Process for the Transformation of the Thiosulphonates of the Indamines and Indophenols into Thiazinic Colouring Matters.
Year: 1896

page_text: Date of Application, 9th Mar., 1896-Accepted, 11th Apr., 1896
[Communicated from abroad by THE SOCIETY OF CHEMICAL INDUSTRY IN
BASLE, Basle, Switzerland, Chemical Manufacturers.]
Process for the Transformation of the Thiosulphonates of the
Indamines and Indophenols into Thiazinic Colouring Matters.
I, OLIVER IMRAY, of No. 28 Southampton Buildings 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 b the following statement :-
The production of thiazinic colouring matters by means of the thiosulphonates
of the corresponding indamines and indophenols has hitherto exclusively taken
place in weak aqueous solution at boiling temperature, and by adding to the said
solution acetic acid, zinc chloride or other condensation agent. This method
furnishes very nearly the half of the thiazinic colouring matters in the form of
leuco compounds which have to be transformed into colouring matters by farther
oxidation; moreover the process with zinc chloride in many cases gives quite
insufficient results as for instance when use is made of the indamine thiosulphonic
acids of metatoluylene diamine, of diethylaniline or of the dialkymetamido-
phenol ethers.
My correspondents have found, in order to effect transformation of the thio-
sulphonates of the indamines and indophenols into thiazinic colouring matters,
a new reaction, which is of general application, and which takes place without
presence of water, advantageously in monohydrated sulphuric acid with or without
addition of fuming sulphuric acid, of chlorosulphonic acid (sulphuric chlorhydrine)
of pyrosulphates, chlorides &c., at ordinary temperatures or temperatures between
60° and 80° C.
By this reaction thiazinic colouring matters are directly obtained in an excellent
state of purity and in crystalline condition.
This reaction in concentrated sulphuric acid is the more remarkable as it is
known that the indamines and indophenols are very sensitive to weak mineral
acids and are caused by these to undergo a decomposition most frequently very
complete.
My correspondents have ascertained that the reaction is applicable with advantage
to all the thiosulphonates obtained by known methods from the dialkylparapheny-
lenediamine thiosulphonic acids, from the monoalkylparatoluylenediamine thio-
sulphonic acids and from the sulphobenzylmonoalkyl paraphenylenediamine
thiosulphonic acids on the one hand, and metatoluylenediamine, alkylmetatoluy-
lenediamines, alphylmetatoluylenediamines, monoalkylmetaphenylenediamines,
dialkylmetaphenylene diamines, monoalky lanilines, dialkyl anilines (dimethylaniline,
diethylaniline, methylethylaniline, methylbenzylaniline, ethylbenzylaniline) ortho-
toluidine, monoalkylorthotoluidines, alkylorthotoluidines, metamidophenylalkyl-
ethers, monealkylmetamidophenolalkylethers, dialky Imetamidophenolalkylethers,
paraxylidine, paracresidine, alphanaphthylamine, monoalkylalphanaphthylamines,
dialkylalphanaphthylamines, naphthylenediamine 2.8, naphthylamine monosulphonic
acid 1.2, naphthylamine disulphonic acid 1.2.6 or 1.2.7, naphthoquinone sulphonic
acid 1.2.4, naphthoquinonedisulphonic acid 1.2.4.6, oxynaphthoquinone sulphonic
cid 7.1.2.4, oxynaphthoic acid 1.2, and oxynaphthoic monosulphonic acid 1.2.7, on
he other hand.

page_text: 2
of green needles with metallic lustre; by recrystallising the colouring matter from
a dilute solution of hydrochloric acid including zinc chloride, the colouring matter
is obtained quite pure. It dyes tanned cotton a greenish blue which resists well:
alkalies.
EXAMPLE V.
5 parts of sulphooxyindophenol-thio-sulphonic acid, obtained by the reaction of
equivalent quantities of the potassium salt of naphthaquinonedisulphonic
acid 1.2.4.6, and of amido-diethylaniline thiosulphonic acid, are well dried, have
added to them 5 parts of Glauber salts free from water, and are then poured in
small doses with careful agitation, into 45 parts of fuming sulphuric acid at 0° C..
The mixture is left for several hours in a close vessel and is then heated about.
an hour on the water bath. The reaction product is then poured into 300 parts of
water. The precipitated colouring matter is filtered, washed and recrystallised
from a large quantity of hot water. The acid colouring matter is transformed in,
the usual way into alkaline salt which crystallises well.
The colouring matter crystallises in scales having bronze lustre, and dyes chromed
wool blue.
In a similar way the indophenolthiosulphonate derived from a molecule of sulpho-
benzylmonomethylparaphenylene diamine thiosulphonic acid or of sulphobenzyl-.
monoethylparaphenylenediaminethiosulphonic acid and a molecule of naphtha-.
quinone sulphonic acid 1.2.4, or of oxynaphthoquinone sulphonic acid 7.1.2.4,
can be transformed into corresponding thiazinic colouring matters which dye.
chromed wool blue-violet.
EXAMPLE VI.
5 parts of thiosulphonate of carboxyindophenol, obtained by simultaneous.
oxidation of sulphobenzylethylparaphenylene diamine-thiosulphonic acid and the
sodium salt of alphaoxynaphthoic acid, are mixed after thorough drying, with
5 parts of sulphate of soda free from water, and then poured into a mixture of
30 parts monohydrated sulphuric acid, and 15 parts chlorosulphonic acid (sulphuric
chlorhydrine) cooled to 0° C. The mixture is left for 1 or 2 days, then poured into.
300 parts water and filtered. The colouring matter is recrystallised from a
solution of carbonate of soda and thus obtained in form of needles with bronze.
lustre. It is readily soluble in water with blue-green colour and dyes wool in an.
acid bath or mordanted with chromium blue-green.
EXAMPLE VII.
5 parts of indaminethiosulphonic acid derived from a molecule of sulphobenzyl-.
methylparaphenylenediaminethiosulphonic acid and a molecule of naphthylamine
sulphonic acid 1.2, are mixed with 5 parts sulphate of soda free from water and
then introduced into a mixture of 30 parts monohydrated sulphuric acid and
15 parts chlorosulphonic acid (sulphuric chlorhydrine) cooled to 0°C. The
mixture left at ordinary temperature for 1 or 2 days is then added to a mixture of
100 parts water and 50 parts ice, from which the colouring matter is directly
precipitated in crystalline condition. From dilute hydrochloric acid it crystallises.
in needles having bronze lustre. It dyes wool in an acid bath an indigo blue
tint.
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 process described for. the transformation of the thiosulphonates of
indamiues and indophenols into thiazinic colouring matters, the said process
consisting in transforining the said thiosulphonates, but without presence of water,

page_text: oncentrated sulphuric acid having added to it with advantage anhydrous
uric acid, cehlorosulphonic acid (sulphuric chlorhydrine), pyrosulphates,
on salt, or other substances acting in a similar way.
For carrying out the process set forth in the preceding claim, the use of :-
a.) Indaminethiosulphonates, derived from a molecule of dimethylpara-
phenylenediamine thiosulphonic acid, diethylparaphenylenediamine thio-
sulphonic acid, methylethylparaphenylenediaminethiosulphonic acid, mono-
methylparatoluylenediamine thiosulphonic acid, monoethylparatoluylene-
diamine thiosulphonic acid, sulphobenzylmonomethylparaphenylene diamine-
thiosulphonic acid or sulphobenzylmonoethylparaphenylenediaminethio-
sulphonic acid, and from a molecule of metatoluylenediamine, monomethyl-
metatoluylenediamine, monoethylmetatoluylenediamine, dimethylmeta-
toluylenediamine, diethylmetatoluylenediamine, monomethylmetaphenylene-
diamine, monoethylmetaphenylenediamine, dimethylmetaphenylenediamine
diethylmetaphenylenediamine, naphthylenediamine 2.8, dimethylaniline,
methylethylaniline, diethylaniline, metamidophenolalkyl ethers, mono-
methylmetamidophenolalkyl ethers, monoethylmetamidophenolalkyl ethers,
diethylmetamidophenolalkylethers, paraxylidine, paracresidine, ortho-
toluidine, monoalkylorthotoluidines, dialkylorthotoluidines, alphylmeta-
toluylenediamines, alphanaphthylamine, monoalkylalphanaphthylamines,
dimethylalphanaphthylamine, diethylalphanaphthylamine, naphthylamine-
monosulphonic acid 1.2, and naphthylaminedisulphonic acid
or 1.2.7-
1.2.6
3.) Indophenolthiosulphonates derived from a molecule of dimethylpara-
phenylenediamine thiosulphonic acid, diethylparaphenylenediamine thio-
sulphonic acid, methylethylparaphenylene diamine thiosulphonic acid, mono-
methylparatoluylenediamine thiosulphonic acid, monoethylparatoluylene-
diaminethi sulphonic acid,
thios'
sulphobenzylmethylparaphenylenediamine
acid or sulphobenzylethylparaphenylenediamine thiosulphonic
acid and a molecule of naphthoquinonedisulphonic acid 1.2.4.6, naphtha-
quinonemonosulphonic acid 1.2.4, oxynaphthoquinonemonosulphonic
acid 7.1.2.4, alphaoxynaphthoic acid or oxynaphthoicmonosulphonic
acid 1.2.7.
As new products the thiazinic colouring matters obtained as set forth in the
preceding claims and derived from metamidophenylalkyl ethers, monoalkyl-
midophenolalkylethers, dialkylmetamidophenolalkyl-ethers, paraxylidine,
aphthoic acid 1.2, naphthylamine sulphonic acid 1.2, naphthylamine
phonic acid 1.2.6 or 1.2.7, and oxynaphthoic monosulphonic acid 1.2.7.
Dated this 9th day of March 1896.
ABEL & IMRAY,
Agents for the Applicant.