IMPROVEMENTS IN THE TREATMENT OF AROMATIC SECONDARY MONAMINES FOR OBTAINING COLORING MATTER
Year: 1869

page_text: LETTERS PATENT to George Tomlinson Bousfield, of Loughborough,
Park, Brixton, in the County of Surrey, for the Invention of.
"IMPROVEMENTS IN THE TREATMENT OF AROMATIC SECONDARY MONAMINES
FOR OBTAINING COLORING MATTER."-A communication from abroad
by Adam Charles Girard, Chemist, and Georges Ernest Camille de
Laire, Chemist, residing at Paris, in the Empire of France.
Sealed the 24th May 1870, and dated the 18th December 1869.
PROVISIONAL SPECIFICATION left by the said George Tomlinson
Bousfield at the Office of the Commissioners of Patents, with his
Petition, on the 18th December 1869.
I, GEORGE TOMLINSON BOUSFIELD, of Loughborough Park, Brixton,
in the County of Surrey, do hereby declare. the nature of the said '
Invention for "IMPROVEMENTS IN THE TREATMENT OF AROMATIC SECONDARY
MONAMINES FOR OBTAINING COLORING MATTERS," a communication from
abroad by Adam Charles Girard, Chemist, and Georges Ernest Camille.
de Laire, Chemist, two persons resident at Paris, in the Empire of.
France:-
This Invention consists, firstly, in preparing new non-coloring sub-
stances derived from methylaniline, methyltoluidine, diphenylamine,.

page_text: phenyltoluylamine, ditoluylamine, and homologous substances by intro-
ducing amidst these aromatic secondary monamines an aromatic or other
alcoholic radical, such as the benzyle, the tolyle, for instance.
Secondly. In transforming the said substances, which are from them-
selves non-coloring, into coloring matters applicable to dyeing and
printing purposes.
To this end I heat into a digesting apparatus from one part and a half
to three parts of chloride or bromide of benzyle, tolyle, or homologous
for one part of methylaniline under a pressure of about three atmo-
spheres, and at a temperature of 210° Centigrades (410° Fahr.), or in
the same apparatus and under a pressure of one atmosphere, a mixture
of one part and a half chloride of benzyle for two parts of diphenylamine
or ditoluylamine, or homologous. The operation will last three hours at
most. The product of the reaction is the chlorhydrate of these new
bases. This may be employed directly for producing coloring matters.
It may, however, be purified also in being treated by caustic soda in
aqueous dissolution, washing then with water, so as to remove the excess
of alkali, and purify the bases thus obtained through cristallization &
distillation.
In order to transform into coloring matters the chlorhydrate or brom-
hydrate, and principally that of méthylbenzylphénylamine, which yields
a beautiful coloring matter, violet-blue or blue-violet, I cause to react by
a temperature well maintained and long kept on one of these oxydizing
mixtures well known in trade and industry nowadays, and used daily to
produce the aniline black in printing, as, for instance, a mixture of
chlorate of potash or bi-chromate of potash, and bi-sulphate of potash or
sulphate of copper in presence of water and of an inert body which
divides the mass. I may also, to transform into coloring matters the
same bases, cause to react upon them the sesqui-chloride of carbon, or
any other body able of removing hydrogen, in which case I heat between
about 140° and 180° Centigrades (284" and 356° Fahr.). The operation
will last for three hours. In these conditions the benzyldiphénylamine
yields a beautiful coloring matter blueish-green or greenish-blue, the
benzylphenyltoluylamine yields blue and violet matters, the methyl-
benzyltoluylamine coloring matters of orange hue, and the benzyl-
ditoluylamine coloring matters of chestnut hue. As the chlorides,
bromides of benzyle and tolyle and homologous, though existing in
trade already, are not yet, however, in general use, I deem it useful to

page_text: observe in this place that these bodies are obtained in causing to pass
into the vapors of the toluene, xylene, or homologous bodies when in
ebullition a stream of chlorine or brome in the state of vapors.
SPECIFICATION in pursuance of the conditions of the Letters Patent,
filed by the said George Tomlinson Bousfield in the Great Seal
Patent Office on the 18th June 1870.
TO ALL TO WHOM THESE PRESENTS SHALL COME, I, GEORGE
TOMLINSON BOUSFIELD, of Loughborough Park, Brixton, in the County
of Surrey, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her
Letters Patent, bearing date the Eighteenth day of December, in the
year of our Lord One thousand eight hundred and sixty-nine, in the
thirty-third year of Her reign, did, for Herself, Her heirs and successors,
give and grant unto me, the said George Tomlinson Bousfield, Her
special licence, that I, the said George Tomlinson Bousfield, my exe-
cutors, administrators, and assigns, or such others as I, the said George
Tomlinson Bousfield, 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 TREATMENT OF AROMATIC SECONDARY
MONAMINES FOR OBTAINING COLOURING MATTER," a communication to me from
abroad by Adam Charles Girard, Chemist, and Georges Ernest Camille
de Laire, Chemist, two persons resident at Paris, in the Empire of
France, upon the condition (amongst others) that I, the said George
Tomlinson Bousfield, 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 George Tomlinson Bousfield, do
hereby declare the nature of the said Invention, and in what manner the

page_text: same is to be performed, to be particularly described and ascertained in
and by the following statement thereof, that is to say :-
This Invention relates, firstly, to preparing new non-colouring sub-
stances derived from methylaniline, methyltoluidine, diphenylamine, and
phenyltoluylamine, ditoluylamine, and their homologues by introducing
amidst any or either of these aromatic secondary monamines any suitable
aromatic alcoholic radical, such as, for instance, the radical called benzyle,
or the radical styled tolyle.
Secondly. The Invention consists in converting these substances,
which are of themselves colourless, non-colouring, into colouring matters
and pigments applicable to dyeing and printing purposes, such trans-
formation being effected by subjecting said substances to the action of
bodies capable of oxidizing, removing, or eliminating hydrogen.
I first describe the preparation of methylbenzylphenylamine and the
like bases. I heat in a digesting apparatus from one part and a half to
three parts of chloride or bromide of benzyle, tolyle, or their homologues
and one part of methylaniline or homologues under a pressure of about
three atmospheres, and at a temperature of 210 degrees Centigrade
(410 Fahrenheit), or otherwise by applying a pressure of about one
atmosphere in the same apparatus the proportions of the mixture may be
one part and a half of chloride of benzyle to two of diphenylamine or
phenyltoluylamine, or ditoluylamine, or their homologues, the operation
lasting three hours in both cases. The proportions of the secondary
monamine and the aromatic chloride may be varied without interfering
with the final result aimed at. I have, however, found the best pro-
portions to be as follows:-Two equivalents or a little more of methyl-
phenylamine or its homologues, one equivalent of chloride of benzyle or
the homologues thereof. Although the use of high pressure be advan-
tageous, inasmuch as it creates a more rapid reaction, yet it may be
dispensed with. At an ordinary pressure and at the boiling point of the
mixture an alcoholic dissolution of methylaniline or its homologues will
still act upon the chloride of benzyle and the homologues thereof, giving
rise to methylbenzylphenylamine. In this case I operate by means of
an ordinary colobating apparatus. Lastly, the same reaction may be
obtained by exposing to the common or atmospheric temperature a
mixture of chloride of benzyle and of methylaniline in alcoholic solution
for a long period, several days, for instance. The product of this re-

page_text: action, whichever of three processes just mentioned may have been
worked, is chlorhydrate of methylbenzylphenylamine or its homologues.
This product may be employed at once for manufacturing colouring
and dyeing matters; it may, however, be previously purified, which is
effected by treating the same with caustic soda in an aqueous solution,
then washing it in water, so as to remove the excess of alkali, and
finally distilling or crystallizing the free bases obtained.
I will now describe the conversion of methylbenzylphenylamine and
its homologues into colouring matters.
In order to transform the chlorhydrate and bromohydrate of methyl-
benzylphenylamine and its homologues into colouring matters I use the
reaction at a gentle and long maintained temperature of one of those
oxydizing mixtures which are now so well known to manufacturers, and
are daily used for making aniline black for printing, such as a mixture
of chlorate of potash or of bi-chromate of potash with bi-sulphate of
potash or sulphate of copper, such reaction taking place in presence of
water and some inert or inactive body to divide the reactive mass.
Sesqui-chloride of carbon may also be employed. In this case a mixture
of four equivalents of the base used (methylphenylbenzylamine or its
homologues) with three equivalents of sesqui-chloride of carbon has to
be calorized or heated to a temperature of from 140 to 180 degrees
Centigrade (284 to 356 degrees Fahrenheit). Lastly, another process,
which, in certain cases may be advantageous, (as, for instance, when the
benzyldiphenylamine or the methyldiphenylamine are to be converted
into coloring matters) consists in dissolving the base in alcohol, and in
causing a current of vapours of bromine mixed with air to pass through
this alcoholic solution. The product obtained is then heated with a new
quantity of the base originally used at a temperature of from 140° to 160°
Centigrade (284° to 320° Fahrenheit) for three or four hours.
The modus operandi I most approve of is as follows:-I put into an
apparatus furnished with an agitator and a cohobator,―
15 pounds weight methylbenzylphenylamine or its homologues,
pounds chlorate of potash,
2
40
100
وو
• water,
non alveous sand

page_text: time a solution of sulphate of copper, at the rate, say, of five pounds
weight of sulphate of copper to fifteen or twenty pounds of water. In this
process temperature is maintained for 24 or 30 hours below 100° Centigrade
(212 degrees Fahrenheit), as much as possible between 50 and 80 degrees
Centigrade (122° to 176° Fahrenheit). At the end of that time reaction
has worked its task. Lime water, or a bath of either caustic soda or
caustic potash, is superadded to the solution, so as to exactly saturate to
a nicety the mass, and then a vein or jet of steam is injected into the
apparatus, in order to carry away that portion of the base which has not
been converted. The mass is then taken up over again by a small
quantity of chlorhydric acid, so that the mixture may turn out slightly
acid, and the total residue of colouring matters is afterwards dissolved
by washing or lixiviating in boiling hot water. The coloring and
dyeing matters are then precipitated by means of common salt (chloride
of sodium), and the precipitates being collected on a filter and properly
dried will be found to constitute the coloring matters, which will of
course vary according to the chemicals employed, according to the
Patent. Thus, in case I use methylbenzylphenylamine, I obtain a
bright spendid coloring matter of a violet-blue or a blue-violet shade.
When benzyldiphenylamine has been acted upon the color will be a
blueish-green or a greenish-blue. With benzylphenyltoluylamine I obtain
blue and violet coloring matters. With methylbenzyltoluylamine I
obtain orange colouring matters. With benzylditoluylamine I obtain
brown or chesnut coloring matters. And with methyldiphenylamine I
obtain blue colouring matters.
The chlorides and bromides of benzyle, of tolyle, and their homologues,
although well known in manufacture, are not yet in common use, I
therefore think fit to mention that these bodies may be obtained by
causing a current of chlorine or vapors of bromine to pass through
vapours of toluene, xylene, or their homologues whilst they are in
ebullition.
Having thus described the nature of the said Invention and the
manner of performing the same, I would have it understood that I do
not confine myself to the exact details described; but what I claim is,-
Firstly. Preparing new non-coloring substances derived from methyl-
aniline, methyltoluidine, diphenylamine, phenyltoluylamine, ditoluyl-

page_text: amine, and homologous substances, by introducing amidst these aromatic
secondary monamines an aromatic or other alcoholic radical, such as the
benzyle, the tolyle, for instance.
Secondly. Transforming the said substances, which are from them-
selves non-coloring, into coloring matters applicable to dyeing and
printing purposes, by the action upon these substances of bodies able of
oxydizing or of removing hydrogen.
In witness whereof, I, the said George Tomlinson Bousfield, have
hereunto set my hand and seal, this Eighteenth day of June,
in the year of our Lord One thousand eight hundred and
seventy.