Improvements in the Production of Colouring Matters for Cotton.
Year: 1897

page_text: Date of Application, 20th Sept., 1897
Complete Specification Left. 19th July, 1898-Accepted 20th Aug., 1898
Improvements in the Production of Colouring Matters for Cotton.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton Moor, near
Stockport, in the County of Lancaster, and ANDRÉ RAOUL WAHL, of 331, Ashton New
Road, Clayton, near Manchester, in the said County, both Chemists to the Clayton
Aniline Company, Limited, do hereby declare the nature of our invention to be as
follows:-
This invention relates to the preparation of colouring matters from di-nitro-diphenyl
ethane-disulphonic acid
C. By condensation and reduction.
D. From certain of the products obtained according to B and C by diazotisation
and coupling with amines and phenols or the like. The colouring matters
so obtained all have a direct affinity for cotton which they dye a great
variety of shades ranging from yellow and orange to red, dark brown, and
black
By the action of weak reducing agents in presence of caustic alkalies upon dinitro-
diphenyl-ethane-disulphonic acid the latter is converted into yellow and orange
colouring matters which are closely similar and probably identical with the colours
obtained by the action of caustic alkalies and oxidisable substances upon paranitro-
toluene sulphonic acid. By stronger reduction (for instance with stannous chloride
or sodium amalgam): diamidodiphenyl ethanedisulphonic acid is obtained. Suitable
reducing agents are zinc dust, ferrous hydrate sodium stannite, glucose, glycerine,
benzaldehyde, and the like, but we do not confine ourselves to these as any substance
may be used which is capable of taking up oxygen without itself undergoing
condensation..
EXAMPLE 1.
50 lbs. of dinitrodiphenylethane disulphonate of soda are dissolved in 100 gallons
of water. 18 gallons of a 10 per cent. solution of glucose are added together with
5 gallons of aqueous caustic soda (30 per cent. NaOH) and the mixture is heated at
about 80° Centigrade for several hours. After neutralising the excess of soda the
colour is filtered off and dried. It forms a reddish powder which dissolves in concen-
trated sulphuric acid forming a red solution and it dyes cotton yellowish-orange. By
employing a larger quantity of glucose than that herein before given products are

page_text: On reducing colouring-matters obtained under head B by weak alkaline reducing
agents, a further series of colouring-matters is obtained. These when obtained from
diazotisable colours also possess the property of being diazotised. They differ from the
unreduced colouring matters in dyeing a redder shade of yellow, or orange, and in
the bluer colour of their solution in concentrated sulphuric acid. The reduction may
be performed subsequently to the condensation or both condensation and reduction
may be performed simultaneously. As reducing agents we may use glucose, glycerine,
ferrous hydrate, sodium stannite, sodiuin arsenite, and the like, all in alkaline solution.
Moreover in some cases the same substance may act both as a component for
condensation and as a reducing agent.
EXAMPLE 6.
50 lbs. of the yellow colouring matter obtained according to Example 3 from
dinitrodiphenylethane disulphonic acid and dehydrothio-toluidine sulphonic acid are
dissolved in 100 gallons of water. The solution is heated at 80° to 90° Centigrade
and 1 gallon of a 10 per cent. solution of glucose is added and afterwards 1 gallons of
aqueous caustic soda (30 per cent. NaOH) are added. The mixture is kept at
80° to 90° Centigrade for 2 or 3 hours, and the colour is then salted out, filtered
off, and dried. It dyes orange upon cotton and dissolves in concentrated sulphuric
acid forming a violet blue solution.
D.
As already mentioned certain of the products obtained under heads B and C contain
a free amido group and are therefore diazotisable. A very wide range of colours is
obtained by combining these diazo compounds with suitable amines and phenols such
for instance as metaphenylene diamine, metatoluylene diamine salicylic acid, phenol,
resorcin, alpha- and beta-naphthol, the naphthol sulphonic acids the naphthylamine
sulphonic acids, the sulphonic acids of 18 dioxynaphthalene, the sulphonic acids
of (18) amidonaphthol, naphthylamine ether, and other well known azo-dyestuff
components. The combination can be made either upon the fibre or in substance.
The colours produced in substance dye unmordanted cotton directly. A further
series of colouring matters can also be produced by employing either of the above
diazotised colouring matters as one component of a disazo or polyazo colouring matter
into which another diazo or tetrazo compound also enters according to the now well
known methods of preparing such colours.
EXAMPLE 7.
With betanaphthol
resorcin
"
"
"
""
metatoluylene diamine
betanaphtholdisulphonic acid R
alphanaphthylamine
red.
orange.
brown.
maroon.
dark purple.
The above examples are given to illustrate the general method of carrying out
this invention but we do not limit ourselves to the exact conditions or proportions
therein as these may be varied greatly.

page_text: Improvements in the Production of Colouring Matters for Cotton.
We, ARTHUR GEORGE GREEN, F.I.C., F.C.S., of 13, Kings Drive, Heaton Moor,
near Stockport, in the County of Lancaster, and ANDRÉ RAOUL WAHL, of 331, Ashton
New Road, Clayton, near Manchester, in the said County, both Chemists to the
Clayton Aniline Company, Limited, 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 preparation of colouring matters from di-nitro-
diphenyl-ethane-disulphonic acid (otherwise known as dinitrodibenzyldisulphonic
acid)—
[4:2:1] NO(SO₂H)CH¸¨CH₂ CH₂CH¸(SO₂H)NO, [1:2:4].
2
C. By condensation and reduction.
риеното, от не пке,
D. From certain of the products obtained according to B and C by diazotisation
and coupling with amnines, phenols, or the like. The colouring-matters so
obtained all have a direct affinity for cotton which they dye a great variety
of shades ranging from yellow and orange to red, dark brown, and
black.
A.
By the action of weak reducing agents in presence of alkalies upon dinitro-
diphenyl-ethane-disulphonic acid the latter is converted into yellow and orange
colouring-matters which are closely similar to and possibly identical with, the colours
obtained by the action of caustic alkalies and oxidisable substances upon paranitroto-
luene sulphonic acid. By stronger reduction, (for instance with stannous chloride, or
sodium amalgam), diamido-diphenylethane-disulphonic acid is obtained. Suitable
reducing agents are zinc dust, ferrous hydrate, sodium stannite, glucose, glycerine,
benzaldehyde, and the like, but we do not confine ourselves to these.
EXAMPLE 1.
50 lbs. of dinitro-diphenylethane-disulphonate of soda are dissolved in 100 gallons
of water. 18 gallons of a 10 per cent. solution of glucose are added together with
5 gallons of aqueous caustic soda (30 per cent. NaOH), and the mixture is heated at
about 80° Centigrade for several hours. After neutralising the excess of soda the
colour is filtered off and dried. It forms a reddish powder which dissolves in con-
centrated sulphuric acid forming a red solution and it dyes cotton yellowish-orange.
By employing a larger quantity of glucose than that herein before given products are
obtained which dye reddish-orange shades on cotton and dissolve in concentrated
sulphuric acid giving a violet to blue solution.
When dinitro-diphenylethane-disulphonic acid is heated in the presence of caustic
alkalies with amines, phenols, amidophenols, nitroamines, or their sulphonic or
carboxylic acid derivatives (either of the benzene or of the naphthalene series) a

page_text: water.
47 lbs. of dinitrodiphenylethane-disulphonate of soda are dissolved in 100 gallons of
15 lbs. of alpha-naphthol and 5 gallons of aqueous caustic soda (30 per cent.
NaOH) are added and the mixture is boiled for several hours. The product is a
dark powder, soluble in concentrated sulphuric acid forming a violet solution. It
dyes orange-brown upon cotton and can be diazotised upon the fibre.
C.
On reducing colouring-matters obtained under head B by weak alkaline reducing
agents, a further series of colouring -matters is obtained. These when obtained from
diazotisable colours also possess the property of being diazotised. They differ from
the unreduced colouring matters in dyeing a redder shade of yellow, or orange, and
in the bluer colour of their solution in concentrated sulphuric acid.
may be performed subsequently to the condensation, or both condensation and
The reduction
reduction may be performed simultaneously. As reducing agents we may use
glucose, glycerine, ferrous hydrate, sodium stannite, sodium arsenite, and the like,

page_text: all in alkaline solution. Moreover in some cases the same substance may act both as
a component for condensation and as a reducing agent.
EXAMPLE 6.
50 lbs of the yellow colouring matter obtained according to Example 3 from
dinitro-diphenylethane disulphonic acid and dehydro-thiotoluidine sulphonic acid,
are dissolved in 100 gallons of water. The solution is heated at 80° to 90°
Centigrade and 1 gallon of a 10 per cent. solution of glucose. is added and afterwards
1 gallons of aqueous caustic soda (30 per cent. NaOH) are added. The mixture is
kept at 80° to 90° Centigrade for 2 or 3 hours, and the colour is then salted out,
filtered off, and dried. It dyes orange upon cotton and dissolves in concentrated
sulphuric acid forming a violet blue solution.
D.
As already mentioned certain of the products obtained under heads B and C
contain a free amido group and are therefore diazotisable. A very wide range of
colours is obtained by combining these diazo compounds with suitable amines and
phenols, such for instance as metaphenylene diamine, metatoluylene diamine,
salicylic acid, phenol, resorcin, alpha- and beta-naphthol, the naphthol sulphonic acids,
the naphthylamine sulphonic acids, the sulphonic acids of (1: 8)-dioxynaphthalene,
the sulphonic acids of (1: 8)-amidonaphthol, naphthylamine ether, and other well
known azo-dyestuff components. The combination can be made either upon the
fibre, or in substance. The colours produced in substance dye unmordanted cotton
directly. A further series of colouring matters can also be produced by employing
either of the above diazotised colouring matters as one component of a disazo, or
polyazo, colouring matter into which another diazo, or tetrazo, compound also
enters according to the now well known methods of preparing such colours.

page_text: 3. The hereinbefore described process for the conversion of the colouring-matters
obtained according to the preceding Claim 2 into colouring-matters of redder shade
by limited reduction in alkaline solution.
4. The herein before described process for the conversion of such of the colouring-
matters obtained according to the preceding Claims 2 and 3 as contain a free amido
group into further colouring-matters of darker shade, by diazotisation and coupling
with the usual azo-dyestuff components, whether in substance, or upon the fibre,
or by the employment of the diazo compound as one constituent of a mixed polyazo
colour.
5. The process described in the preceding Example 3 for the preparation of a
yellow colouring-matter by condensation of dinitro-diphenylethane disulphonic acid
of Letters Patent. 5351 of 1897 with dehydro-thiotoluidine sulphonic acid in caustic
alkaline solution.
6. The process described in the preceding Example 6 for the preparation of an
orange colouring-matter by the action of an alkaline reducing agent upon the
product of the preceding Claim 5.
7. As new products the direct dyeing cotton colouring-matters such as are obtained
according to the processes of the preceding Claims 1, 2, 3, 4, 5 and 6, with exception
of those which are identical with the products of known processes.
ATC 10 fun mor BOOST
1030
JOHNSON & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
JOHNSON & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.