IMPROVEMENTS IN THE MANUFACTURE OF COLOURING MATTERS
Year: 1866

page_text: LETTERS PATENT to. Clinton Edgcumbe Brooman, of the Firm of
Robertson, Brooman, and Company, of 166, Fleet Street, in the City of
London, Patent Agents, for the Invention of "IMPROVEMENTS IN THE
MANUFACTURE OF COLOURING MATTERS."-A communication from abroad.
hy Charlos Louth of Ponia Timenca
PROVISIONAL SPECIFICATION left by the said Clinton Edgcumbe Brooman
at the Office of the Commissioners of Patents, with his Petition, on the
5th December 1866.
I, CLINTON EDGCUMBE BROOMAN, of the Firm of Robertson, Brooman, and
Company, of 166, Fleet Street, in the City of London, Patent Agents, do hereby
declare the nature of the said Invention for "IMPROVEMENTS IN THE MANU-
PACTURE OF COLOURING MATTERS," to be as follows:-
In the year 1861 the present Inventor, Charles Lauth, published several works
upon methylaniline, and shewed that the introduction of methylene (CH³,)
into aniline communicates to the latter the property of giving violet colouring
matters under the influence of agents which with aniline would produce
red colouring matters; later M. Hoffmann carrying out the same principle
showed that analogous colours could be produced by reversing M. Lauth's
process, that is to say, by first producing the red colouring matter and
afterwards introducing alcoholic radicals; more recently Messrs. Poirrier and
Chappat, recurring to M. Lauth's works of 1861, have shown some new
reactions of methylaniline and a method of transforming it into violet.

page_text: Now this Invention consists in certain processes relating to this manufacture.
When different salts of methylaniline are submitted to the action of heat
they produce violet.
I take for example one part of methylaniline or dimethylaniline, or a
mixture of these two bases, and mix it with a half part of hydrochloric acid
and ten times its weight of sand; the mixture is then heated to about 245°
or 250° Fahrenheit, and this temperature is kept up until the mass becomes
a beautiful deep violet, at this moment it is treated by water, which casily
dissolves the colouring matter, and the product is purified by the processes
ordinarily employed in the manufacture of colour from aniline; oxydizing
agents give similar results, the greater part of those used in the manufacture
of rosaniline may be successfully adopted, but those which produce the best
results are nitrate of copper, which is employed in about the proportion of
half the weight of methylaniline or acetate of mercury which is made to
react in the same proportions upon acctate of methylaniline, the formation of
violet takes place at about 212° Fahrenheit.
The proportions I have mentioned, the temperature, and the length of the
operation, will vary according to the more or less blue shade desired to be
obtained.
This Invention therefore consists in the formation of colouring matters
obtained by the decomposition of the salts of methylaniline by means of
heat, or by the oxidation of methylaniline under the influence of oxygenated
compound such as and analogous to nitrate of copper, acid acetate of mercury,
and other oxidizing agents.
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Clinton Edgcumbe Brooman in the Great Seal Patent Office
on the 5th June 1867.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, CLINTON
EDGCUMBE BROOMAN, of the Firm of Robertson, Brooman, and Company,
of 166, Fleet Street, in the City of London, Patent Agents, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Fifth day of December, in the year of our Lord
One thousand eight hundred and sixty-six, in the thirtieth year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto me, the said
Clinton Edgcumbe Brooman, Her special licence that I, the said Clinton
Edgcumbe Brooman, my executors, administrators, and assigns, or such others

page_text: as I, the said Clinton Edgcumbe Brooman, 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 THE MANUFACTURE OF COLOURING MATTERS," (communicated
to me from abroad by Charles Lauth, of Paris, France,) upon the condition
(amongst others) that I, the said Clinton Edgcumbe Brooman, 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 Clinton Edgcumbe Brooman, 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, that is to say :-
In the year 1861 the present Inventor, Charles Lauth, published several
works upon the obtaining commercially of a fine violet colouring matter
derived from methylaniline, and indicated that this product would die silk,
wool, or cotton, and if he did not continue the manufacture it was only he
states because it was found at that time that this colour did not sufficiently
resist the action of air; later Mr. Hofmann produced colours analogous to
those of Mr. Lauth by reversing the latter's process, that is to say, by
introducing one of the alcoholic radicals into rosaniline; more recently
Messrs.Poirrier and Chappat have shewn several new processes for obtaining
violet from methylaniline..
Now this Invention consists in certain processes relating to this manufacture.
When a salt of methylaniline, particularly a hydrochlorate in the presence of
an excess of base, is submitted to the action of heat it is transformed into
violet; for this reaction, and for those following, I add sand in sufficiently
large quantity.
The following is my mode of operating:-One part of methylaniline, or of
dimethylaniline, or of a mixture of these two bases is mixed with a half part
of hydrochloric acid of commerce, and about ten times its weight of sand, this
mixture is heated in an open vessel to a temperature of about 245° or 250
Fahrenheit, and the temperature is kept up until the mass becomes hard and
of a dusky or bronzed appearance, which takes place in about from 5 to 8 hours.

page_text: The whole is withdrawn and thrown into boiling water, about 100 times the
weight of the methylaniline employed, the violet is dissolved therein, it is
filtered, some sea salt is added to the liquor, and the colour is precipitated in
the state of a brilliant greenish mass which is the commercial product, nothing
further is necessary than to dry it. The dry product re-dissolves in hot
water, and dyes silk, wool, or cotton, the two first without acid, or mordant,
the last by the processes usually employed for aniline dyes. I also transform
methylaniline or dimethylaniline into violet by other processes, by mixing them
with nitrate of copper or chloride of copper in the proportion of one part
of methylaniline or dimethylaniline, or of a mixture of these two bases, and
a half part of salt of copper, and by operating in the same manner as for hydro-
chlorate of methylaniline only it is not necessary to heat to a temperature
beyond 212° Fahrenheit, the reaction even takes place below this temperature.
I employ under the same conditions of proportion, temperature, &c.
mercurial acetate, which is made to react on acetate of methylaniline.
Lastly, aqua regia employed in the proportion of 50 per cent. of the weight of
the alkaloid transforms it into violet at a temperature of about 245° or 250°;
ferric sulphate employed under the same conditions give the same results.
The quantities described, the temperature, and the length of the operation may
be more or less varied.
9.
And having now described the nature of the said Invention, and in what
manner the same is to be performed, I declare that I claim the manufacture
of violet colouring matters from methylaniline or from dimethylaniline, or
from a mixture of these two bases, by either of the processes herein-before
described, that is to say, by heating a salt of methylaniline or of dimethyl
aniline, or of a mixture of these two bases, particularly a hydrochlorate, or by
heating one of the salts herein-before indicated, viz., nitrate of copper, chloride
of copper, and ferric sulphate with methylaniline or with dimethylaniline,
or with a mixture of these two bases, or mercurial acetate with the acetate of
these alkaloids, or aqua regia with these alkaloids.
In witness whereof, I, the said Clinton Edgcumbe Brooman, have here
unto set my hand and seal, the Thirty-first day of May, One thousand
eight hundred and sixty-seven.
C. E. BROOMAN. (L.S.)