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

page_text: Date of Application, 15th Sept., 1899
Complete Specification Left, 6th June, 1900-Accepted, 28th July, 1900
PROVISIONAL SPECIFICATION.
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:-
This invention relates to our important discovery that ortho-diamines, ortho-
amidophenols ortho-dihydroxybenzenes, or amidated, hydroxylated, or other
substitution, products of the same; such, for instance, as orthoparatriamido-
benzene; (1: 2: 4: 5 )--tetraamidobenzene; and the like, when oxidised in
the presence of thiosulphuric acid, are substituted by the SOH group and thus
give rise to a class of new thiosulphonic acids of wide technical application. By
further oxidation and subsequent heating in acid solution of these intermediate
products they are readily converted into fast substantive colouring-matters
which dye unmordanted cotton from an alkaline sulphide bath. If the oxida-
tion be performed in the presence of a phenol, amine, amidophenol, diamine, or
oxyphenol of the aromatic series, or of the ortho compound used as mother sub-
stance of the thiosulphonic acid, these components will enter into the constitu-
tion of the final product, the colouring-matters which result therefrom being
characterised by the same valuable properties.
As shewn in the specification of our application for Letters Patent No. 22460
dated October 25th 1898 the thiosulphuric acid can generally be replaced by sul-
phuretted hydrogen and with like effect, but this substitution does not appear
to offer any technical advantages in the present case.
The quantity of thiosulphuric acid employed may be varied within wide
limits but the number of thiosulphonic groups (S,O,H) which take part in the
reaction cannot at present be determined with certainty although the fact observed
in many cases that the shade of the product is influenced by the quantity of thio-
sulphate employed leads to the assumption that both mono- and di-thiosulphonic
acids of the ortho-diamine, or ortho-amidophenol, may be formed. The isolation
of these intermediate products, which presents great difficulties, is however un-
necessary for the carrying out of this invention, nor is it necessary to separate
the formation of the thiosulphonic acid from its further convertion into colour-
ing-matter but the whole series of changes may be carried out in one operation.
Up to the present we have found that the ortho compounds most suitable for the
purpose of this invention are such as contain, at least, two amido groups in ortho
position to each other, such, for instance, as orthophenylenediamine, orthotoly-
lenediamine, the triamidobenzene and triamidotoluene obtained by reduction of
the mono-azo colouring-matters of metaphenylene diamine and metatolylene
diamine, and the tetraamidobenzene obtained by reduction of the disazo col-
ouring-matters of metaphenylene diamine.
In general we perform the operation in the following manner:-The ortho

page_text: compound employed is dissolved in just sufficient acid to render the solution
slightly acid to Congo paper. The oxidation is usually effected with a bichromate
solution which contains, for each atom of available oxygen, one equivalent of
sulphuric acid: The quantity of oxygen depends on the amount of thiosulphate
employed, but is also influenced by the shade which is required to be produced
and by the nature of the ortho compound employed. In general for one molecu-
lar proportion of ortho compound and for 1 to 2 molecular proportions of thio-
sulphate about 1 to 3 atomic proportions of oxygen will be required. The whole
of the constituents may be mixed at once, or either may be added in successive
stages.
EXAMPLE.
BROWN DYESTUFF FROM ORTHOPHENYLENE DIAMINE.
A solution of 108 g. of orthophenylene diamine in 103 c.c. of hydrochloric acid
(385 g. HCE per liter) and 1 liter of water are mixed with a solution of 187 g.
sodium thiosulphate in 300 c.c. of water and oxidised by running in 1750 c.c. of
sodium bichromate solution containing 103 g. of sodium bichromate and 50 g.
concentrated sulphuric acid per litre. During the oxidation the temperature
is kept at 10° to 20° C. by addition of ice. Afterwards 146 g. of concentrated
sulphuric acid diluted with 1 liter of water, are added and, after having stood
for say from 1 to 2 hours, treated further with 500 c.c. more of the above bi-
chromate solution. Finally 380 g. additional concentrated sulphuric acid are
added, the mixture boiled until the dyestuff separates and the latter filtered off,
washed with water, and dried. It forms a coffee-brown powder insoluble in water
and dilute acids, only slightly soluble in carbonated, or caustic, alkalies, but
easily soluble in sodium sulphide with a pure brown colour and, in concentrated
sulphuric acid with a violet-black colour. It dyes unmordanted cotton from a
sulphide bath full brown shades of considerable fastness to washing. By a sub-
sequent passage through a bath containing a copper salt, or a bichromate the
fastness is greatly increased, the shade at the same time becoming darker.
If, in the above example, there is used, in place of orthophenylene diamine,
equivalent quantities of the triamidobenzene, or triamido toluene obtained by
the reduction of benzene-azo-metaphenylene diamine, or benzene-azo-metatolyl-
ene diamine, brown dyestuffs of varying shades are obtained. A brown dyestuff
is also formed from the tetra-amido-benzene obtained by the reduction of di-
benzene-disazo-metaphenylene diamine and a dark violet-brown dyestuff from
the diamido phenol (O'H; NH; N'H₂).
* Total the thil law of Cantamban 1900
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
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 and in what manner the same is to be
performed to be particularly described and ascertained in and by the following
statement:
This invention relates to the important discovery that ortho-diamines, ortho-
amido phenols ortho-dihydroxybenzenes, or amidated, hydroxylated, or other

page_text: substitution products of the same: such, for instance, as ortho para triamido-
benzene; (1 2: 4: 5-tetraamido benzene; and the like, when oxidised in
the presence of thiosulphuric acid are substituted by the S,OH group and thus
give rise to a class of new thiosulphonic acids of wide technical application. By
further oxidation and subsequent heating in acid solution these intermediate
products are readily converted into fast substantive colouring matters
which dye unmordanted cotton from an alkaline sulphide bath. If the oxida-
tion be performed in the presence of a phenol, amine, amidophenol, diamine, or
oxyphenol of the aromatic series or in the presence of the ortho compound used
as mother substance of the thiosulphonic acid, these components will enter into
the constitution of the final product, the colouring matters which result thereby
being characterised by the same valuable properties.
As shewn in the specification of Letters Patent No. 22460 dated
October 25th 1898 the thiosulphuric acid can generally be replaced by sul-
phuretted hydrogen with like effect, but this substitution does not appear
to offer any technical advantages in the present case.
The quantity of thiosulphuric acid employed may be varied within wide
limits but the number of thiosulphonic groups (S,OH) which take part in the
reaction cannot at present, be determined with certainty although the fact observed
in many cases that the shade of the product is influenced by the quantity of thio-
sulphate employed leads to the assumption that both mono- and di-thiosulphonic
acids of the ortho diamine, or ortho-amido phenol are formed. The isolation
of these intermediate products presents great difficulties but such isolation is un-
necessary in carrying out this invention, nor is it necessary to conduct the forma-
tion of the thiosulphonic acid separately from its further conversion into colour-
ing matter as the whole series of reactions may be carried out in one operation.
Up to the present we have found that the ortho compounds most suitable for the
purpose of this invention are such as contain, at least, two amido groups in ortho
position to each other, such, for instance, as orthophenylenediamine, ortho toly-
lene diamine, the triamido benzene and triamidotoluene obtained by the reduction
of the mono-azo colouring-matters from metaphenylene diamine and metatolylene
diamine, and the tetraamidobenzene obtained by the reduction of the disazo col-
ouring-matters from metaphenylene diamine.
In general we perform the operation in the following manner: The ortho
compound employed is dissolved in just sufficient acid to render the solution
slightly acid to Congo paper. The oxidation is usually effected with a bichromate
solution which contains for each atom of available oxygen one equivalent of
sulphuric acid. The quantity of oxygen depends on the amount of thiosulphate
employed but is also influenced by the shade which is required to be produced
and by the nature of the ortho compound employed. In general for one molecu-
lar proportion of ortho compound and for one to two molecular proportions of
thiosulphate about one and a half to three atomic proportions of oxygen will be
required. The whole of the constituents may be mixed at once or they may be
added in successive stages.
The following is an example of ways in which this invention can be practically
performed. The parts are by weight.
EXAMPLE.
BROWN DYESTUFF FROM ORTHOPHENYLENE DIAMIME.
A solution of 108 parts of orthophenylene diamine in 113 parts of hydro-
chloric acid (35 per cent. HCl.) and 1000 parts of water are mixed with a solu-
tion of 187 parts sodium thiosulphate in 300 parts of water and oxidised by run-
ning in a solution containing 180 parts of sodium bichromate and 87 parts of
concentrated sulphuric acid in 1500 parts of water. During the oxidation the
temperature is kept at from 10° to 20° Centigrade by the addition of ice. After-
wards 146 parts of concentrated sulphuric acid, diluted with 1000 parts of water,
are added and after the mixture has stood for say from one hour to two hours it

page_text: is treated further with a solution of 51 parts of sodium bichromate and 25 parts
of sulphuric acid in 500 parts of water. Finally 380 parts additional concentrated
sulphuric acid are added and the mixture boiled until the dyestuff separates, and
the latter is then filtered off, washed with water and dried. It forms a coffee-
brown powder which is insoluble in water and dilute acids, only slightly soluble
in carbonated or caustic alkalies but easily soluble in sodium sulphide (the solu-
tion in which is a pure brown) and in concentrated sulphuric acid (the solution
in which is violet-black). It dyes unmordanted cotton, from a sulphide bath,
full brown shades of considerable fastness against washing. By subsequently
passing the dyed goods through a bath containing a copper salt, or a bichromate,
the fastness is greatly increased, the shade at the same. time becoming darker.
If in the above example, there be used in place of ortho phenylene diamine,
equivalent quantities of the triamido benzene, or triamido toluene, obtained by
the reduction of benzene-azo-meta phenylene diamine, or benzene azo-metatolylene
diamine brown dyestuffs of varying shades are obtained. A brown dyestuff is
also formed in like manner from the tetra amido benzene obtained by the reduc-
tion of di-benzene disazo-metaphenylene diamine, and a dark violet brown dye-
stuff from the diamidophenol (0¹H; N¹H₂; N¹H₂).
Having now particularly described and ascertained the nature of our said
invention 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
(which dye cotton in fast dark shades direct from a sulphide bath) by oxidation
in presence of thiosulphuric acid of an orthodiamine, orthoamidophenol or ortho-
dihydroxybenzene or of amidated, hydroxylated, or other substitution products
thereof such as triamidobenzene, triamidotoluene, tetraamido-benzene diamido-
phenol and the like, with or without the addition of a second component which
may be a body of the same class as the first component or other amine phenol
amidophenol or diamine, the product being finally heated in acid solution sub-
stantially as herein before described.
2. The manufacture and production of fast brown colouring matters as described
in the foregoing example.
3. As new articles of manufacture the colouring matters containing sulphur
and dyeing cotton in fast dark shades direct from a sulphide bath such as can be
obtained according to the processes claimed by the preceding claiming clauses.
Dated this 6th day of June 1900.
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.