The Manufacture and Production of New Cotton Colouring Matters.
Year: 1896

page_text: Date of Application, 11th June, 1896
Complete Specification Left, 5th Mar., 1897-Accepted, 8th May, 1897
PROVISIONAL SPECIFICATION.
The Manufacture and Production of New Cotton Colouring
Matters.
We ARTHUR GEORGE GREEN F.I.C. F.C.S. of 13 Kings Drive, Heaton Moor
near Stockport in the County of Lancaster and ANDRE RAOUL WAHL of
77 Mawson Street Ardwick Manchester in the said county both Chemists to The
Clayton Aniline Company Limited do hereby declare the nature of this invention
to be as follows:-
In 1883 Walter shewed that by heating paranitrotoluene sulphonic acid with
aqueous caustic soda the said acid was converted into a condensation product which
dyed unmordanted cotton an orange-yellow of considerable fastness to light
(Bulletin de la Soc. Industrielle de Mulhouse 1887, 99). This product is known
in commerce by the names of Sun Yellow; Curcumine S; and Direct Yellow G;
amongst others. In the Specification of English Letters Patent No. 2664 of 1888
it was shewn that by performing this condensation in the presence of oxidisable
substances new bodies were obtained which dyed unmordanted cotton various shades
of orange and brown and which are known in commerce as Mikado orange and
Mikado brown and were afterwards proved to be reduction products of the first
condensation product (curcumine) and could be obtained by treating it with reducing
agents in alkaline solution (see the Specification of English Letters Patent
No. 23672 of 1892). A very similar colouring-matter known as chloramine
orange is obtained (according to the Specification of English Letters Patent
No. 16708 of 1893) by oxidizing diamidostilbenedisulphonic acid by means of
alkaline hypochlorites. Great analogy with all these substances (especially in
fastness to light and the extreme oxidisability of their leuco compounds) is
exhibited by the yellow colouring matters known as oxyphenine, chloramine
yellow and the like which are obtained by the action of alkaline oxidising agents
upon dehydrothiotoluidine-sulphonic acid and primuline. We were therefore led
to believe that a similar constitution must be ascribed to both series of colours, and
to seek the existence of an intermediate class of colours derivable from para-
nitrotoluenesulphonic acid on the one hand and dehydrothio compounds on the
other. Such products we have been able to obtain by heating a mixture of para-
nitrotoluene sulphonic acid and a dehydrothio compound with weak aqueous
caustic potash or caustic soda. The new compounds thus obtained are very
valuable colouring-matters which dye unmordanted cotton orange-yellow shades
distinguished by great resistance to light, chlorine, alkalies and acids. We have
also found that by subjecting them to the action of reducing agents they are
converted into further new colouring-matters which dye unmordanted cotton
bright shades of orange which are also distinguished by great resistance to light
chlorine alkalies and acids. As dehydrothio compounds we may employ dehydrothio-
paratoluidine sulphonic acid, dehydrothioxylidine sulphonic acid, dehydrothio-
pseudocumidine sulphonic acid, primuline xylidine primuline, and analogous bodies.
For the conversion of the first formed condensation products into the more orange
reduction products any suitable oxidisable substance may he used such as ferrous
hydrate, zinc dust, sodium arsenite, sodium stannite, glucose, glycerine, formaldehyde,
and the like, the operation being performed in alkaline solution. The following

page_text: will serve to illustrate the invention further but they are only given as examples
and the invention is not limited thereto.
EXAMPLE I.
28 lbs. of sodium paranitrotoluene sulphonate (85 per cent.) and 17 lbs. of sodium
dehydrothioparatoluidine sulphonate are dissolved in 10 gallons of water and heated
with gallon of caustic soda solution (24 per cent. NaOH) for say 3 or 4 hours at
90° to 100° Centigrade. The product separates from the hot solution as a bright
orange precipitate which is filtered off and dried. It dyes unmordanted cotton a
bright orange-yellow fast against the action of light, chlorine, alkalies, and acids.
The filtrate contains a little curcumine formed as a bye-product. The product is
less soluble in water than in curcumine, being completely precipitated from its
aqueous solution on the addition of a small quantity of common salt. Its aqueous
solution is completely precipitated by dilute hydrochloric acid. Under the same
conditions a solution of curcumine gives no precipitate. It dissolves in concentrated
sulphuric acid with a violet red colour.
EXAMPLE II.
50 lbs. of the product obtained according to the previous example are dissolved
in 80 gallons of water with the addition of 2 gallons of aqueous caustic soda
(24 per cent. NaOH). A solution of 10 lbs. of glucose in 10 gallons of water is
then added and the mixture is boiled until a sample dissolves in concentrated
sulphuric acid with a blue colour. The product is then precipitated by common
salt, filtered off, and dried. It forms an orange-brown powder which dyes
unmordanted cotton a bright reddish-orange colour which is fast against the action
of light, alkalies, and acids. Its aqueous solution gives a reddish-brown precipitate
with dilute acids. Under the same conditions Mikado orange gives a yellow-green
solution but no precipitate.
Dated this 11th day of June 1896
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Cotton Colouring
Matters.
We, ARTHUR GEORGE GREEN, F.I.C. F.C.S. of 13 Kings Drive, Heaton
Moor, near Stockport in the County of Lancaster, and ANDRE RAOUL WAHL,
of 77 Mawson Street, Ardwick, 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:-
In 1883 Walter shewed that by heating paranitrotoluene sulphonic acid with
aqueous caustic soda the said acid was converted into condensation products which
dyed unmordanted cotton orange Fellow shades of considerable fastness to light
(Bulletin de la Soc. Industrielle de Mulhouse 1887, 99). The said condensation
products are known in commerce by the names of Sun Yellow, Circumine S, and
Direct Yellow G, amongst others. In the Specification of English Letters
Patent No. 2664 of 1888 it was shewn that by performing this condensation in the
presence of oxidisable substances new bodies were obtained which dyed unmordanted

page_text: cotton various shades of orange and brown and which are known in commerce as
Mikado orange and Mikado brown and were afterwards proved to be reduction
products of the first condensation products, and could be obtained by treating said
first condensation products with reducing agents in alkaline solution (see the
Specification of English Letters Patent No. 23672 of 1892). A very similar
colouring matter is obtained (according to the Specification of English Letters
Patent No. 16708 of 1893) by oxidizing diamidostilbenedisulphonic acid by means
of alkaline hypochlorites. Great analogy with all these substances (especially in
fastness to light, and the extreme oxidisability of their leuco compounds) is
exhibited by the yellow colouring matters known as oxyphenine, chloramine
yellow, and the like, which are obtained by the action of alkaline oxidising agents
upon dehydrothiotoluidine-sulphonic acid and primuline. We were therefore led
to believe that a similar constitution must be ascribed to both series of colours and
to seek the existence of an intermediate class of colours derivable from paranitro-
toluene sulphonic acid on the one hand and dehydrothio compounds on the other.
Such products we have been able to obtain by heating a mixture of paranitrotoluene
sulphonic acid and a dehydrothio compound with weak aqueous caustic potash, or
caustic soda. The new compounds thus obtained are very valuable colouring
matters which dye unmordanted cotton orange-yellow shades distinguished by great
resistance to light, chlorine, alkalies, and acids.
We have also found that by subjecting these new products to the action of
reducing agents they are converted into further new colouring matters which dye
unmordanted cotton bright shades of orange which are also distinguished by great
resistance to light, chlorine, alkalies, and acids. As dehydrothio compounds we
may employ dehydrothioparatoluidine sulphonic acid, dehydrothioxylidine
sulphonic acid dehydrothiopseudocumidine sulphonic acid, primuline, xylidine-
primuline, and analogous bodies.
For the conversion of the first formed condensation products into the more
orange reduction products, any suitable oxidisable substance may be used, such
as ferrous hydrate, zinc dust, sodium arsenite, sodium stannite, glucose, glycerine,
formaldehyde, and the like, the operation being performed in alkaline solution.
The following will serve to illustrate the invention further and the manner in
which it can be performed but they are only given as examples and the invention
is not limited thereto.
EXAMPLE 1.
28 lbs. of sodium paranitrotoluene sulphonate (85 per cent.) and 17 lbs. of
sodium dehydrothioparatoluidine sulphonate are dissolved in 10 gallons of water
and heated with gallon of caustic soda solution (24 per cent. NaOH) for say
3 or 4 hours at 90° to 100° Centigrade. The product separates from the hot
solution as a bright orange precipitate which is filtered off and dried. It dyes
unmordanted cotton a bright orange-yellow fast against the action of light, chlorine,
alkalies, and acids. The filtrate contains a little curcumine formed as a bye-product.
The product is less soluble in water than is curcumine, being completely precipitated
from its aqueous solution on the addition of a small quantity of common salt.
aqueous solution is completely precipitated by dilute hydrochloric acid. (Under
the same conditions a solution of curcumine gives no precipitate.) It dissolves in
concentrated sulphuric acid with a violet-red colour. It is further sharply
distinguished from curcumine, direct yellow and the like by its behaviour with
sodium bi-sulphite as in a strong solution thereof it dissolves with a yellow colour
whilst curcumine, direct yellow, and the like are nearly insoluble in such a
solution.
Its

page_text: (24 per cent. NaOH). A solution of 10 lbs. of glucose in 10 gallons of water is
then added and the mixture is boiled until a sample dissolves in concentrated
sulphuric acid with a blue colour. The product is then precipitated by common
salt, filtered off, and dried. It forms an orange brown powder which dyes
unmordanted cotton a bright reddish orange colour which is fast against the action
of light, alkalies, and acids. Its aqueous solution gives a reddish-brown precipitate
with dilute acids. Under the same conditions Mikado orange gives a brownish
solution but no precipitate.
If in the above example either a smaller quantity of the reducing agent, or a less
aotive reducing agent be employed the product then obtained will dye cotton an
orangeless red in shade and will dissolve in concentrated sulphuric acid with a
violet colour.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed, we declare that what we
⚫ claim is :-
1. The manufacture of colouring matters by the condensation of paranitrotoluene
-sulphonic acid with a dehydrothio compound, such as dehydrothioparatoluidine
suiphonic acid, dehydrothio xylidine sulphonic acid, dehydrothio pseudocumidine
sulphonic acid, primuline, xylidine-primuline, and analogous bodies in caustic
alkaline solution.
2. As new articles of manufacture colouring matters such as can be obtained by
the process claimed by the preceding first claiming clause.
3. The manufacture of colouring matters by treating the colouring matters of the
preceding claiming clauses in alkaline solution with an oxidisable substance such as
ferrous hydrate, ziuc dust, sodium arsenite, sodium stannite, glucose, glycerine,
formaldehyde and the like.
4. As new articles of manufacture, colouring matters such as can be obtained by
the process claimed by the preceding third claiming clause.
Dated this 5th day of March 1897.
JOHNSONS & WILLCOX,
47 Lincoln's Inn Fields, London, W.C.