IMPROVE- MENTS IN THE MODE OF PRODUCING CERTAIN COLOURING MATTERS
Year: 1878

page_text: LETTERS PATENT to William Spence, of S, Quality Court, Chancery Lane,
in the County of Middlesex, Patent Agent, for the Invention of "IMPROVE-
MENTS IN THE MODE OF PRODUCING CERTAIN COLOURING MATTERS." A
communication from abroad by Adolphe Herran, of Paris, Mining Engineer,
and Alfred Chaudé, of Yerres, Seine et Oise, France, Chemist.
PROVISIONAL SPECIFICATION left by the said William Spence at the
Office of the Commissioners of Patents on the 23rd October 1878.
WILLIAM SPENCE, of S, Quality Court, Chancery Lane, in the County of
Middlesex, Patent Agent. "IMPROVEMENTS IN THE MODE OF PRODUCING CERTAIN
COLOURING MATTERS." A communication from abroad by Adolphe Herran, of
Paris, Mining Engineer, and Alfred Chaudé, of Yerres, Seine et Oise, France,
Chemist.
This Invention has for its principal object the production of fuschine without the
use of arsenic acid, so injurious to health, and which renders the manufacture of this
colouring matter dangerous in many cases. It is also intended to produce this
colouring matter at a more remunerative price and with better proceeds than by
the ordinary processes.
And the Invention consists in obtaining blue, red, and grey colouring substances
by the treatment of aniline, or a superior homologue like toluidine, by a simple or
double metallic chloride, the combination thus formed having added to it nitro-
benzoline, or an homologue, the whole being heated; then the result of the operation
being treated with hot water when red colour is to be extracted; with sulphuric
acid of Nordhausen or concentrated sulphuric acid, when it is desired to obtain blue
and grey colour, in the condition of soluble sulpho-compound products. The said
process is based on the following chemical re-actions :-If aniline or its homologues,
or a mixture of these bodies, be taken and treated with a simple or a double chloride
[Price Adl

page_text: anhydrous or nearly anhydrous, there results a combination with a great number of
these chlorides. If these combinations be treated with nitro-benzine, binitro-
benzine, or their homologues, and heated at a temperature of from 140 to 210 degrees
Centigrade, according to the nature of the chlorides and of the bodies brought in
contact, colouring matters are formed. The combinations of pure aniline] with
simple or double chorides treated with nitro-benzine or binitro-benzine produce
colouring matters insoluble in water, but these matters treated with the acid of
Nordhausen or with concentrated sulphuric acid yield sulpho-compound products of
blue colour soluble in water. The combinations of the superior homologues of
aniline with the simple or double chlorides treated with nitro-benzine or binitro-
benzine or their homologues produce red and grey colouring matters which can be
separated by hot water, the red being soluble, the grey not being so.
matters treated with the acid of Nordhausen, or concentrated sulphuric acid, yield
sulpho-compound products which are soluble in water. A mixture of aniline or its
homologues with nitro-benzoline, binitro-benzoline, or their homologues, treated with
simple or anhydrous or nearly anhydrous chlorides, yields equally blue, red, and'
grey colouring matters.
The grey
The chlorides to be employed are the following:-Protochloride of antimony,
perchloride of antimony, chloride of aluminium, protochloride of iron, perchloride
of iron, chloride of zinc, sesquichloride of chromium, bichloride of titanium, proto-
chloride of tin, bichloride of tin, bichloride of copper.
Also the double chlorides formed by the union of any metallic chloride with one
of the following chlorides-Chloride of aluminium, perchloride of iron, sesqui-
chloride of chromium, bichloride of titanium, bichloride of tin. These double
chlorides may be obtained in the anhydrous or nearly anhydrous state by inixing
hot and concentrated solutions of the simple chlorides which serve to form them!
using heat in order to evaporate the water.
Any one of these simple or double chlorides may be employed in applying this
Invention, but for economy and for better product preference has hitherto been
given to double chlorides, and particularly to the double chloride of aluminium and
magnesium, the double chloride of aluminium and calcium, the double chloride of
aluminium and manganese, the double chloride of aluminium and zinc, the double
chloride of aluminium and sodium, the double chlorides formed by the union of per-
chloride of iron and proto-chloride of iron, perchloride of iron and chloride of man-
ganese, per-chloride of iron and chloride of magnesium.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said William Spence in the Great Seal Patent Office on the 23rd
April 1879.
WILLIAM SPENCE, of 8, Quality Court, Chancery Lane, in the County of
Middlesex, Patent Agent. "IMPROVEMENTS IN THE MODE OF PRODUCING CERTAIN
COLOURING MATTERS." A communication from abroad by Adolphe Herran, of
Paris, Mining Engineer, and Alfred Chaudé, of Yerres, Seine-et-Oise, Chemist.
This Invention of "Improvements in the Mode of Producing certain Colouring
Matters" consists in the production of red, red-violet, orange-red, violet blue,
and grey colouring matters by the action of double metallic chlorides on anilino
or its homologues in presence of nitro-benzine or binitro-benzine or their
homologues or nitronaphtaline.
The process is based on the following chemical re-actions:-If aniline or its
homologues, or a mixture of these bodies, be taken and treated with a double
metallic chloride, anhydrous or containing water of crystallization or hygroscopic
water, there is a combination with a great number of these double chlorides.
If these combinations be treated with nitrobenzine, or binitrobenzine, or their
homologues, or their products of substitution, or nitronaphtaline, and heated at
tomperatures varying from one hundred and fifty to two hundred and ten
degrees Centrigrade, according to the nature of the double chlorides and of the
bodies brought in contact, colouring matters are formed.
The combinations of pure aniline with the double chlorides treated with
pure nitrobenzine or pure binitrobenzine give rise to colouring matters in-
soluble in water, but these matters treated with concentrated sulphuric acid,
either ordinary or containing sulphuric anhydride, yield sulphoconjugated pro-
ducts of blue grey or violet-tinted colour, the alkaline salts of which are soluble
in water.
The combinations of pure aniline with the double chlorides treated with nitro-
naphtaline give rise to a colouring matter of a vinous red, soluble in water,
and to another colouring matter insoluble, which treated with sulphuric acid
yields sulphoconjugated products of violet colour, the alkaline salts of which
are soluble in water.
The combinations of the superior homologues of aniline with the double chlorides
treated with nitrobenzine or binitrobenzine, or their homologues, give rise to red
and grey colouring matters which can be separated by the aid of hot water, the reds
being soluble, the greys being scarcely if at all so. The grey matters treated with
concentrated sulphuric acid, either ordinary or containing sulphuric anhydrate,
yield sulphoconjugated products, the salts of which are soluble in water.
The combinations of toluidine with the double chlorides treated with nitro-
naphtaline give rise to red-violet and violet colouring matters which are separated.
by the aid of hot water, the red-violet being soluble, the violet not so, or scarcely
so. The violet colouring matters treated with sulphuric acid yield sulphoconjugated
products, the salts of which are soluble in water.
The double chlorides to be employed are the following:-The double chlorides.
formed by the union of any metallic chloride with one of the following chlorides, —
chloride of aluminium, perchloride of iron, sesquichloride of chromium, bichloride
of titanium, bichloride of tin, perchloride of antimony.
These double chlorides may be obtained in a suitable condition by mixing hot
and concentrated solutions of the simple chlorides which serve to form them, and
using heat in order to evaporate the water as much as possible.
Any one of these double chlorides may be employed in applying this Invention,
but for economy and for a better yield preference has hitherto been given to the
double chlorides or mixture of the double chlorides following, that is to say,-
double chloride of aluminium and, magnesium, double chloride of aluminium and

page_text: calcium, double chloride of aluminium and manganese, double chloride of aluminium
and iron, double chloride of aluminium and zine, double chloride of aluminium and
sodium, double chloride of perchloride of iron and protochloride of iron, double
chloride of perchloride of iron and chloride of manganese, double chloride of per-
chloride of iron and magnesium, double chloride of perchloride of iron and zinc,
double chloride of perchloride of iron and calcium.
The above named double chlorides can be equally obtained in a suitable condition
by mixing their hot and concentrated solutions, and causing their evaporation in
vacuo at a temperature of about one hundred degrees.
In order that this Invention, and the mode of applying it, may be more fully 1
understood, the detailed operations will now be described by way of example, by
which can be obtained the blues with aniline, the reds, red-violets, and violets with
aniline and nitronaphtaline, the reds and the greys with toluidine or any other
superior homologue of aniline.
In order to obtain blue there are taken two parts of pure aniline and one part to 1
a part and a half of a double chloride in the above-nanied conditions, for instance,
the double chloride of aluminium and zinc. There is an intimate mixture made,
and heat applied until the beginning of evaporation of the alkaloid in order to
facilitate the reaction and drive out the water, then there is introduced about a
part to a part and a quarter of pure nitro-benzine; heat is applied at a temperature 2
of from one hundred and sixty degrees to one hundred and ninety degrees
centigrade for a period of about two hours, care being taken to stir constantly.
This is allowed to cool, and the mass is treated with concentrated sulphuric and
either ordinary or containing sulphuric anhydride until completely dissolved, then
the mass is poured slowly into a small quantity of water; the sulphates of the 2
metals remain dissolved in the liquor, and the sulpho-conjugated colouring matter
is precipitated, and is collected by the ordinary means.
In order to obtain red-violet there is taken about two parts of pure aniline and
one part and a quarter to a part and a half of a double chloride in the condi-
tions above named, for instance, the double chloride of aluminium and manganese; 3
an intimate mixture is made and heated until the beginning of evaporation of the
alkaloid in order to facilitate the reaction and drive out the water, then there is
introduced about a part and a half to a part and three-quarters of nitro-naphtaline,
and heat is applied at a temperature of about one hundred and eighty degrees for
about an hour and a half, care being taken to keep the mass well stirred until a 3
sample assumes a bronzed appearance and breaks after cooling. The mass is then
treated with hot water, which dissolves the red-violet which is precipitated by the
aid of common salt. As to the insoluble part it is treated with sulphuric acid until
dissolved, then the mass is poured into a small quantity of water, the sulphates of
the metals remain dissolved in the liquor, and the sulpho-conjugated violet 4
colouring inatter is precipitated, and is collected by ordinary means.
In order to obtain red and grey there are taken about two parts of toluidine of
commerce, one part to one part and a half of a double chloride or a mixture of
double chlorides, for instance, the double chloride of aluminium and protochloride
of iron; these are carefully mixed and heated until the beginning of evaporation of 4
the alkaloid, and there is added about a part and a quarter of pure nitro-benzine,
or a part and a half of nitrotoluene. Heat is applied at a temperature of one
hundred and ninety degrees centigrade until the mass becomes a paste and a
sample taken out assumes a bronzed appearance and breaks after cooling; the
result of this operation is a mixture of red and grey, which is treated with boiling 50
water. The red is insoluble and crystallizes, the grey which has remained insoluble
is treated with concentrated sulphuric acid, ordinary or containing sulphurić
anhydride, as herein-before stated, and the product sulpho-conjugated grey which
results from it is treated like the blue and violet in the preceding operations.
If instead of taking in these different operations aniline and toluidine there are 55
taken their anhydrous hydrochlorates, or the mixture of these alkaloids and their
anhydrous hydrochlorates, and these are treated as described with nitro-benzine or

page_text: nitro-toluene and the double chlórides, colouring matters are formed. These
colouring matters are blue when a reaction takes place between the hydrochlorate
of aniline or mixture of hydrochlorate of aniline and aniline and pure nitro-benzine
and double chlorides; they are red when it is the hydrochlorate of toluidine or
mixture of hydrochlorate of toluidine and of toluidine that is caused to react with
nitrotoluene or nitro-benzine and the double chlorides.
The quantity of double chlorides to be employed in these different cases is less
than that shewn in the instances cited, and so much less as the proportion of
hydrochlorate in the mixture is stronger.
In all the different operations for red orange-tinted reds can be obtained with the
greatest facility; it is sufficient for that purpose to prolong a little the action of the
heat, and afterwards to submit the whole mass to a very slow cooling.
Having thus described the nature of the said Invention communicated to me
from abroad as aforesaid, and in what manner the same is to be performed, I
hereby declare that what I claim as of the said Invention is,-The mode or modes
described of obtaining colouring matters, red, red-violet, orange-red, blue, violetish
and grey in the following manner, that is to say, the treatment of aniline or one of
its homologues or a mixture of these bases or their anhydrous hydrochlorates or
mixture of their anhydrous hydrochlorates and their bases with the metallic double
chlorides, the transformation of the combinations thus formed by the treatment?
with nitrated aromatic bodies or substances at a high temperature into colouring
matters, red, red-violet, orange red, blue, violetish and grey, the separation of which
is effected in the manner herein-before described.
In witness whereof, I, the said William Spence, have hereunto set my hand
and seal, this Twenty-third day of April, in the year of our Lord One
thousand eight hundred and seventy-nine.
Witness,
FRANK REDMAN,
8, Quality Court,
Chancery Lane.
WILLIAM SPENCE. (L.S.)
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