IMPROVEMENTS IN PREPARING AND OBTAINING COLOURING MATTERS
Year: 1870

page_text: LETTERS PATENT to Charles Bardy, of Boulevard de Strasbourg, 23,
à Paris, Chemist, for the Invention of "IMPROVEMENTS IN PREPARING
AND OBTAINING COLOURING MATTERS."
Sealed the 19th July 1870, and dated the 9th February 1870.
PROVISIONAL SPECIFICATION left by the said Charles Bardy at the
Office of the Commissioners of Patents, with his Petition, on the
9th February 1870.
I, CHARLES BARDY, of Boulevard de Strasbourg, 23, à Paris, Chemist,
5 do hereby declare the nature of the said Invention for "IMPROVEMENTS
IN PREPARING AND OBTAINING COLOURING MATTERS," to be as follows:-
The new colouring matters which I obtain have for their base a new
substance, which I term "methyldiphenylamine." I obtain this sub-
stance by reacting upon diphenylamine or its salts, cither with methylic
alcohol or with the combination of this alcohol with different substances.
which afford substitution products. This reaction takes place at variable
S

page_text: temperatures according to the substances employed. Thus the diphenyl-
amine (a weak base) reacts under pressure at 212° Fahrenheit upon
iodide of methyle. A crystallized hydrate of iodine is obtained, which
when treated with a caustic alkali gives a new base. This reaction
succeeds very well without pressure, but in that case the vapours must
be made to flow off. The hydrochlorate of diphenylamine on the con-
trary only reacts under pressure upon methylic alcohol at a temperature
of from 450° to 540° Fahrenheit. The product is treated, as before, with
a caustic alkali. Whatever process may be employed the new base
presents itself in the form of an oily substance, even at 32° Fahrenheit,
of which the boiling point is near that of diphenylamine. It is very
easily distinguished from diphenylamine by the fact that under the
influence of nitric acid it develops a colour identical with that of the
aqueous solution of permanganate of potash, whereas the other base
under the same influence assumes a blue colour.
For transforming the new alkaloid into colouring matters I react upon
it with all substances capable of eliminating bydrogen, whether directly
or indirectly, to which reactions the base very readily submits.
Thus
I obtain blue or violet or a mixture of both in reacting at variable
temperatures according to the energy of the reagent employed with the
following substances :-Arsenic acid, metallic nitrates, or mixtures of the
same, haloid salts of metals, the iodide and chlorate of potassa, sesqui-
chloride of carbon, picric acid, and in fact all substances capable of
eliminating hydrogen and of grouping the residues without destruction
into another form. The nitrate of mercury, for instance, reacts upon
methyldiphenylamine at a temperature of about 104° Fahrenheit, and
the reaction is so powerful that sometimes the mixture begins to burn.
The perchloride of iron at a temperature near 212° Fahrenheit rapidly
transforms the base into a resinous substance of a brownish red tint, but
which when dissolved in alcohol becomes a pure blue. The methyl-
diphenylamine if heated to from 374° to 392° Fahrenheit with sesqui-
chloride of carbon gives in a very short time a resinous substance which
affords a reddish blue colour when dissolved in alcohol. Hydrochloric
acid precipitates the pure blue of this solution, while a violet colour
remains in the mother liquor.
The proportions of the reagents are not fixed; they may vary between

page_text: The new colouring matters obtained are purified by known processes
employed for the purification of aniline colours; they act directly as
dyes.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said Charles Bardy in the Great Seal Patent Office on
the 21st July 1870.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CHARLES
BARDY, of Boulevard de Strasbourg, 23, à Paris, Chemist, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Ninth day of February, in the year
of our Lord One thousand eight hundred and seventy, in the thirty-
third year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said Charles Bardy, Her special licence
that I, the said Charles Bardy, my executors, administrators, and
assigns, or such others as I, the said Charles Bardy, my executors,
administrators, and assigns, should at any time agree with, and no
others, from time to time and at all times thereafter during the term
therein expressed, should and lawfully might make, use, exercise, and
vend, within the United Kingdom of Great Britain and Ireland, 'the
Channel Islands, and Isle of Man, an Invention for “IMPROVEMENTS IN
PREPARING AND OBTAINING COLOURING MATTERS," upon the condition (amongst
others) that I, the said Charles Bardy, my executors or administrators,
by an instrument in writing under my, or their, or one of their hands
and seals, should particularly describe and ascertain the nature of the
said Invention, and in what manner the same was to be performed,
and cause the same to be filed in the Great Seal Patent Office within six
calendar months next and immediately after the date of the said Letters.
Patent.
NOW KNOW YE, that I, the said Charles Bardy, do hereby declare
the nature of the said Invention, and in what manner the same is to
be performed, to be particularly described and ascertained in and by
the following statement thereof, that is to say :-
The new colouring matters which I obtain have for their base a new
substance which I term "methyldiphenylamine."
I obtain this sub-

page_text: -
stance by reacting upon diphenylamine or its salts, either with methylic
alcohol or with the combination of this alcohol with different substances.
which afford substitution products. This reaction takes place at variablo
temperatures according to the substanees employed. Thus the diphenyl-
amine (a weak base) reacts under pressure at 212° Fahrenheit upon iodide
of methyle. A crystallized hydrate of iodine is obtained, which when
treated with a caustic alkali gives the new base. This reaction succeeds.
very well without pressure, but in that case the vapours must be made
to flow off. The hydrochlorate of diphenylamine on the contrary only
reacts under pressure upon methylic alcohol at a temperature of from
482 to 572° Fahrenheit. The product is treated, as before, with a
caustic alkali. Whatever process may be employed the new base
presents itself in the form of an oily substance at the ordinary tem-
perature, and even at 32° Fahrenheit, of which the boiling point is near
that of diphenylamine. It is very easily distinguished chemically from
diphenylamine by the fact that under the influence of nitric acid it
develops a colour identical with that of the aqueous solution of per-
manganate of potash, whereas the other base under the same influence
assumes a blue colour.
For transforming the new alkaloid into colouring matters I react upon
it with all substances capable of eliminating hydrogen, whether directly
or indirectly, to which reactions the base very readily submits. Thus
I obtain blue or violet, or a mixture of both, in reacting at variable
temperatures according to the energy of the reagent employed with the
following substances :-Arsenic acid, metallic nitrates, or mixtures of the
same, haloid salts of metals, the iodide and chlorate of potassa, sesqui-
chloride of carbon, picric acid, and in fact all substances capable of
eliminating hydrogen and of grouping the residues without destruction
into another form. The nitrate of mercury, for instance, reacts upon
methyldiphenylamine at a temperature of about 101° Fahrenheit, and
the reaction is so powerful that sometimes the mixture begins to burn.
The perchloride of iron at a temperature near 212° Fahrenheit rapidly
transforms the base into a resinous substanco of a brownish red tint, but
which when dissolved in alcohol becomes a pure blue. A mixture of
1 part methyldiphenylamine, 0.5 part iodine, and 2 parts chlorate of
potash heated firstly to about 140° Fahrenheit, and then to from 212" to
248° Fahrenheit to complete the reaction, gives a brownish product very
rich in colouring matter. The soluble salts are removed by washing

page_text: with boiling water, and afterwards the iodine by treating with alkalies.
The methyldiphenylamine, if heated to from 374° to 392° Fahrenheit with
sesquichloride of carbon, gives in a very short time a resinous substance
which affords a reddish blue colour when dissolved in alcohol. Hydro-
chloric acid precipitates the pure blue of this solution, while a violet
colour remains in the alcoholic mother liquor.
The proportions of the reagents are not absolute; they may vary
between wide limits without preventing the production of the new
colouring matters.
The new colouring matters obtained are purified by known processes
employed for the purification of aniline colours. They act directly as
dyes.
Having thus described the nature of my Invention, and in what
manner the same is to be performed, what I claim under the herein-
before in part recited Letters Patent is,—
First. The production of the new substance termed methyldiphenyl-
amine, herein-before described.
Second. The application of the said substance to the production of
colouring matters, whether blue, violet, or mixtures of these.
Third. The application of such colouring matters to industrial
purposes.
In witness whereof, I, the said Charles Bardy, have hereunto set
my hand and seal, this Fourteenth day of July, in the year of
our Lord One thousand eight hundred and seventy.
Witnesses,
C. LAFOND,
Civil Engineer,
23, Boulevart de Strasbourg,
Paris.
CH. BARDY. (L.S.)