IMPROVEMENTS IN THE MANUFACTURE OF CERTAIN ALKALOIDS DERIVED FROM ANILINE AND ITS HOMOLOGUES, AND IN THEIR TRANSFORMATION INTO COLORING MATTERS SUITABLE FOR DYEING AND PRINTING
Year: 1866

page_text: ETTERS PATENT to George Tomlinson: Bousfield, of Loughborough Park,
Brixton, in the County of Surrey, for the Invention of "IMPROVEMENTS
IN THE MANUFACTURE OF CERTAIN ALKALOIDS DERIVED FROM ANILINE AND ITS
HOMOLOGUES, AND IN THEIR TRANSFORMATION INTO COLORING MATTERS SUITABLE
FOR DYEING AND PRINTING."-A. communication from abroad by Alcide
Poirrier and Charles Chappat, residing at 23, Rue d'Hauteville, Paris,
in the Empire of France.
PROVISIONAL SPECIFICATION left by the said George Tomlinson Bousfield
at the Office of the Commissioners of Patents, with his Petition; on
the 23rd July 1866.
,
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 MANUFACTURE OF CERTAIN ALKALOIDS DERIVED FROM
ANILINK AND ITS HOMOLOGUES, AND IN. THEIR. TRANSFORMATION INTO COLORING
MATTERS SUITABLE FOR. DYEING AND PRINTING," to be as follows:-
The object of this Invention is, firstly, to obtain methylated, ethylated,
amylated, and phenylated alkaloids, derivatives of aniline and its homologues;
secondly, to transform these alkaloids into coloring matter. suitable for dyeing,
and especially to transform the methyl aniline alkaloid and the corresponding
compounds resulting from the homologues of aniline, and also the dimethyl

page_text: aniline alkaloid, or still more methylated bodies into violet coloring matters
suitable for dyeing.
1st. To produce the alkaloids I proceed as follows:-I cause a salt of aniline
or of a homologue thereof (the hydrochlorate by preference), to react upon the
alcohol of which it is desired to obtain the radical, and work in a close vessel
under pressure. If I desire to obtain methylated alkaloids I carry the tem-
perature to 175° to 210° centigrade, and I maintain the heat for three or four
hours, or the temperature may be raised to 250 or even to 300° centigrade,
and then the change takes place in a shorter time, say, an hour or two hours,
or thereabouts. In general I employ less heat to obtain the methylated
alkaloids than for the others; a greater heat than that before indicated should
be used in operating on the higher alcohols, the proportions which I employ
are 100 to 150 parts of alcohol to cach 100 parts of aniline salt, according
as I wish to carry the transformation a greater or less length. When the
operation is finished a hydrochlorate of the new alkaloid remains, which I
decompose by means of soda, potash, or ammonia, and obtain a mixture of
alkaloids containing one or more molecules of the alcoholic radical; these
alkaloids may be separated by fractional distillation. Or in place of this
process I take aniline or its homologue and mix it with an alcohol, and also
with a salt, by preference a chloride, it may be the chloride of ammonium,
zinc, iron, or other base. I mix, by preference, 100 parts of aniline, 80 to
100 parts of chloride of ammonium, 100 to 150 parts of the alcohol, and I
work, as above described, in a vessel under pressure at a temperature of 275°
to 300° centigrade, which heat I maintain from two to four hours, or there
abouts. When the reaction is complete the liquid will separate into two
layers, one of which is oily and contains the new alkaloids. Or, again, I can
obtain the said alkaloids by mixing together, under pressure, an alcoholic salt
(the nitrate or chloride by preference) and aniline or a homologue thereof,
either in equivalent proportions or two equivalents of the alcoholic salt to one
'of aniline (or homologue) if it is desired to carry the transformation further;
this mixture is heated for 3 or 4 hours to 100° or 150° centigrade; for the
nitrate a temperature of 100° is sufficient, or the same result may be arrived
at without heat if the mixture is allowed to stand for some days. The salts
of the new alkaloids are decomposed, and if it is wished to carry the trans-
formation further they may be a second time submitted, in the manner already
described, to the action of an alcoholic salt. By these several processes I am
able to group upon aniline or its homologue different alcoholic radicals at a
'single operation by putting the aniline or its homologue, or a salt thereof, in
contact with several alcohols according to the processes above described; o

page_text: the same result may be obtained by successive actions by acting on the alkaloid
first obtained with an alcohol of another nature, and so on.
2nd. To obtain violet coloring matters from alkaloids such as are produced
by the processes before described I proceed as follows:-The reagents which
I employ are the chlorides, chlorates, bromides, bromates, iodides, and iodates,
cyanides, bichloride of tin, mercury (this last mixed as we will presently
describe), biniodide of mercury, cyanide of iodine, the chloride of iodine,
iodine and equivalents reagents, and the chlorine and bromine derivatives of
benzine. I work generally with distilling apparatus at a temperature not
exceeding 100° centigrade, and the operation may be conducted under pressure.
By raising the temperature above 100° the colours obtained are deteriorated;
also by the use of oxidizing agents colours may be obtained, but they are less
pure and permanent. Red violets are obtained when I use the methyl aniline
alkaloid, and bluer violets when I employ dimethyl aniline alkaloid or bodies
which are still more methylated.. After purification these violets are soluble
in water, alcohol, and acetic acid, they are suitable for dyeing.
The following is the mode of working:-In a distilling apparatus I put
one part of methyl aniline alkaloid or homologue thereof, or the dimethyl
compound, or a compound still more methylated, or methyl ethyl aniline
alkaloid, or methyl amyl aniline alkaloid, also five or six parts of chloride of
tin, added little by little, and I heat the mixture to 100° centigrade until the
mass becomes hard; it is then washed several times with alkaline liquid to
dissolve out the tin, the residue is then washed with acid, and so a magnificent
violet colour is obtained. In the same way I employ biniodide of mercury
and the cyanide of iodine diffused in one or two parts of water, or a mixture
of products which produce these bodies. I proceed as before, and if the product
is not sufficiently pure 1 treat it with boiling water to which a little alcohol
or acid is added; on cooling the color precipitates as a green crystalline
powder. I also employ the chloride of iodine diffused in from. 5 to. 10. parts
of water, or a mixture which produces a chlorate, and iodine in the proportion
of 100 parts of methylated alkaloid, 80 parts of chlorate of potash,. 20. parts
of iodine, or a mixture of chlorine, bromine, iodine, with a chlorate,. or bin-
iodide of mercury and chlorate, iodide of potassium and chlorate, bichloride of
mercury and chlorate. I employ one part of methylated alkali, three parts of
biniodide of mercury, and one part of chlorate of potash. I heat as above to
100° centigrade, and I follow the same treatment, that is to say, with boiling
water, soda, and acid; or one part of alkali, one and a half parts of bichloride of
mercury, and one part of chlorate of potash; the bichloride of mercury employed
alone developes very little colour. The terchloride of benzine and the chlorine

page_text: 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 23rd January 1867.
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 Twenty-third day of July, 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 George Tomlinson Bousfield, Her special license that I, the said George
Tomlinson Bousfield, my executors, 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 torm 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 CERTAIN ALKALOIDS DERIVED
ANILINE AND ITS HOMOLOGUES, AND IN THEIR TRANSFORMATION INTO COLORING
MATTERS SUITABLE FOR DYEING AND PRINTING," a communication to me from
abroad by Alcide Poirrier and Charles Chappat, persons resident at 23, Rue
d'Hauteville, Paris, in the Empire of France, upon the condition (amongst
others) that I, the said George Tomlinson Bousfield, my executors or adminis,
trators, 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 tho
'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.
PROM
NOW KNOW YE, that I, the said George Tomlinson Bousfield, 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 object of this Invention is, first, to obtain methylic, ethylic, amylic,
and phenylic alkaloids, derivatives of aniline and its liomologues (toluidine,

page_text: cumidine, &c.), or of mixtures of aniline with its homologues; secondly, to
transform these alkaloids into coloring matters suitable for dyeing, and
especially to transform the methyl aniline alkaloid and the corresponding
compounds resulting from the homologues of aniline, and also the dimethyl
aniline alkaloid or still more methylic bodies, cither alone or mixed with
methyl aniline, into violet coloring matters suitable for dyeing silk, wool,
cotton, and other materials. To produce the methylic, ethylic, amylic, and
phenylic alkaloids a salt of aniline, or of a homologue thereof, or a mixture.
of these salts (hydrochlorate by preference) is caused to react upon the alcohol.
of which it is desired to obtain the radical. The hydrochlorate of aniline (or
homologue) and the alcohol of which it is desired to obtain the radical are
put into a close metal vessel enamelled or otherwise; this vessel is furnished
with a safety valve and a pressure gauge indicating the pressure within; it is
placed in an oil bath, or it may be in a bath of sand, melted metal, or hot air,
the temperature of which is registered by a thermometer. If it is desired to
obtain methylic alkaloids the temperature is carried to 175° to 210° centi-.
grade, and the heat maintained for three or four hours, or the temperature,
may be raised to 250° or even to 300° centigrade, and then the change takes
place in a shorter time, say an hour or two hours, or thereabouts. At the
lower heat (175 to 210) the action may be continued longer than 4 hours.
If ethylic alcohol is employed the heat may rise to 320° centigrade; for amylic
alcohol the heat may rise to 340 degrees, and for phenylic alcohol the heat
may rise to 350 degrees. If in place of hydrochlorate of aniline the hydro-
bromate is taken, or the hydroiodate, the temperature should range between
100 and 200 degrees. The proportions to be employed are by preference 100
to 150 parts of the alcohol to each 100 parts of aniline salt or the homologue,
according as it is wished to carry the transformation to a greater or less
length. When the operation is finished a salt, say hydrochlorate, of the new
alkaloids remains, which is then decomposed by means of soda, potash, or
ammonia, and a mixture is obtained of alkaloids containing one or more
molecules of the alcoholic radical; these alkaloids may be separated by
fractional distillation, that is to say, a thermometer is plunged in the distilling.
apparatus, and that which distils at a temperature of 192 degrees centigrade,
or thereabout, is methyl aniline; that which distils at 202 degrees, or there-
about, is dimethyl aniline; all that distils above this point are products of
condensation.
'
Or, secondly, the same results may be obtained by mixing aniline, or its
homologue, or a mixture of these, with the alcohol of which the radical is
required, and a salt, by preference the chlorides, bromides, or iodides of

page_text: ammonium, aluminium, calcium, magnesium, zinc, iron, or other metal. By
preference 100 parts of aniline, 80 to 100 parts of chloride of ammonium,
100 to 150 parts of the alcohol are mixed and heated as above described in a
vessel under pressure at a temperature of 275° to 300° centigrade, which heat
is maintained from two to four hours, or thereabouts. When the reaction
is complete the liquid will separate into two layers, one of which is oily and
floats, and which is the alkaloid itself. If in place of hydrochlorate of
ammonia one or other of the salts above indicated is employed it should be
substituted for the hydrochlorate of ammonia in equivalent proportions.
Or, thirdly, the said alkaloids can be obtained by mixing in the close vessel.
above mentioned an alcoholic salt (by preference a nitrate) and aniline, or a
mixture of aniline and its homologues, either in equivalent proportions or two-
equivalents of the alcoholic salt; if it is desired to carry the transformation.
further the mixture is heated for three or four hours to a temperature of 100.
degrees centigrade, or thereabout. In place of employing the alcoholic nitrate
above mentioned an alcoholic chloride can be employed; in this case the heat
should be raised to 220 degrees centigrade, or thereabout. When the
alcoholic nitrate is employed the process may be conducted in an earthenware
or iron vessel without heat, but then the operation will require several days.
The salts of the new alkaloid. are next decomposed, and if it is desired to
carry the transformation further these alkaloids may be submitted again to
tho action of the alcoholic salt, the process being conducted as before described.
By these several processes also there may be grouped upon aniline, or its
homologue, or a mixture thereof, different alcoholic radicals at a single
operation, by putting the aniline, or its homologue, or a salt thereof, in con-
tact with several alcohols, according to the processes above described; or the
same result may be obtained by successive actions by acting on the alkaloid
first obtained, or upon a salt of this alkaloid with an alcohol of another nature,
and so on. Similarly there may be caused to react on the alkaloids of alcoholic
radicals, or on the salts of these alkaloids, the same alcohol or alcohols which
have served to produce them or other alcohols, the operation being conducted
as we have already described for aniline or salts of aniline.
To obtain violet, violet red, and violet blue coloring matters from methylic,
methyl ethylic, and methyl amylic alkaloids, such as are produced by the
processes before described, the reagents employed are the chlorides and
chlorates, bromides and bromates, iodides and iodates, as bichloride of tin or
mercury (this last mixed as presently described), biniodide of mercury, iodide
of cyanogen, and the chloride of iodine, also iodine, bromine, and the chlorine
and bromine derivatives of benzine. The materials are heated together in a

page_text: distilling apparatus at a temperature not exceeding. 100° centigrade. The
operation may be conducted under pressure, but by raising the temperature
above 100° the colors obtained are deteriorated.
Red violets are obtained when the methyl aniline alkaloids are used, and
bluer violets when dimethyl aniline alkaloid or bodies which are still more
methylic are used. After purification these violets are soluble in water,
alcohol, and acetic acid; they are suitable for dyeing and printing in the
same way as other aniline colors are used.
The following is the mode of working employed by preference:-In a dis-
tilling apparatus there is put one part of methyl aniline alkaloid or homologue
thereof, or the dimethyl compound, or a compound still more methylic or
methyl ethyl aniline alkaloid, or methyl amyl aniline alkaloid, &c., and five or
six parts of bichloride of tin are added little by little. The mixture is heated,
but not higher than 100° centigrade, until the mass becomes hard; or if heat
is not employed, colour is formed simply by the contact of bichloride of tin and
methyl aniline; the whole is treated repeatedly with a solution of alkali
(soda, potash, or ammonia,) then the whole is thrown upon a filter ;. the
precipitate which is on the filter is taken and put into a bath of boiling water,
to which acid is added, so as to obtain a neutral salt; the filtering is
repeated, and then the colour which is in solution in the filtered liquid is
precipitated; by the addition of common salt a beautiful green precipitate is
formed, which can be separated by filtration. This green powder if dissolved
in hot water, or even in cold, is a beautiful violet colour, and the solution dyes
a magnificent violet. In the same way biniodide of mercury and the cyanide
of iodine diffused in one or two parts of water may be used. Or in place of
adding these bodies directly a mixture of products which produce them may
be employed.
The process is conducted as before described, and if the product is not
sufficiently pure after the further treatment already specified it is treated with
boiling water, to which a little alcohol or acid is added, on cooling the color
precipitates as a green crystalline powder, the precipitation is facilitated by
the addition of common salt. When the chloride of iodine is employed it is
diffused in from 5 to 10 parts of water and the process conducted as already
described; or in place of chloride of iodine a mixture which produces it may
be used, say 80 parts of chlorate of potash and 20 parts of iodine to 100.
parts of methylic alkaloid. These proportions may be varied, or we sometimes
employ a mixture of biniodide of mercury and chlorate, of iodide of potassium
and chlorate, of bichloride of mercury and chlorate. There may also be
employed with the alkaloids above mentioned the following mixtures of a

page_text: chloride and a chlorate, or of bromine and a chlorate, or of a bromide and a
chlorate, or of an iodide and a chlorate. Thus there may be employed one
part of methylated alkali, three parts of biniodide of mercury, and one part of
chlorate of potash; the mixture is heated as above to 100° centigrade, and
the same, treatment followed, that is to say, with boiling water, soda, and
regeneration with acid, or one part of alkaloid, one and a half parts of
hichloride of mercury, and one part of chlorate of potash. The violet color is
also obtained by putting together 100 parts of methylic alkaloid, 80 to 100.
parts of a chlorate, 80 to 100 parts of hydriodic acid, and heating to a tem-
perature not higher that 100 degrees; or the hydriodic acid may be replaced
by: hydrobromic acid, or by others, it may be by sulphuric acid; in this last
case a sulphate is first prepared, and two or three parts of water are added to
it. Further the violet colour may be obtained by putting together an iodate,
say, the iodate of potash and a hydrochlorate of methyl aniline or homologue,
say, 100 parts of hydrochlorate of methyl aniline, and 100 parts of iodate of
potash; the mixture is heated as before. If the iodate is dissolved in water, say
in 100 parts of water, or thereabout, and the mixture exposed to a moderate licat
or even allowed to remain cold, the violet forms at the end of a few hours; in
place of an iodate a bromate may be used under the same conditions; or iodic
acid or bromic acid may be taken and made to act at a moderate heat on
methyl aniline, say, 100 parts of methyl aniline, 150 parts of syrupy iodic acid
dissolved in 1,500 parts of water. If bromic acid be taken it should similarly
be mixed with water.
The bichloride of mercury alone developes very little color. The terchloride
of benzinc and the chlorine derivatives of phenic acid, say, terchlorophenic
acid, also develope a violet color, but the temperature has to be raised to
150° centigrade.
Having thus described the nature of this Invention, and the manner of
performing the same, I would have it understood that the Invention is not
confined to the exact details described; but what is claimed is,―
First. The manufacture of alkaloids derived from aniline or from its
homologues by the reaction of hydrochlorate of aniline or of the hydrobromate
or of the hydriodate, or of corresponding salts of its homologue, or of a
mixture of these salts upon a methylic alcohol or other alcohol, the action is
aided by heat and pressure as already described.
Second. The manufacture of alkaloids derived from aniline or from its
homologues by the reaction upon aniline or its homologues, or upon a mixture
of aniline with one or more of its homologues, of a methylic alcohol or other
alcohol employed conjointly with the chlorides or the bromides, or the iodides of

page_text: ammonium or of aluminium, or of calcium, or of magnesium, or of iron, or of
zinc, or of other metal, the action being aided by heat and pressure, as already
described.
Third. The manufacture of alkaloids derived from aniline or from its homo
logues by the reaction upon aniline or its homologues, or aniline mixed with
one or more of its homologues, of a methylic or other alcoholic nitrate or
chloride, in the manner herein-before described.
Fourth. The manufacture of other alkaloids by employing either of the three
processes above set forth to cause to react on alcohol, radical alkaloids derived
from aniline (or from its homologue, or from a mixture of aniline with ono or
more of its homologues) the same alcohol or alcohols which served to produce
them, the alkaloid being substituted in the process for aniline itself.
Fifth. The transformation as above described of methylic or methyl ethylic
or methyl amylic alkaloids, or the other alkaloids herein-before set forth, into
violet coloring matter suitable for dyeing and printing, by treating these
alkaloids by the processes described, employing the substances mentioned, the
anhydrous bichloride of tin, or the biniodide of mercury alone or mixed with
a chlorate or the cyanide of iodine, or the bichloride of mercury conjointly with
a chlorate or the chloride of iodine, or the bromide of iodine, or bromine or
iodine, these two last conjointly with a chlorate or an acid conjointly with a
chlorate, either hydriodic acid or hydrobromic acid, or sulphuric acid, or an
iodate or a bromate, or iodic acid or bromic acid.
In witness whereof, I, the said George Tomlinson Bousfield, have here-
unto set my hand and seal, this Nineteenth day of January, in the
year of our Lord One thousand eight hundred and sixty-seven.