouring matter immediately commences to
be precipitated the precipitation being completed in the addition of common salt.. It
is filtered off and employed direct as a paste dyeing chrome mordanted wool a
beautiful blue.
Similar colouring matter is obtained when the amido leuco bases are first
oxidised in the usual manner, diazotised and then allowed to react on dyestuff
components.
Another method of obtaining this azo triphenyl methane colouring matter results
from the discovery that the diazo compounds of the amido tetra substituted triphenyl
methane leuco bases can be oxidized smoothly. The resulting diaze triphenyl
colouring matter can then be coupled with the dyestuff components.
Another effect obtained by means of this invention is as follows:-
It is known that the amido tetra substituted triphenyl methane leuco bases and
colouring matters by diazotising followed by boiling the diazo compound with diluted
sulphuric acid are converted into the desired blue oxy tetra substituted diamido
triphenyl methane colouring matter, not quantitatively but at the utmost only to the
extent of 70 per cent.

page_text: The present new process enables conversions of this nature to take place smoothly.
The following may be given as an example of the process for the production of the
diazo combination of the tetra substituted triamido triphenyl methane.
34.5 kilos. of meta amido tetra methyl diamido triphenyl methane are dissolved in
300 litres of water and 60 kilos. of hydrochloric acid at 33 degrees Baumé or
sulphuric acid at 60 degrees Baumé, cooled to 0 degrees Centigrade and run into a
solution of 7 kilos. of nitrite.
To oxidize the diazo combination which is immediately formed it is mixed with
84 kilos. of a 28 per cent. paste of peroxide of lead and the lead is precipitated by the
addition of 300 kilos. of 10 per cent. sulphuric acid and separated by filtration.
The diazo compound thus obtained is heated to 60 degrees Centigrade until all the
nitrogen has escaped and is thus converted into the oxy combination the colouring
matter obtained being isolated by salting out and purified by solution.
The coupling of the diazo compound is proceeded with as hereinbefore described.
For example, to obtain a green, mordant dyeing colouring matter it is caused to
run into 14 kilos. of an alkaline solution of salicylic acid and allowed to stand.
Dated this 3rd day of March 1800
J. H. JOHNSON & Co.,
Agents.
COMPLETE SPECIFICATION.
Improvements in the Manufacture of Mordant Dyeing Azo Colouring
Matters of the Triphenylmethane Group.
1 BENJAMIN WILLCOX of 47 Lincoln's Inn Fields in the County of Middlesex,
Patent Agent do hereby declare the nature of this invention, which has been com-
municated to me from abroad by The Farbenfabriken vormals Friedrich Bayer & 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 the meta and para-amido tetra-
substituted diamido-triphenyl methanes can be diazotised with ease and the resulting
diazo compounds combined with dyestuff components to form new azo bodies which on
oxidation afford a new group of triphenyl methane colouring matters termed azo
triphenyl methane dyes.
By these means green or blue to deep blue-black colouring matters are obtained
according as the meta- or para-amido-compounds are employed.
The dyestuff components such as amides phenols and the like exert in themselves
little influence on the colour which depends chiefly on the position of the amido group
to be diazotised. The fastness of the new product, however largely depends on the
selection of the dyestuff components. As far as has been ascertained at present they
do not all afford practically useful results. The best results are obtained in particular
by the employment of carboxy acids of phenols and certain dihydroxynaphthalenes
that is to say in general terms such components as afford azo colouring matters
capable of forming lakes.
Products are thus obtained which dye beautiful fast colours with the aid of metallic
mordants, chromium mordants in particular, and which are especially well suited for
printing purposes and also for dyeing wool previously mordanted with chromium
mordants.
Of the triamido triphenyl methane derivatives (diamido triphenyl methane being
hereinafter represented for the sake of brevity by the letter D) all the tetra substituted
such as the-
meta and para amido tetra methyl D
meta amido dimethyl diethyl D
meta amido tetra ethyl D
meta amido diethyl dibenzyl D
are found to be suitable for the purposes of the present invention.

page_text: On diluting the filtrate with water the colouring matter inmediately commences.
to be precipitated the precipitation being completed on the addition of common salt.
It is filtered off and employed direct as a paste, dyeing chromium mordanted wool a.
beautiful blue.
Similar colouring matter is obtained when the amido leuco bases are first oxidised!
in the usual manner diazotised and then allowed to react on dyestuff components.
Another method of obtaining this azo triphenyl methane colouring matter results.
from the discovery that the diazo compounds of the amido tetra substituted triphenyl
methane leuco bases can be directly oxidised. The resulting diazo triphenyl colouring.
matter can then be coupled with the dyestuff components.
Another effect obtained by means of this invention is as follows.
It is known that by diazotising and boiling the diazo compound with diluted'
sulphuric acid the amido tetra substituted triphenyl methane leuco bases and colouring
matters are not quantitatively but at the utmost only to the extent of 70 per cent..
converted into the desired blue hydroxy tetra substituted diamido triphenyl methane-
colouring matter.
The present new process enables conversions of this nature to take place in a
complete manner.
The following may be given as an example of the process for the production of the
diazo combination of the tetra substituted triamido triphenyl methane.
34.5 kilos. of meta amido tetra methyl diamido triphenyl methane are dissolved in
300 litres of water and 60 kilos. of hydrochloric acid at 33 degrees Baumé or sulphuric
acid at 60 degrees Baumé, cooled to 0 degree Centigrade and ran into a solution of
7 kilos. of nitrite of soda.
To oxidise the diazo combination which is immediately formed it is mixed with
84 kilos. of a 28 per cent. paste of peroxide of lead and the lead is precipitated by the
addition of 300 kilos. of 10 per cent. sulphuric acid and separated by filtration.
The diazo compound thus obtained is heated to 60 degrees Centigrade until all the
nitrogen has escaped and is thus converted into the hydroxy combination the colouring
matter obtained being isolated by salting out and purified by solution.
Th coupling of the oxidised diazo compound is proceeded with as hereinbefore.
described.
For example to obtain a green, mordant dyeing colouring matter, the diazo
compound oxidized in the above described manner is caused to run into 14 kilos. of
an alkaline solution of salicyclic acid and the mixture allowed to stand for a suitable.
time until the coupling is effected.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed, I declare that what I
claim is:
1. The manufacture of green and blue to deep blue black colouring matters.
(called azo tripbenyl methane dies).
a. By the action of one molecular proportion of meta or para diazo tetra substi
tuted diamido triphenyl methanes upon one molecular proportion of a phenol,
naphthol, phenolcarboxy acid, naphthol carboxy acid or dihydroxynaphthalene
and oxidizing the resulting azo compounds;
b. By diazatizing the oxidized meta or para amido tetra substituted diamido
triphenyl methanes and acting with the diazo compounds upon phenols,
naphthols phenol-carboxy acids, naphthol-carboxy acids, or dihydroxy-
naphthalenes;
c. Ry oxidising the diazitised meta or para amido tetra substituteu diamido
triphenyl methanes and acting with the diazo-compounds upon phenols,
naphthols, phenol carboxy acids, naphthol carboxy acids or dihydroxy-
naphthalenes.
2. As new articles of manufacture the new products such as are obtained according
to the processes hereinbefore claimed.

page_text: 3. The process for oxidizing the diazo compounds of the meta amido tetrasubstituted
diamido triphenyl methanes with oxidizing agents.
Dated this
day of December 1800
J. H. JOHNSON & Co.,
Agents.