Improvements in the Production of Aromatic Bases Containing Sulphur, and of their Sulphonic Acids.
Year: 1894

page_text: Date of Application, 8th Jan., 1894
Complete Specification Left, 8th Oct., 1894-Accepted, 10th Nov., 1894
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE, vormals MEISTER LUCIUS
& BRUNING, of Hoechst a/ Main, Germany, Chemical Manufacturers.]
Improvements in the Production of Aromatic Bases Containing
Sulphur, and of their Sulphonic Acids.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows:-
For several years, as is known, there have been produced by the action, at higher
temperatures, of sulphur upon the homologues of aniline, sulphurous bases, which
under various denominations as thiochromogen, polychromine, primulin, are employed
in the manufacture of coal tar colours.
My foreign correspondents have discovered a different and novel mode of producing
similar bases.
C₁₁N, +3S = 2 H₂S + CH,N,S.
14
If this base, which hereafter is termed "Thiobase I," is again heated to higher
temperature, evolution of sulphuretted hydrogen again takes place and a novel base
is formed hereafter termed "Thiobase II." Each of these bases still contains a
diazotisable amido-group, but they differ widely in their chemical and physical
qualities.
Thiobase I is in form of a highly yellow crystalline powder which melts at about
80° C.; it is insoluble in water, sparingly soluble in the usual solvents, acetone
excepted, in which it is very easily soluble, giving a yellow colour.
In diluted mineral acids the base dissolves easily with yellow colour. From
these solutions alkalies precipitate it in unchanged condition. The sulphate is
nearly insoluble in water, it is obtained in the form of a yellow precipitate when the
solution of the hydrochlorate is precipitated by dilute sulphuric acid.
It has
Thiobase II is in form of an orange-yellow powder, which melts at nearly
200° C. it is quite insoluble in all the usual solvents, also in acetone.
feeble basic character and is not capable of forming with acids stable salts.
:
Both bases are by weak fuming sulphuric acid converted into sulphonic acids, the
alkali-salts of which are easily soluble in water with yellow colour. These sulphonic
acids also still contain diazotisable amido-groups.

page_text: 100 kilos. of the thiobase I or of thiobase II are at a temperature of 50° to 60° C.,
slowly and with active agitation, introduced into 400 kilos. of fuming sulphuric acid
of 20 per cent. of SO,.
The sulphonation is complete, when a sample, precipitated by means of water
and washed, is entirely soluble in diluted alkali-lye or in ammonia. When this
point is attained the sulphonation product is poured into 1,500 kilos. of iced-water,
then is heated to boiling, the sulphonic acid which separates is filtered off, perfectly
washed with water and converted into an alkali or ammonia salt.
The sulphonic acid of the thiobase I is in the form of a highly yellow coloured
powder, soluble with difficulty in water; its salts dissolve easily in water with light
yellow colour.
The sulphonic acid of the thiobase II is in the form of a brown powder insoluble
in water; its salts dissolve easily in water with orange-yellow colour.
Dated this 8th day of January 1894.
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Improvements in the Production of Aromatic Bases Containing
Sulphur, and of their Sulphonic Acids.
I, OLIVER IMRAY, of No. 28, Southampton Buildings, Chancery Lane, 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 by the following statement :—
For several years, as is known, there have been produced by the action, at higher
temperatures, of sulphur upon the homologues of aniline, sulphurous bases, which

page_text: under various denominations as thiochromogen, polychromine, primulin, are employed
in the manufacture of coal tar colours.
My foreign correspondents have discovered a different and novel mode of
producing similar bases.
TL
1
AT

page_text: manufacturing purposes; it can however be further purified by dissolving it in
concentrated sulphuric acid and precipitating by water.
SULPHONIC ACIDS OF THE TWO THIOBASES.
100 kilos. of the thiobase I or of thiobase II are at a temperature of 50° to
60° C., slowly and with active agitation, introduced into 400 kilos. of fuming
sulphuric acid of 20 per cent of SO.
The sulphonation is complete, when a sample, precipitated by means of water and
washed, is entirely soluble in diluted alkali-lye or in ammonia.
When this point is
attained the sulphonation product is poured into 1,500 kilos. of iced-water, then is
heated to boiling, the sulphonic acid which separates is filtered off perfectly
washed with water and converted into an alkali or ammonia salt.
The sulphonic acid of the thiobase I is in the form of a highly yellow coloured
powder, soluble with difficulty in water; its salts dissolve easily in water with light
yellow colour.
The sulphonic acid of the thiobase II is in the form of a brown powder insoluble
in water; its salts dissolve easily in water with orange-yellow colour.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same to be performed, I declare that what I
claim is :-
1. The production of a sulphurous base, by melting para-amido benzaniline
together with sulphur at from 170° to 180° C., substantially as described.
2. The production of a sulphurous base by heating to 240° or 250° C. the base
referred to in the preceding claim, substantially as described.
3. The production of sulphonic acids of the sulphurous bases referred to in the
preceding claims by treating the bases with fuming sulphuric acid, substantially as
described.
4. The sulphurous bases and their sulphonic acids produced as hereinbefore
described.
Dated this 8th day of October 1894.
ABEL & IMRAY,
Agents for the Applicant.