Manufacture and Production of New Colouring Matters and of Products for use therein.
Year: 1899

page_text: Date of Application, 20th Dec., 1899
Complete Specification Left, 24th Aug., 1900-Accepted, 24th Nov., 190G
PROVISIONAL DIVIFICATION,
The Manufacture and Production of New Colouring Matters and of
Products for use therein.
I, JAMES YATE JOHNSON, of 47, Lincoln's 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:-
It is known that if para-amido-phenol be treated with one molecular proportion'
of dinitro-chlor-benzene or dinitro-brom benzene in the presence of suitable
reagents for binding acids, such as soda, sodium acetate, and the like, the.
corresponding para-hydroxy, ortho-para-dinitro-diphenylamine is obtained. (See
Nietzki and Simon Berichte 1895, page 2973). In the same way the corre-
sponding compound can be obtained from para-amido-phenol-ortho sulpho acid.
My foreign correspondents, have discovered that the said hydroxy-dinitro-
diphenylamine derivative can be combined with a further molecular proportion
of dinitro-chlor-benzene, so that phenol-ethers are obtained. These presumably
possess the constitution indicated by the following formulae:-
It is unnecessary to effect the condensations with the dinitro-chlor-benzene, or
its equivalent, in two phases. The para-amido-phenol, or its sulphoacid, can,
in one operation, be combined with two molecular proportions of dinitro-chlor-
benzene in the presence of, for instance, soda and the desired new products be
obtained.
Again, other nitrated phenol-ethers can be obtained similarly by treating the
para-hydroxy-ortho-para-dinitro-diphenylamine derivative with ortho-nitro-
chlor-benzene-para-sulphoacid, or with para-nitro-chlor-benzene-ortho-sulphoacid.

page_text: Judging from the method of formation the constitution of these bodies would bo
indicated by the following formula.
All these new phenol ethers can my foreign correspondents have discovered,
be used for the production of substantive colouring matters for cotton, by treat-
ment with sodium sulphide and sulphur. The shades obtained
are dark
greenish-black characterised by considerable beauty and excellent fastness.
On treating the goods, dyed with these colouring-matters, with a bichromate and
sulphuric acid, blueish black shades are obtained.
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:
PRODUCTION OF PARA-DINITRO-PHENOXY-ORTHO-PARA DINITRO-DIPHENYLAMINE META
SULPHOACID.
Dissolve about nineteen parts of para amido phenol ortho sulpho acid in about
one hundred and forty parts of water containing five and a half parts of calcined
soda. Add to the mixture ten and a half parts more calcined soda and forty one
parts of dinitro-chlor benzene. Boil this mixture for about three hours, or until
the dinitro-chlor benzene has practically disappeared, in a vessel provided with
an inverted condenser. The product of the reaction, in the form of its sodium
salt separates out on cooling as light yellow brilliant crystallized flakes. It
dissolves in hot water and alcohol crystallizing out on cooling.

page_text: JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.
COMPLETE SPECIFICATION.
The Manufacture and Production of New Colouring Matters and of
Products for use therein.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been
The Manufacture and Production of New Colouring Matters and of
Products for use therein.
I, JAMES YATE JOHNSON, of 47, Lincoln's Inn Fields, in the County of London,
Gentleman, do hereby declare the nature of this invention (which has been

page_text: 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:---
It is known that if para-amido-phenol be treated with one molecular proportion
of dinitro-chlor-benzene, or dinitro-brom-benzene in the presence of suitable
reagents for binding acids, such as soda, sodium acetate, and the like, the
corresponding para-hydroxy-ortho-para-dinitro-diphenylamine is obtained. (See
Nietzki and Simon, Berichte, 1895, page 2973). In the same way the corre-
sponding compound can be obtained from para-amido-phenol-ortho-sulpho acid.
My foreign correspondents have discovered that the said hydroxy-dinitro-
diphenylamine derivative can be combined with a further molecular proportion
of dinitro-chlor-benzene, so that phenol-ethers are obtained. These presumably
possess the constitution indicated by the following formulae:-
It is unnecessary to effect the condensations with the dinitro-chlor-benzene, or.
its equivalent, in two phases. The para-amido-phenol, or its sulphoacid, can,
in one operation, be combined with two molecular proportions of dinitro-chlor-
benzene in the presence of, for instance, soda, and the desired new products be.
obtained.
Again, other nitrated phenol-ethers can be obtained similarly by treating the
para-hydroxy-ortho-para-dinitro-diphenylamine derivative with ortho-nitro-
chlor-benzene-para-sulphoacid, or with para-nitro-chlor-benzene-ortho-sulphoacid.
Judging from the method of formation the constitution of these bodies would be
indicated by the following formulae.

page_text: Dissolve about twenty-eight parts of para-hydroxy-ortho-para-dinitro-dipheny
lamine in about one hundred and twenty parts of water containing about four
parts of caustic soda. Add a solution of about twenty-six parts of sodium salt
of ortho-nitro-chlor-benzene-para-sulphoacid in one hundred parts of water. Boil
the mixed solutions for about four hours in a vessel furnished with an inverted
condenser. The main quantity of the reaction product separates out on cooling.
Collect by filtration. The product thus obtained is a golden-yellow crystalline
powder soluble in hot water and separating out again on cooling.
In this example an analogous product can be obtained when using the isomeric
para-nitro-benzene ortho-sulphoacid.

page_text: PRODUCTION OF A NEW. COLOURING MATTER.
Mix together about forty parts of sodium salt of para-dinitro-phenoxy-ortho-
para-dinitro-diphenylamine-meta-sulphoacid, (such as can be obtained by working
in accordance with the foregoing Example 2), with eighty parts of sulphur and
two hundred parts of crystallised sodium sulphide. Melt this mixture, in an
iron pot furnished with a stirrer, at a temperature of about one hundred and
forty degrees Centigrade. When the mass no longer froths up but turns solid
the reaction may be regarded as ended. Allow the mass to cool and reduce it
to powder. This powder can be directly used in dyeing. It is readily soluble
in water, the solution being blue-green, and, from it, common salt, or ammonium
chloride, precipitates blue-green flocks, and hydrochloric acid produces a yellow-
brown flocculent precipitate. The colouring matter yields green-black shades on
unmordanted cotton, and these shades possess extraordinary fastness against acids,
alkalies, and soap.
Upon after treatment with bichromate and sulphuric acid beautiful blueish-
black shades are obtained which resist, to an excellent degree, the action of soap,
chlorine, and sulphur fumes.
In a similar manner colouring matters are obtained from the other new con-
densation products hereinbefore indicated. The conditions of working, such as
the temperature of melting, can be varied, in all cases, without departure from
the nature of this invention.
Having now particularly described and ascertained the nature of this invention
and in what manner the same is to be performed I declare that what 1 claim is :-
1. The manufacture of nitrated phenol ethers by the condensation of the
bereinbefore defined hydroxy-dinitro-diphenylamine, or its sulphoacid, with
dinitro-chlor-benzene, or dinitro-brom-benzene, substantially as hereinbefore
described.
2. The manufacture of nitrated phenol-ethers by the condensation of para-
amido-phenol, or its sulphoacid, with two molecular proportions of dinitro-chlor-
benzene, or dinitro-brom-benzene, substantially as herein before described.
3. The manufacture of nitrated phenol-ethers by condensing para-hydroxy-
dinitro-diphenylamine, or its sulphoacid, with a nitro-chlor-benzene-sulphoacid,
substantially as herein before described.
4. The manufacture of new colouring matters by treating the nitrated phenol-
ethers herein before defined with sodium sulphide and sulphur, substantially as
herein before described.
5. The manufacture of nitrated phenol-ethers, and of new colouring matters,
Jubstantially as herein before described in the several examples.
6. As new articles of manufacture the nitrated phenol-ethers, and the new
colouring matters, such as can be obtained substantially as hereinbefore described
and claimed.
Dated this 24th day of Imamat 1000
JOHNSONS & WILLCOX,
47, Lincoln's Inn Fields, London, W.C., Agents.