The Manufacture and Production of New Indigo Colouring Matter."
Year: 1899

page_text: Date of Application, 28th Oct., 1899
Complete Specification Left Ruth July 4000 Accepted
fot Cant
1000
PROVISIONAL SPECIFICATION.
"The Manufacture and Production of New Indigo Colouring Matter."
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been.
communicated to me from abroad by the Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine in the German Empire) to be. as follows;-
Halogen substitution products of indigo are already known, but all these
known products most closely resemble indigo not merely in their property of
subliming and the like, but also in yielding a vat from which they can be dyed
and in dyeing the various fibres giving blue shades.
The present invention relates to the manufacture of a new halogen substituted
indigo colouring-matter which resembles indigo in its chemical properties, in
its manner of being dyed, and in the fastness of the shades obtained, but which
differs from indigo, and from the hitherto known halogen substitution compounds
thereof, in that the colour obtained by dyeing with it is a brilliant red-violet.
If this new colouring-matter be treated with fuming sulphuric acid a soluble
sulpho-acid is obtained which, however, dyes wool, from the acid bath, blue
shades.
The new colouring-matter can be conveniently obtained, starting from para-
chlor-ortho-nitro-toluol (see Berichte volume 19, page 2440). This body is
oxidised by means of manganese peroxide in sulphuric acid, preferably at a high
temperature, so as to obtain para-chlor-ortho-nitro-benzaldehyd.
This ortho-
nitro-benaldehyd derivative is then converted, by treatment with acetone and
alkali, into the new indigo colouring-matter. This can be either done directly,
or the intermediate para-chlor-ortho-nitro-phenol-lactic-acid-methyl-ketone can
be isolated, and either be used as such, or after conversion into its bisulphite
compound for conversion into indigo by treatment with alkali. This conversion
can either be effected on the fibre, or not.
The following examples will serve to further illustrate the nature of the
invention, but the invention is. not. confined to the examples. The parts are
by weight:
EXAMPLE -1.
OXYDATION OF PARA-CHLOR-ORTHO-NITRO-TOLUOL.
Mix together one hundred parts of para-chlor-ortho-nitro-toluol; about two
hundred parts of manganese peroxide, (containing about 80 per cent MnO₂) and
one thousand parts of sulphuric acid, (containing about 63% H₂SO). Heat
this mixture for about four to five hours and at a temperature of from 130° to
1400 centigrade in a lead-lined vessel furnished with an inverted condenser.
When the oxydation is finished, allow the liquid to stand until practically clear.
Then separate the acid from the oil, and wash the oil successively with water
and with a solution of carbonate of soda. Next treat the said oil with sodium.
га
037

page_text: bisulphite, so as to obtain the crystalline bisulphite compounds of the aldehyde.
Dissolve this in water and decompose it with alkali; or acid. Collect in any
suitable way.
EXAMPLE 2:
CONVERSION OF PARA-CHLOR-ORTHO-NITRO-BENZALDEHYDE INTO PARA-DI-CHLOR-
INDIGO.
Prepare a mixture of one hundred parts of para-chlor-ortho-nitro-benzaldehyd,
forty parts of acetone and ten parts of water. To this mixture add, gradually,
whilst keeping the whole mass cool, one thousand parts of dilute caustic soda
lye (containing 1 per cent of NaOH). The para-di-chlor-indigo soon begins to
separate out. Collect by filtering, wash and dry. The new colouring-matter so
obtained is a brown-red powder, which, on rubbing with a hard body, gives an
intensely black metallic streak. Upon heating, it sublimes, evolving violet-red
vapours, which yield a crystalline sublimate It is insoluble in the ordinary
solvents, but is soluble in boiling nitro-benzene, or aniline (the solutions being
violet-red) from which on cooling it separates out. The new indigo derivative
can be dyed like the ordinary indigo from the vat: and it dyes wool and cotton
in this way violet-red shades which are fast to washing and to light. On treat-
ment with fuming sulphuric acid it yields a sulphoacid which is soluble in
water and dyes wool from the acid bath blue shades.
Dated this 28th day of October 1899.
JOHNSONS & WILLCOX
47 Lincolns Inn Fields London WC.
Agents.
"The Manufacture and Production of New Indigo Colouring Matter:"
I, JAMES YATE JOHNSON of 47 Lincolns Inn Fields in the County of London,
Gentleman, do hereby declare the nature of this invention, (which has been
communicated to me from abroad by the Badische Anilin & Soda Fabrik of
Ludwigshafen-on-Rhine in the German Empire) and in what manner the
same is to be performed, to be particularly described and ascertained in and by
the following statement:-
-
Halogen substitution products of indigo are already known, but all these
known products most closely resemble indigo not merely in their property of
subliming and the like, but also in yielding a vat from which they can be dyed,
and in dyeing blue shades on the various fibres.
The present invention relates to the manufacture of a new halogen substituted
indigo colouring matter which closely resembles indigo in its chemical properties,
in its manner of being dyed, and in the fastness of the shades obtained, but which
differs from indigo, and from the hitherto known halogen substitution compounds
thereof, in that the colour obtained by dyeing with it is a brilliant red-violet.
If this new colouring matter be treated with fuming sulphuric acid a soluble
sulphoacid is obtained which, however, dyes wool, from the acid bath, blue
shades.
The new colouring matter can be conveniently obtained, starting from para-
chlor-ortho-nitro-toluene (see Berichte, volume 19, page 2440). This body is
oxidised by means of manganese peroxide in sulphuric acid, preferably at a high
temperature, so as to obtain para-chlor-ortho-nitro-benzaldehyde. This ortho-
nitro-benzaldehyde derivative is then converted, by treatment with acetone and

page_text: CONVERSION OF PARA-CHLOR-ORTHO-NITRO-BENZALDEHYDE INTO NEW INDIGO
COLOURING-MATTER.
Prepare a mixture of one hundred parts of para-chlor-ortho-nitro-benzaldehyde,
four hundred parts of acetone and one hundred parts of water. To this mixture
add, gradually, whilst keping the whole mass cool, one thousand parts of dilute
caustic soda lye. (containing one per cent of NaOH). The new indigo colouring
matter soon begins to separate out. Collect by filtering, wash and dry. The
new colouring matter so obtained is a brown-red powder, which, on rubbing with
a hard body, gives an intensely black metallic streak. Upon heating, it sub-
limes, evolving violet-red vapours, which yield a crystalline sublimate. It is
insoluble in the ordinary solvents, but is soluble in boiling nitro-benzene, or
aniline, (the solutions being violet-red,) from which, on cooling, it separates out.
The new indigo derivative can be dyed from the vat, like ordinary indigo; and
it dyes wool and cotton in this way violet-red shades which are fast to washing

page_text: and to light. On treatment with fuming sulphuric acid it yields a sulphoacid
which is soluble in water and dyes wool, from the acid bath, blue shades.
Having now particularly described and ascertained the nature of this
invention and in what manner the same is to be performed, I wish it to be
understood that I am aware of the Specification of Letters Patent No. 22121
of 1897 granted to George Beloe Ellis and that I do not claim anything described
and claimed therein, but I declare that what I claim is :-
1. As a step in the manufacture of new indigo colouring matter, the production
of para-chlor-ortho-nitro-phenyl-lactic acid methyl-ketone, by condensing para-
chlor-ortho-nitro-benzaldehyde with acetone, substantially as hereinbefore
described.
2. As a step in the manufacture of new indigo colouring matter, the treat-
ment of the ketone, obtainable in accordance with the last preceding claiming
clause for the production of the bisulphite compound thereof.
3. The manufacture of new indigo colouring matter by treating para-chlor-
ortho-nitro-phenyl-lactic acid methyl-ketone, or its bisulphite compound, with
caustic alkali.
4. The manufacture of new indigo colouring matter by condensing para-chlor-
ortho-nitro-benzaldehyde with acetone, substantially as hereinbefore described.
5. The production of new indigo colouring matter by sulphonating the pro-
duct such as can be obtained in accordance with the last preceding claiming
clause.
6. The manufacture of new indigo colouring matter and the several steps
claimed in the preceding claims in its production as described in the foregoing
examples.
7. The new indigo colouring matter such as can be obtained by condensing
para-chlor-ortho-nitro-benzaldehyde with acetone, substantially as hereinbefore
described.
8. The new indigo colouring matter such as can be obtained by sulphonating
the product claimed in the last preceding claiming clause.
Dated this 28th day of July 1000.
JOHNSONS & WILLCOX
47. Lincoln's Inn Fields London, W.C.
Agents.