Improvements in the Manufacture and Production of Colouring) Matters containing Sulphur.
Year: 1898

page_text: Date of Application, 17th Oct., 1898
Complete Specification Left, 17th July, 1899-Accepted, 2nd Sept.,
1899
Improvements in the Manufacture and Production of Colouring)
Matters containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, King's Drive, Heaton Moor,
near Stockport, ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street, Ardwick,
Manchester, and THE CLAYTON ANILINE COMPANY LIMITED, Chemical Manu-
facturers, of Clayton, Manchester, all in the County of Lancaster, do hereby
declare the nature of this invention to be as follows:
The classical researches of Bernthsen upon methylene blue and allied colouring
matters have shewn that by the oxidation of a paradiamine in the presence of
a thiosulphate a monothiosulphonic acid of the diamine is obtained, but up to
the present, no instance of the formation of a dithiosulphonic acid has been
observed.
'
The present invention relates to our important discovery that a whole series
of such dithiosulphonic acids can be obtained and that they are readily formed
by either of the following methods:-
1. By oxidation of hydroquinone para-amidophenol, paraphenylene diamine,
or an alkyl derivative of the latter in the presence of two molecular proportions
of thiosulphuric acid.
2. By the reaction of paranitrosophenol, paranitrose aniline, or alkyl deriva-
tives of the latter or of such quinonoid bodies which are known to be equivalents
of these nitroso compounds upon two molecular proportions of thiosulphuric acid.
3. By the reaction of the unstable oxidation products of the monothiosulphonic
acids upon one molecular proportion of thiosulphuric acid.
Owing to the instability of thiosulphuric acid in the presence of acids, the
above reactions are best carried out in a weakly acid solution, or with employ-
ment of an acid salt of thiosulphuric acid, such as aluminium thiosulphate.
The dithio sulphonic acids thus obtained are colourless bodies which are capable
of a wide technical application as intermediate compounds for the preparation
of a large series of new and valuable colouring matters varying in shade from
brown and dark blue to deep black. These new colouring matters, which pro-
bably belong to the class of dithiazines, all possess the property of dyeing un-
mordanted cotton, from a sodium sulphide bath, very fast shades which resist
long boiling with soap without staining white cotton. They can be obtained
from the dithiosulphonic acids by either of the following methods:-
1. By oxidation of a dithiosulphonic acid in the presence of a diamine, or
amidophenol, and conversion of the intermediately formed indamine into the
final colouring-matter by boiling in strongly acid solution.
2. By the reaction of a dithiosulphonic acid upon paranitrosophenol, para-
nitrosoaniline or its alkyl derivatives, quinoneimides or quinone-chlorimides,
and the conversion of the intermediately formed indamine into the final colour-
ing-matter by boiling in strongly acid solution.
For the purpose of this invention it is not necessary to isolate either the

page_text: dithiosulphonic acid, or the intermediate indamine, but the above reactions may
be carried out in succession, or simultaneously, in the same solution. The new
colouring-matters generally form insoluble, or but sparingly soluble, precipitates,
which can be at once separated from the mother liquor by filtration.
The general method of carrying out this invention is illustrated by the follow-
ing examples but we do not limit ourselves to the exact details given in these
examples.
EXAMPLE I.
A solution of 186 g. of para amidophenol in 67 c.c. of dilute sulphuric acid
(containing 33 per cent. H,SO) and 433 c.c. of water, is mixed with 400 c.c. of a
solution of aluminium sulphate (containing 540 g. per litre) and cooled to 0°
Centigrade. There is then added 400 c.c. of a solution of sodium thiosulphate
(containing 440 g. per litre) and a mixture of 500 c.c. of a solution of potassium
bichromate (containing 91.6 g. per litre) and 144 c.c. of 50 per cent. acetic acid,
the temperature being kept at 0° to 5° Centigrade. When the formation of the
dithiosulphonic acid is complete, a solution is added containing 373 g. of para-
amidophenol in 133 c.c. of dilute sulphuric acid (33 per cent. H, SO) and 67 c.c.
of water and the mixture is oxidised at a temperature of about 15° Centigrade by
the addition of 750 c.c. of aqueous potassium bichromate (916 g. per litre) and
216 c.c. of 50 per cent. acetic acid. There is then added 875 g. of concentrated
sulphuric acid and the mixture is heated slowly to 100° Centigrade and finally
boiled for about half an hour until the colour does not become lighter. After
cooling the insoluble precipitate is filtered off washed with hot water and dried.
It dyes unmordanted cotton a deep black, from an alkaline sulphide bath, and
resists severe soaping without loss of colour.
If, in the second stage of the above reaction, the paraamidophenol be replaced
by a solution of orthophenylenediamine, obtained by reduction of 47 g. of ortho-
nitraniline with zine dust and acid a colouring matter is obtained which dyes
cotton a dark brown becoming slightly redder by coppering and exhibiting a
great resistance to soap.
EXAMPLE II.
If in the previous example, the paraamidophenol be replaced by the same
weight of paraphenylene diamine a dithiosulphonic acid of the latter is obtained.
By oxidation of this with ortho-amidophenol, obtained by reduction with zinc
dust and acid from 47 g. orthonitrophenol, and boiling with sulphuric acid in
the manner herein before described, a product is obtained which dyes cotton a
dark indigo-blue which is considerably deepened by coppering and possesses
great fastness against soaping. If, in the second stage of the reaction, the ortho-
amidophenol be replaced by 37 g. metaphenylene diamine a colouring matter is
obtained which dyes a violet-indigo shade.
EXAMPLE III.
If in Example I the paraamidophenol employed in the first stage be replaced
by 23 g. of paraamidodimethylaniline, and that employed in the second stage
of 37 g. of metaphenvlene diamine, a colouring matter is obtained which dyes
cotton a blue-black which becomes somewhat redder and deeper by coppering.
EXAMPLE IV.
A solution of 31 g. of nitrosodimethylaniline hydrochloride in 500 c.c. of
water is mixed with 420 c.c. of aluminium sulphate solution (540 g. per litre)
and 420 c.c. of sodium thiosulphate solution (440 g. per litre) and gently warmed
until the mixture is colourless.
The solution of the dithiosulphonic acid obtained is then mixed with a solution
of 37 g. of paraphenylene diamine in 100 c.c. of dilute sulphuric acid (33 per cent.
H₂ SO) and 1000 c.c. of water, and oxidised at about 15° Centigrade with a

page_text: mixture of 750 c.c. potassuim bichromate (916 g. per litre) and 216 c.c. of 50 per
cent. acetic acid. When the oxidation is complete 900 g. of strong sulphonic
acid are added and the mixture is boiled. The precipitated product is filtered
off washed and dried. It dyes cotton a pure black. If, in the above process,
the paraphenylene diamine be replaced by 60 g. of nitrosophenol suspended in
600 c.c. of water and the oxidising mixture be omitted, a product is obtained
which also dyes cotton black.
Improvements in the Manufacture and Production of Colouring
Matters containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, King's Drive, Heaton Moor,
near Stockport, ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street, Ardwick,
Manchester, and THE CLAYTON ANILINE COMPANY LIMITED, Chemical Manu-
facturers, of Clayton, Manchester, all in the County of Lancaster, do hereby
declare the nature of this invention and in what manner the same is to be per-
formed, to be particularly described and ascertained in and by the following
statement:.
.
-
In the preparation of sulphur containing direct cotton colouring-matters of
the vidal class the sulphur is introduced by fusing the constituent materials
with sodium sulphide or with sodium sulphide and sulphur. The present inven-
tion relates to a new general method of preparing sulphur-containing colouring-
matters of similar properties by employment of thiosulphuric acid as the sulphur-
introducing agent, the operations being performed in aqueous solution.
The classical researches of Bernthsen upon methylene blue and allied colouring
matters have shewn that by the oxidation of a para-diamine in the presence of
a thiosulphate a monothiosulphonic acid of the diamine is obtained, but up to
the present, no instance of the formation of a dithiosulphonic acid has been
observed. The present inventors have made the important discovery that a
whole series of such dithiosulphonic acids can be obtained, derived not only from
paradiamines, but also from paraamidophenols and from paradioxy benzenes,
and that they are readily formed by either of the following methods:-
1. By oxidation of hydroquinone paraamidophenol, paraamidocresol, para-
phenylene diamine, paratolylene diamine or an alkyl derivative of paraphenylene
diamine in the presence of two molecular proportions of thiosulphuric acid.
2. By the reaction of paranitrosophenol, paranitrosoaniline or alkyl derivatives
of paranitrosoaniline or of such quinonoid bodies as are known to be equivalents
of the said nitroso compounds, upon two molecular proportions of thiosulphuric
acid.
3. By the reaction of the unstable oxidation products of the monothiosulphonic
acids upon one molecular proportion of thiosulphuric acid.
Owing to the instability of thiosulphuric acid in the presence of acids, the
above reactions are best carried out in a weakly acid solution, or with the
employment of an acid salt of thiosulphuric acid, such as aluminium thiosul-
phate. The dithiosulphonic acids, thus obtained, are colourless bodies which
are capable of a wide technical application as intermediate compounds for the
preparation of a large series of new and valuable colouring matters varying in
shade from brown and dark blue to deep black. These new colouring matters

page_text: all possess the property of dyeing unmordanted cotton, from a sodium sulphide
bath, very fast shades which resist long boiling with soap, without staining
white cotton. They can be obtained from the dithiosulphonic acids by either of
the following methods.
1. By oxidation of a dithiosulphonic acid in the presence of a diamine, or
amidophenol, and conversion of the intermediately formed product into the final
colouring matter by boiling in acid solution.
2. By the reaction of a dithiosulphonic acid upon paranitrosophenol, para-
nitrosoaniline, or its alkyl derivatives, a quinoneimide or a quinonechlorimide,
and the conversion of the intermediately formed products into the final colouring
matter by boiling in acid solution.
For the purpose of this invention it is not necessary to isolate either the
dithiosulphonic acid, or the intermediate oxidation-product, as the aforesaid
reactions can be carried out in succession, or simultaneously, in the same solution.
The new colouring-matters, generally form insoluble, or but sparingly soluble,
precipitates which can be at once separated from the mother liquor by filtration.
As it is not always possible to bring the whole of the thiosulphate employed
into the reaction, a portion undergoing decomposition and oxidation it is often
advisable to employ an excess of thiosulphate and consequently also of the
oxidising agent in amount proportionate thereto.
The general method of carrying out this invention is illustrated by the follow-
ing examples, of which the first illustrates the isolation of a typical dithiosul-
phonic acid, the other examples illustrating the preparation of the colouring-
matters direct, without isolation of the intermediate dithiosulphonic acids. In
these examples we do not bind ourselves to the exact details and proportions
therein given.
EXAMPLE I. 54 g. of para-phenylene diamine are dissolved in a mixture of
60 g. of glacial acetic acid and 500 c.c. of water. A solution of 500 g. of crystal-
lised sodium thiosulphate, made up to one litre is added at 0° Centigrade and,
whilst the mixture is cooled to 30 Centigrade and well stirred, a mixture of
1300 c.c. of sodium bichromate solution (103 g. per litre) and 208 g. of glacial
acetic acid is gradually added. The dark liquid, so obtained, is neutralised with
caustic soda until only faintly acid to litmus, and is then saturated with
potassium chloride (about 500 g.) A crystalline precipitate of a lilac colour is
formed, which is filtered off and decomposed by boiling with about 1½ liters of
water and adding potassium carbonate in slight excess. After filtering from
the precipitated chromium hydrate, the solution is saturated cold with potassium
chloride when the potassium salt of paraphenylene-diamine-dithiosulphonic acid
crystallises out in greenish-yellow crystals. When purified, by recrystallisation
from boiling water with the addition of animal charcoal, it forms light yellow.
lamine, or prisms.
EXAMPLE II. A. solution of 24'8 g. of paraamidophenol hydrochloride, in
100 c.c. of water, is mixed with 400 c.c. of a solution of aluminium sulphate (con-
taining 540 g. per liter) and cooled to 0° Centigrade. There is then added 400 c.c.
of a solution of sodium thiosulphate (containing 440 g. per liter) and a mixture
of a solution of potassium bichromate (containing 916 g. per liter) and 144 c.c.
of 50 per cent. acetic acid, the temperature being kept at 0° 5° Centigrade.
When the formation of the dithiosulphonic acid is complete, a solution is added
containing 496 g. of paraamidophenol hydrochloride in 200 c.c. of water and
the mixture is oxidised at. a temperature of about 15° Centigrade by the addition
of 375-750 c.c. of aqueous potassium bichromate (916 g. per litre) and 108-
216 c.c. of 50 per cent. acetic acid. There is then added 875 g. of concentrated
sulphuric acid and the mixture is heated slowly to 100° Centigrade, and finally
boiled, for about half-an-hour, until the colour does not become lighter. After
cooling, the insoluble precipitate is filtered off, washed with hot water, and
dried. It dyes unmordanted cotton a deep black, from an alkaline sulphide
bath, and resists severe soaping without loss of colour.

page_text: If, in the second stage of the above reaction, the paraamidophenol be replaced
by a solution of orthophenylenediamine, obtained by reduction of 47 g. of ortho-
nitraniline with zinc dust and acid, a colouring matter is obtained which dyes
cotton a dark brown which becomes slightly redder by coppering and exhibits a
great resistance to soap.
EXAMPLE III. If, in the previous example, the paraamidophenol be replaced
by the same weight of paraphenylene diamine, a dithiosulphonic acid of the
latter is obtained. By oxidation of this with orthoamidophenol, obtained by
reduction with zinc dust and acid from 47 g. of orthonitrophenol, and boiling
with sulphuric acid, in the manner herein before described, a product is obtained
which dyes cotton a dark indigo-blue which is considerably deepened by copper-
ing and possesses great fastness against soaping. If, in the second stage of the
reaction, the orthoamidophenol be replaced by 37 g. of metaphenylene diamine
a colouring matter is obtained which dyes a violet-indigo shade.
EXAMPLE IV. If, in Example II the paraamidophenol employed in the first
stage be replaced by 23 g. of paraamidodimethylaniline, and that employed in
the second stage by 37 g. of metaphenylene diamine, a colouring matter is
obtained which dyes cotton a blue-black which becomes somewhat redder and
deeper by coppering.
EXAMPLE V. A solution of 31 g. of nitrosodimethylaniline hydrochloride in
500 c.c. of water is mixed with 420 c.c. of aluminium sulphate, (540 g. per litre),
and 420 c.c. of sodium thiosulphate solution (440 g. per litre) and gently warmed
until the mixture is colourless.
The solution of the dithiosulphonic acid obtained, is then mixed with a solu-
tion of the hydrochloride of 37 g. of paraphenylenediamine in 1000 c.c. of water,
and oxidised at about 15° Centigrade with a mixture of 375-750 c.c. potassium
bichromate (916 g. per litre) and 108-216 c.c. of 50 per cent. acetic acid. When
the oxidation is complete 900 g. of strong sulphuric acid are added and the mix-
ture is boiled. The precipitated product is filtered off, washed and dried. It
dyes cotton a pure black. If, in the above process, the paraphenylene diamine
be replaced by 60 g. of nitrosophenol suspended in 600 c.c. of water, and the
oxidising mixture be omitted, a product is obtained which also dyes cotton black.
Having now particularly described and ascertained the nature of this inven-
tion, and in what manner the same is to be performed, we declare that what we
claim is:
1. In, or for, the manufacture of colouring matters the preparation of a dithio-
sulphonic acid by oxidation of hydroquinone, paraamidophenol, paraamidocresol,
paraphenylenediamine, paratoluylene diamine or an alkyl derivative of para-
phenylene diamine in the presence of two molecular proportions of thiosulphuric
acid.
2. In, or for, the manufacture of colouring matters the preparation of a dithio-
sulphonic acid by the reaction of paranitrosophenol, paranitrosoaniline, or alkyl
derivatives of paranitrosoaniline, or of quinonoid bodies which are equivalents
of the said nitroso compounds, upon two molecular proportions of thiosulphuric
acid:
3. In or for, the manufacture of colouring matters the preparation of a dithio-
sulphonic acid by the reaction of the unstable oxidation products of a monothio-
sulphonic acid upon one molecular proportion of thiosulphuric acid.
4. The manufacture of colouring matters by subjecting dithiosulphonic acid
to oxidation in the presence of a diamine, or amidophenol, and boiling in acid
solution the intermediate product formed.
5. The manufacture of colouring matters by causing dithiosulphonic acid to
react upon paranitrosophenol, paranitrosoaniline, or its alkyl derivatives, or a
quinoneimide, or quinone chlorimide, and boiling, in acid solution, the inter-
mediate product formed.
6. The manufacture and production of colouring matters by carrying out

page_text: successively, or simultaneously, in the same solution, the production of dithio-
sulphonic acid, according to either of the preceding Claims 1, 2 and 3, and the
conversion into colouring matters, according to either of the preceding Claims 4
and 5.
7. The manufacture and production of colouring matters according to the
several examples herein before given.
8. In the manufacture of sulphur-containing colouring-matters dyeing cotton
direct in fast shades from a sodium sulphide bath, the employment of thiosul-
phuric acid, or thiosulphate, as the sulphur-introducing agent substantially as
herein before described.
9. As new articles of manufacture the colouring matters and intermediate
products such as can be produced according to the processes herein before
described and claimed.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.