Improvements in the Manufacture and Production of Colouring. matters Containing Sulphur.
Year: 1899

page_text: Date of Application, 7th Mar., 1899
Complete Specification Left, 21st Nov., 1899-Accepted, 30th Dec., 1899
Improvements in the Manufacture and Production of Colouring.
matters Containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton
Moor, near Stockport, ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street,
Ardwick, Manchester, and the CLAYTON ANILINE COMPANY LIMITED, Chemical
Manufacturers, of Clayton, Manchester, all in the County of Lancaster, do hereby
declare the nature of this invention to be as follows:
In the Specification of our application for Letters Patent dated October 17th
1898 and numbered 21832 we have described new, general means for the pre-
paration of fast direct-dyeing cotton colouring-matters containing sulphur by
the production of a dithiosulphonic acid of a paraphenylene diamine, paraamido-
phenol or hydroquinone (called the first component) and condensation of this
dithiosulphonic acid with a second component: In the Specification of our
application for Letters Patent dated October 25th 1898 and numbered 22460
we have further shewn that in place of the thiosulphuric acid, sulphuretted
hydrogen may be employed, in many cases with like effect, the reactions being
of a similar character. These methods of introducing sulphur had previously
only been employed for the production of colouring-matters of the methylene
blue class, and their application to the preparation of direct cotton dye stuffs
is an entirely novel one, and constitutes a great technical advance over the
method of fusion with sodium sulphide or sodium sulphide and sulphur hitherto
employed, in enabling the reactions to be better determined and controlled and
affording a greater range of possible combinations.
As the result of further study we have now found that these processes admit
of a still greater extension both with regard to the character of the components,
and to the quantity of thiosulphuric acid (or sulphuretted hydrogen) employed.
The properties of the colouring-matters thus obtained are in general similar to
those obtained according to the herein before mentioned previous applications.
They dye cotton from an alkaline sulphide bath in dark shades, varying from
brown to black, and possessing great fastness against the action of alkalies,
acids, soap, and the air. On treatment with chromic acid, or with copper salts,
the shades become more intense and their fastness still further increased.
I. In the hereinbefore mentioned applications for Letters Patent the compounds
employed as second components were diamines, or amidophenols, their substitu-
tion products or equivalents. We have now found that in place of these there may
be employed:
(a) Aromatic monamines; such as aniline, orthotoluidine, paratoluidine, di-
methylaniline, alphanaphthylamine and the like.
(b) Phenols; such as phenol, resorcin, alphanaphthol and the like.
(c) Mono- or di-thiosulphonic acids of para-phenylenediamine, paraamidophenol,
or derivatives thereof. This, when a single component is used, resolves itself into
the oxidation of the intermediate product by itself,

page_text: The manner in which these combinations are brought about admits of very
considerable variation, for the order of the several stages may be varied, or all
may be performed, more or less, together. It is seldom necessary to isolate the
thiosulphonic acid, and its solution can be used at once for the condensation
with the second component; or formation and condensation of the thiosulphonic
acid may take place simultaneously. Instead of preparing the thiosulphonic acid
first and then condensing it with the second component, the two components may
be mixed together and then oxidised in the presence of the thiosulphate. Or,
when the first and second component on oxidation alone give an indamine, or
indophenol, the latter may be caused to react with the thiosulphate; or the
diphenylamine derivative obtained by reduction of such indamine, or indophenol,
may be oxidised in the presence of the thiosulphate. As first components in
these, reactions we have found the paraphenylene-diamine or paraamidophenol to
be most suitable but certain alkyl, alphyl, or substituted alphyl, derivatives, of
these bodies may also be used; such as dimethyl-paraphenylenediamine, phenyl-
paraphenylene diamine diamidophenylparaamidophenol, and the like. Sulphu-
retted hydrogen may be employed in many cases as an equivalent for the thio-
sulphuric acid, but its use does not appear to offer any advantages over the
latter: In the preparation of all these colouring matters the general method
of procedure is substantially the same as that described in the herein before
mentioned specifications of our earlier applications, except that we have found
that, in many cases, it is unnecessary, or even inadvisable, to effect the final
transformation by boiling with a large excess of acid, a smaller amount answering
the purpose better.
II. The quantity of thiosulphate employed, can, as our later observations have
shewn, be varied within very wide limits. Thus in many cases it is advantageous
to employ three or four molecular proportions of thiosulphate, since, under certain
conditions, a considerable proportion of the latter is destroyed by oxidation and
does not take part in the reaction. On the other hand the thiosulphate may be
diminished below two molecular proportions even as low as one molecular pro-
portion. We have made the unexpected observation that the mono-thiosulphonic
acids some of which have been long known, and readily isolated, are capable of
undergoing condensations similar to the dithiosulphonic acids when oxidised with
a second component (excluding those which form, under these conditions, dye-
stuffs of the methylene blue series) such for instance, as paraphenylenediamine,
para-amidophenol, or even with a second quantity of the same, or another mono-
thiosulphonic acid. The colouring-matters thus produced are dark browns, and
we have found in general that with the employment of the same components, and
otherwise constant conditions of experiment, the shade of the resulting coloring-
matter becomes darker and approaches more and more to deep black as the
proportion of thiosulphate is increased.
The following examples illustrate the general method of carrying out our
invention but we do not bind ourselves to the exact details given since these are
only typical.
EXAMPLE I.
DYESTUFF FROM PARAPHENYLENE DIAMINE AND ANILINE.
27 g. of paraphenylene diamine are dissolved in 220 c.c. of water together
with 30 c.c. of hydrochloric acid (27%, HCl) and mixed with a solution of 321 g.
of aniline hydrochloride in 200 c.c. of water. Into the mixture 125 g. of
crystallized sodium thiosulphate are stirred and, when dissolved, there is run in
a solution of 100 g. of sodium bichromate in 150 c.c. of water acidified with 45 g.
of concentrated sulphuric acid. During the reaction the temperature is kept at
0° to 5° C. by addition of ice. After standing for some time 100 g. of concentrated
sulphuric acid, diluted with 150 c.c. of water, are added, and the solution is
boiled for half-an-hour. The precipitated colouring-matter is filtered off, washed

page_text: DYESTUFF FROM PARAAMIDOPHENOL AND ANILINE.
145 g. of paraamidophenol hydrochloride and 130 g. of aniline hydrochloride
are dissolved in 2 litres of water and mixed with a solution of 625 g of sodium.
thiosulphate, in 1 litre of water. The mixture is then oxidised at 0°. C. with a
solution of 425 g. of sodium bichromate and 150 g. of concentrated sulphuric acid
in 2 litres of water. After standing, 600 g. of concentrated sulphuric acid
diluted with 1000 c.c. of water, are added and the mixture is boiled and the colour
filtered off, washed, and dried. It dyes cotton black from a sulphide bath.
EXAMPLE V.,
DYESTUFF FROM PARAPHENYLENE DIAMINE AND RESORCIN.
A solution of 108 g. of paraphenylene diamine, 111 g. of resorcin, 900 g. alu-
minium sulphate, and 110 c.c. of hydrochloric acid (27%) in 8 litres of water,
is mixed with 1800 c.c. of a sodium thiosulphate solution containing 440 g.
per litre and oxidised with 5400 c.c. of a solution of potassium bichromate con-
taining 90 g. per litre, and 1600 c.c. of 50% acetic acid. 2400 c.c. of concentrated
sulphuric acid are then added, and the mixture is boiled until the dystuff
separates.

page_text: (444 g. per litre) and 112 c.c. sodium thiosulphate solution (440 g. per litre),
is oxidised at 0° C. with 327 c.c. of potassium bichromate solution (90 g. per
litre) and 44 g. of acetic acid. After the addition of 200 g. of concentrated. sul-
phuric acid the mixture is boiled and the product filtered off washed, and dried.
It dyes cotton black.
EXAMPLE VII.
DYESTUFF FROM PARAPHENYLENEDIAMINE MONOTIOSULPHONIC ACID AND
PHENYLENE DIAMINE.
PARA-
26 g. of paraphenylenediamine monothiosulphonic acid and 11 g. of para-
phenylene diamine are dissolved in 400 c.c. of water. This solution, kept cold
by ice, is oxidised by the addition of 20'6 g. of sodium bichromate and 30 g.
of concentrated sulphuric acid dissolved in 200 c.c. of water. Finally 90 c.c. of
dilute sulphuric acid (33% H2SO4) are added and the mixture is boiled. The
separated colouring-matter is filtered off, washed, and dried. It dyes colton
brown, from a sulphide bath.
1000
Improvements in the Manufacture and Production of Colouring-
matters Containing Sulphur.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton
Moor, near Stockport, ALEXANDER MEYENBERG, Ph.D., of 13, Nelson Street,
Ardwick, Manchester, and the CLAYTON ANILINE COMPANY LIMITED, Chemical
Manufacturers, of Clayton, Manchester, all in the County of Lancaster, do hereby
declare the nature or 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 Specification of Letters Patent granted to us dated October 17th 1898
and numbered 21832 we have described new general means for the prepara-
tion of fast direct-dyeing cotton colouring-matters containing sulphur by the
production of a dithiosulphonic acid of a paraphenylene diamine, paratolylene
diamine, para amido phenol, para amidocresol or hydroquinone (called the first
component) and condensation of this dithiosulphonic acid with a second component.
In the Specification of our application for Letters Patent dated October 25th 1898
and numbered 22460 we have further shewn that in place of the thiosulphuric
acid described in the specification of the aforesaid former Patent 2183208 sulphu-
retted hydrogen may be employed, in many cases with like effect, the reactions
being of a similar character. These methods of introducing sulphur had pre-
viously only been employed for the production of colouring-matters of the methy-
lene blue class, and their application to the preparation of direct cotton dyestuffs
is an entirely novel one, and constitutes a great technical advance over the method
of fusion with sodium sulphide, or sulphur and sodium sulphide hitherto em-
ployed, because the reactions can be better determined and controlled and there
is a greater range of possible combinations than in the case of using the aforesaid
method of fusion.
As the result of further study we have now found that these processes admit
of a still greater extension both with regard to the character of the components.

page_text: and to the quantity of thiosulphuric acid (or sulphuretted hydrogen) employed.
The properties of the colouring-matters thus obtained are in general similar to
those obtained according to the herein before mentioned previous applications for
Letters Patent. Like the latter they dye cotton from an alkaline sulphide bath.
dark shades, varying from brown to indigo blue and black, and possessing great
fastness against the action of alkalies, acids, soap, and air. On treatment with
chromic acid, or with copper salts, the shades become more intense and their
fastness is still further increased.
I. In the hereinbefore mentioned applications for Letters Patent the compounds
employed as second components were diamines, or amidophenols, their substitu-
tion products or equivalents. We have now found that in place of a part or.
the whole of such components there may be employed the following bodies or
mixtures of the same:-
(a) Aromatic monamines; such as aniline, orthotoluidine, dimethylaniline,
metatoluidine; paraxylidine, orthoanisidone, alpha-naphthylamine and the like.
(h) Phenols such as phenol, orthocresol, metacresol, pyrocatechin, recorcin,
guaiacol, alpha-naphthol and the like.
2
() Mono- or di-thiosulphonic acids of paraphenylenediamine, para amidophenol,
or derivatives thereof this, when both first and second component are the same
resolves itself into the oxidation of the intermediate product by itself.
The manner. in which these combinations are brought about admits of very.
considerable variation, for the order of the several steps of the process may be
varied, or all may be performed more or less together. It is seldom necessary
to isolate the thiosulphonic acid, but its solution can be used at once for the.
condensation with the second component; or formation and condensation of the
thiosulphonic acid may take place simultaneously. Further instead of preparing
the thiosulphonic acid first and then condensing it with the second component,
the two components may be mixed together and then oxidised in the presence
of the thiosulphate. Or, when the first and second component on oxidation alone
give an indamine, or indophenol, the latter may be caused to react with the
thiosulphate; or the diphenylamine derivative obtained by reduction of such
indamine, or indophenol, may be oxidised in the presence of the thiosulphate. As
first components in these reactions we have found the paraphenylenediamine or
paraamidophenol to be most suitable-but certain alkyl; alphyl, or substituted
alphyl derivatives, of these bodies may also be used, such as dimethyl-para-
phenylenediamine paratolylene diamine, paraxylyleneparadiamine, diamido-
phenylparaamidophenol, and the like. Sulphuretted hydrogen may be employed
in many cases as an equivalent for the thiosulphuric acid, but its use does not
appear to offer any advantages over the latter. In the preparation of all these
colouring matters the general method of procedure is substantially the same .as.
that described in the specifications of the hereinbefore mentioned earlier appli-
cations for Letters Patent except that we have found that, in many cases, it
is unnecessary, or even inadvisable, to effect the final transformation by boiling
with a large excess of acid, a smaller amount answering the purpose 'better.
II. The quantity of thiosulphate employed, can, as our later observations have
shewn, be varied within very wide limits. Thus in many cases it is advantageous
to use three or four molecular proportions of thiosulphate, especially when two
molecular proportions of the second component are employed, so that possibly in
some cases more than two thiosulphonic groups enter.
On the other hand when browner shades of colour are required the thiosulphate
may be diminished below two molecular proportions even as low as one molecular
proportion. In this relation we have made the unexpected observation that the
mono-thiosulphonic acids (some of which have been long known) are capable of
undergoing condensations similar to the dithiosulphonic acids. We have found.
in fact that such mono-thiosulphonic acids yield dark brown colouring-matters.
when oxidized with a second component such for instance as paraphenylene-
diamine, paratolylene diamine, paraamidophenol, or even with a second quantity

page_text: of the same, or another monothiosulphonic acid excluding however such mixtures
which under the conditions employed give rise to dyestuffs of the methylene blue
series. The colouring-matters thus produced have very similar dyeing and
chemical properties to those derived from the dithiosulphonic acids. With the
employment of the same components and otherwise constant conditions of experi-
ment the shade of the resulting colouring-matter becomes darker and approaches
more and more to deep black as the proportion of thiosulphate in increased.
The following examples illustrate the general method of carrying out our in-
vention but we do not bind ourselves to the exact details given, since these are
only typical, nor to the molecular quantities of the second component since in
many cases these may be widely varied. The parts are by weight.
TARAJ HENLENM 11AMINE AND UKTHOTOLUIDINE.
27 parts of paraphenylene diamine and 26'8 parts of orthotoluidine are dis-
solved in 350 parts of water and 77 parts of hydrochloric acid (27 per cent. HCl);
188 parts of sodium thiosulphate dissolved in 100 parts of water are then added
and the mixture is treated with a solution of 100 parts of sodium bichromate and
48 parts of concentrated sulphuric acid in 200 parts of water, whilst it is kept
cold by addition of ice. At the conclusion 130 parts of concentrated sulphuric
acid diluted with 130 parts of water are added, and, after standing for some time,
a further 30 parts of sodium bichromate are added, followed by 54 parts more
sulphuric acid. The mixture is then boiled for half-an-hour and the product is
filtered off, washed and dried. It dyes cotton black from a sulphide bath.
EXAMPLE III.
DYESTUFF FROM PARATOLYLENE DIAMINE AND ANILINE.
15 parts of paratolylene diamine and 23 parts of aniline are dissolved in
700 parts of water and 50 parts of hydrochloric acid (27 per cent. HCl). The
solution is cooled by means of ice and 125 parts of crystallised sodium thiosulphate
are added. The mixture is oxidised by running into it a solution of 75 parts of
sodium bichromate and 38 parts of sulphuric acid in 200 parts of water, after
which 103 parts of sulphuric acid are added. After standing several hours 27
parts more sulphuric acid are added, the mixture is boiled, and the dyestuff
is filtered off, washed, and dried. It dyes cotton, from a sulphide bath, black
which is of somewhat greener shade than that dyed by the corresponding dyestuff
from paraphenylene diamine.

page_text: EXAMPLE IV,"
DYESTUFF FROM PARAAMIDOPHENOL AND ANILINE.
145 parts of paraamidophenol hydrochloride and 130 parts of aniline hydro-
chloride are dissolved in 2000 parts of water, and mixed with a solution of
625 parts of sodium thiosulphate in 1000 parts of water. The mixture is then
oxidised at 0° Centigrade with a solution of 425 parts of sodium bichromate and
150 parts of concentrated sulphuric acid in 2000 parts of water. After standing,
600 parts of concentrated sulphuric acid, diluted with 1600 parts of water are
added, the mixture is boiled, and the colouring matter is filtered off, washed,
and dried. It dyes cotton black from a sulphide bath.
EXAMPLE V.
DYESTUFF FROM PARAPHENYLENE DIAMINE AND PHENOL.
27 parts of paraphenylene diamine are dissolved in 450 parts of water and 88
parts of hydrochloric acid (27 per cent. HC1). 125 parts of crystallised sodium
thiosulphate are added and the mixture is oxidised with a solution of 50 parts
of sodium bichromate and 70 parts of concentrated sulphuric acid in 200 parts of
water, keeping the temperature at 0° Contigrade by the addition of ice. 235
parts of phenol are then added and the mixture is oxidized by a further addition
of 50 parts of sodium bichromate in 100 parts of water. After standing for some
time 156 parts of concentrated sulphuric acid, diluted with water, are slowly added;
and the mixture is then boiled and the product filtered off, washed, and dried. It
dyes cotton black a sulphide bath. If in place of phenol, ortho- or meta-cresol
be employed similar colouring-matters are obtained.
EXAMPLE VI.
DYESTUFF FROM PARAPHENYLENE DIAMINE AND RESORCIN..
792 parts of crystallised sodium thiosulphate are added to a cooled solution of
108 parts of paraphenylene diamine, 111 parts of resorcin, 900 parts of aluminium
sulphate, and 120 parts of hydrochloric acid (27 per cent. HCl) in 9000 parts of
water. The mixture is oxidised by the addition of 486 parts of sodium bichromate
dissolved in 500 parts of water acidified with 800 parts of glacial acetic acid.
4300 parts of concentrated sulphuric acid are then added, and the mixture is
boiled until the dyestuff separates out. It dyes cotton black.
EXAMPLE VII.
DYESTUFF FROM PARAPHENYLENE DIAMINE AND PYROCATECHIN.
A solution of 55 parts of the potassium salt of paraphenylenediaminedithio-
sulphonic acid (prepared according to Example I of the Specification of the
aforesaid Letters Patent 21832 of 1898) and 133 parts of pyrocatechin dissolved
in 1000 parts of water, is cooled and oxidised with a solution of 25 parts of sodium
bichromate and 31 parts of concentrated sulphuric acid in 500 parts of. water.
After standing several hours 63 parts of concentrated sulphuric acid are added
and the mixture is boiled for half-an-hour, the colouring-matter filtered off,
pressed, and dried. It dissolves in concentrated sulphuric acid and in aqueous
sodium sulphide the solution being dark violet. From a bath containing the
latter it dyes cotton indigo-blue.
-
EXAMPLE VIII.
DYESTUFF FROM PARAPHENYLENE DIAMINE MONOTHIOSULPHONIC ACID AND PARA-
PHENYLENE DIAMINE.
260 parts of paraphenylenediamine mono thiosulphonic acid and 110 parts of
paraphenylene diamine are dissolved in 4000 parts of water. This solution (kept.
cool by ice) is oxidised by the addition of 206 parts of sodium bichromate and

page_text: 300 parts of concentrated sulphuric acid dissolved in 2000 parts of water. т папу
300 parts of sulphuric acid diluted with 600 parts of water are added and the
mixture is boiled. The precipitated colouring-matter is filtered off, washed,
and dried. It dyes cotton brown from a sulphide bath.
EXAMPLE IX.
DYESTUFF FROM PARATOLYLENE DIAMINE AND THIOSULPHURIC ACID.
A solution of 31 parts of the mono-hydrochloride of paratolylene diamine in
500 parts of water is stirred with 45 parts of crystallised sodium thiosulphate
and, when all is dissolved, there is run thereinto a solution of 37 parts of
sodium bichromate and 18 parts of concentrated sulphuric acid in 80 parts of
water, the mixture being cooled to from 20° to 25º Centigrade. There is then
added 30 parts of concentrated sulphuric acid diluted with 40 parts of water and
after standing for from 2 to 3 hours 13 parts more of sodium bichromate are
added followed by 38 parts of concentrated sulphuric acid. The mixture is
boiled until the dyestuff completely separates and the dyestuff is filtered off
washed with water and dried. The product forms a dark powder, soluble in
sodium sulphide forming a brown solution and in concentrated sulphuric acid
forming a greenish-black solution. It dyes cotton, from a sulphide bath, dark
brown.
Having now particularly described and ascertained the nature of our inven-
tion and in what manner the same is to be performed we declare that what
we claim is:-
1. The manufacture and production of colouring-matters containing sulphur
by conjoint oxidation of a dithiosulphonic acid of a paradiamine or paraamido-
phenol with a compound belonging to one of the following classes or with a
mixture thereof, in manner substantially as hereinbefore described.
(a.) Aromatic monamines such as aniline, orthotoluidine, dimethylaniline,
metaloluidine, paraxylidine, orthoanisidine, alphanaphthylamine and the
like.
(b.) Phenols such as phenol, orthocresol, metacresol, pyrocatechin, resorcin,
guaiacol, alphanaphthol and the like.
(c.) Mono- or di-thiosulphonic acids of paraphenylene diamine, paraamido-
phenol, or derivatives thereof.
2. The manufacture and production of colouring-matters containing sulphur
by conjoint oxidation of a dithiosulphonic acid of a paradiamine or paraamido-
phenol with an amine, or a phenol, or a thiosulphonic acid (as defined in the pre-
ceding claiming clause under (a) (b) and (c)) and a diamine or amidophenol,
substantially as hereinbefore described.
3. The manufacture and production of colouring-matters containing sulphur,
substantially as hereinbefore described, by conjoint oxidation of a monothio-
sulphonic acid of a paradiamine or a paraamidophenol together with an amine,
phenol, diamine, amidophenol, or a thiosulphonic acid of the two latter; excepting
such mixtures as under these conditions, are known to give rise to colouring-
matters of the methylene blue class.
4. The manufacture and production of colouring-matters containing sulphur
substantially as herein before described by conjoint oxidation of a mixture of
the mono- and di-thiosulphonic acids of a paradiamine or a paraamidophenol
together with an amine, phenol, diamine, amidophenol, or a thiosulphonic acid
of the two latter excepting such mixtures as, under these conditions, are known
to give rise to colouring matters of the methylene blue class.
5. The manufacture and production of colouring-matters containing sulphur
by carrying out successively or simultaneously in the same solution, the pro-
duction of dithiosulphonic acid or of mono- thiosulphonic acid of a mixture of
dithiosulphonic acid and monothiosulphonic acid and the conversion into colouring-
matters according to the preceding Claims 1, 2, 3, or 4,

page_text: 6. The manufacture and production of colouring-matters containing sulphur
substantially as hereinbefore described by conjoint oxidation, in the presence of
two or more molecular proportions of thiosulphuric acid, of paraphenylene-
diamine, paratolylene diamine, paraxylylene diamine, paraamidophenol, para-
amidocresol, and the like (called the first component) and a second component
which may be one of the following compounds or a mixture thereof, viz.
(a.) Aromatic monamines such as aniline orthotoluidine, dimethylaniline,
metatoluidine, paraxylidine, orthoanisidine, alphanaphthylamine and
the like.
(b.) Phenols such as phenol, orthocresol, metacresol, pyrocatechin, resorein,
guaiacol, alphanaphthol, and the like.
(c.) Mono- or di-thiosulphonic acid of paraphenylene diamine, paraamido-
phenol or derivatives thereof.
7. The manufacture and production of colouring-matters containing sulphur
by the reaction of thiosulphuric acid with an indamine or indophenol of the benzene
series, or with the corresponding diphenylamine derivatives obtained by the
reduction thereof, in the presence of an oxidising agent such as chromic acid,
substantially as hereinbefore described.
8. The manufacture and production of colouring-matters containing sulphur
by conjoint oxidation, in the presence of one to two molecular proportions of thio-
sulphuric acid, of paraphenylene diamine, paratolylene diamine, paraamidophenol,
paraamidocresol, and the like (called the first component) with a second component
which may be the same or another of the above-named paradiamines or para-
amidophenols substantially as hereinbefore described.
Dated this 21st day of November 1899.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.