IMPROVEMENTS IN THE MANUFACTURE OF DYES FROM ANILINE AND ITS ANALOGUES
Year: 1863

page_text: LETTERS PATENT to Robert Thomson Monteith, of Saint Malo, in the
Empire of France, British Vice Consul, and Robert Monteith, of 64,
Crystal Terrace, Cecil Street, Greenheys, Manchester, in the County of
Lancaster, Gentleman, for the Invention of "IMPROVEMENTS IN THE
MANUFACTURE OF DYES FROM ANILINE AND ITS ANALOGUES."- A communi-
cation from abroad by Georges Auguste Jules Delvaux, residing at
No. 37, Rue Corneille, Paris, in the Empire of France.
Sealed the 3rd July 1863, and dated the 8th January 1863.
PROVISIONAL SPECIFICATION left by the said Robert Thomson
Monteith and Robert Monteith at the Office of the Commissioners of
Patents, with their Petition, on the 8th January 1863.
We, ROBERT THOMSON MONTEITH, of Saint Malo, in the Empire of France,
British Vice Consul, and ROBERT MONTEITH, of 64, Crystal Terrace, Cecil
Street, Greenheys, Manchester, in the County of Lancaster, Gentleman, do
hereby declare the nature of the said Invention for "IMPROVEMENTS IN THE
MANUFACTURE OF DYES FROM ANILINE AND ITS ANALOGUES," to be as follows:-
The said Invention consists in producing dyes capable of dying cotton, silk,
woollen, and other similar fabrics from aniline and its analogues, such as
toluidine and cumidine, the colours produced being red, yellow, different
shades of brown, violet, green, and blue. To produce the red dye hydro-
chlorate of aniline or its analogues, or sulphate of aniline or its analogues is
heated with aniline, in the case of the hydrochlorate to a temperature of 302°
Fahrenheit, and in the case of the sulphate to 482° Fahrenheit, until the red
colour appears. The most convenient way of performing this process is to heat
a mixture of equal parts. by weight of aniline and hydrochloric acid, a portion

page_text: of the aniline combining with the hydrochloric acid forms hydrochlorate of
aniline, sufficient free aniline remaining to produce the red colour. Sulphuric
acid may be used instead of hydrochloric, the number of equivalents of
sulphuric acid being the same as the equivalents of bydrochloric. The red
colour may also be produced by heating dry sulphate of aniline alone to 418°
Fahrenheit, but care must be taken not to go beyond this temperature, as in
that case the red will not be free from violet. The red is also produced by
heating aniline with the salts of ammonia, such as sulphate or hydro-
chlorate of ammonia from 302° to 392° Fahrenheit. The same colour
may also be produced by heating hydrochlorate or sulphate of aniline
with napthaline to 392° Fahrenheit. A very fine red may be produced
by heating one part by weight of dry hydrochlorate of aniline and five
parts by weight of sand, well mixed in a covered vessel for one hour at 302°
Fahrenheit, and afterwards for two hours at 356° Fahrenheit, by means of
an oil bath. When cool the product must be exhausted with boiling water,
and the colour obtained purified in the ordinary way of purifying aniline dyes.
By heating hydrochlorate or sulphate of aniline mixed with sand to about 392°
Fahrenheit, both red and violet are produced, but these may be separated, the
former being soluble in water and the latter in alcohol. The process may be
performed as follows:-Two parts of dry hydrochlorate of aniline is mixed
with one part of aniline and ten parts of sand, and heated in a covered vessel
from 374° to 392° Fahrenheit for three hours or upwards, and when cooled
treated with boiling water, which dissolves the red color, the residue after
filtration being treated with alcohol, which dissolves the violet. The red may
be also produced by heating hydrochlorate of aniline and aniline in a close
vessel, or by heating dry bydrochlorate of aniline in an open vessel with a
thick layer of sand at the top, or heating a mixture of it with gelatinous silicic
acid or fluoride of calcium in an open or closed vessel; in these cases the heat
must be from 212° to 392° Fahrenheit; a yellowish brown known as "cuir "
or "havanne" can be produced by heating hydrochlorate of aniline either dry
or moistened with water in a close vessel to 482° Fahrenheit, different shades
of this colour can be produced by varying the length of time the heat is
continued.
Hydrochlorate of toluidine either alone or with toluidine or. napthaline, and
either with or without water when heated to 356 Fahrenheit in either open
or close vessel produces a golden yellow.. If the heat is increased to from
482° to 536° Fahrenheit green is produced. Blue is produced by heating
hydrochlorate of aniline or its analogues with aniline or its analogues from
392° to 482° Fahrenheit in a closed vessel either with or without sand. If

page_text: aniline is used the proportions should be 129 parts by weight of the hydro-
chlorate to 93 parts by weight of aniline. If any of the analogues of aniline
are used the proportions must be varied according to their equivalents. If
the temperature is carried beyond 482° Fahrenheit green is produced. The
blue is soluble both in water and alcohol.
All the above colours may be used for dying in the same way as the known
aniline dyes
SPECIFICATION in pursuance of the conditions of the Letters Patent, filed
by the said Robert Thomson Monteith and Robert Monteith in the
Great Seal Patent Office on the 8th July 1868.
TO ALL TO WHOM THESE PRESENTS SHALL COME, we, ROBERT
THOMSON MONTEITH, of Saint Malo, in the Empire of France, British Vice
Consul, and ROBERT MONTEITH, of 64, Crystal Terrace, Cecil Street, Greenheys,
Manchester, in the County of Lancaster, Gentleman, send greeting.
WHEREAS Her most Excellent Majesty Queen Victoria, by Her Letters
Patent, bearing date the Eighth day of January, in the year of our Lord
One thousand eight hundred and sixty-three, in the 26th year of Her reign,
did, for Herself, Her heirs and successors, give and grant unto us, the said
Robert. Thomson Monteith and Robert Monteith, Her special licence, that
we, the said Robert Thomson Monteith and Robert Monteith, our executors,
administrators, and assigns, or such others as we, the said Robert Thomson
Monteith and Robert Monteith, our 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 DYES FROM ANILINE AND ITS
ANALOGUES," being a communication to us by Georges Auguste Jules Delvaux,
residing at No. 37, Rue Corneille, Paris, in the Empire of France, upon the
condition (amongst others) that we, the said Robert Thomson Monteith and
Robert Monteith, our executors or administrators, by an instrument in writing
under our, 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,

page_text: NOW KNOW YE, that we, the said Robert Thomson Monteith and
Robert Monteith, do hereby declare the nature of our said Invention, and
in what manner the same is to be performed, to be particularly described
and ascertained in and by the following statement :-
The said Invention consists in producing dyes capable of dyeing cotton,
silk, woollen, and other similar fabrics from aniline and its analogues, the
colours produced being red and different shades of brown and violet. To
produce the red dye hydrochlorate of aniline or its analogues, or sulphate of
aniline or its analogues is heated with aniline, in the case of the hydro-
chlorate to a temperature of 302° Fahrenheit, and in the case of the
One way of
sulphate of 482° Fahrenheit until the red colour appears.
performing this process is to heat to the temperatures above mentioned a
mixture of equal parts by weight of aniline and hydrochloric acid. A portion
of the aniline combining with the hydrochloric acid forms bydrochlorate of
aniline, sufficient free aniline remaining to produce the red colour. Sulphuric
acid may be used instead of hydrochloric acid, a quantity of the former
chemically equivalent to the latter being employed. The red colour may also
be produced by heating dry sulphate of aniline alone to 428° Fahrenheit,
but care must be taken not to go beyond this temperature, as in that
case the red will not be free from violet. The red may also be produced
by heating aniline along with the salts of ammonia, such as sulphate
or bydrochlorate of ammonia from 302° to 392° Fahrenheit. A very fine
red may be produced by heating by any ordinary method one part by
weight of dry hydrochlorate of aniline and certain parts, we prefer to
use 10 parts by weight of sand, well mixed in a covered vessel, we prefer
one that is not hermetically closed for a certain time, we prefer for 3
or 4 hours continuously at 302° Fahrenheit. When cool the product must
be treated with boiling water, and the color obtained purified in the ordinary
way of purifying aniline dyes.
The best mode of conducting the above-mentioned process for producing
red is to heat by any ordinary method to a temperature of 240° Fahrenheit
for 40 hours a mixture consisting of 69 parts by weight of dry hydrochlorate
of aniline of commerce, 50 such parts of aniline of commerce, and 4,000 such
parts of dry sand. When the mass is cool the red is extracted with boiling
water, until no more color comes away. Another method is to heat to'a
temperature from 230° to 248° Fahrenheit, from 25 to 30 hours in a retort'a
mixture consisting of 69 parts by weight of dry bydrochlorate of aniline of
commerce, 250 such parts of aniline of commerce, and 1000 such parts of dry
sand, first placing upon the top of the mixture another 1000 parts by weight

page_text: of sand. A little aniline is distilled. When cool the mass is treated with
lime, and a current of steam blown through which causes all the untransformed
aniline to distil. The process will succeed if 50 parts by weight of 'aniline of
commerce are substituted for the before-mentioned 250 parts of that material,
but a less yield of red will be produced. Both red and violet may be pro-
duced by heating by any.ordinary method 'hydrochlorate or sulphate of aniline
mixed with sand to about 392° Fahrenheit, and these again may be separated,
the colouring matter of the former being soluble in water, and that of the
latter in alcohol. These processes may be performed as follows:-Two parts
by weight of dry hydrochlorate of aniline are mixed with one such part of aniline
and ten such parts of -sand, and heated in a covered but not hermetically
closed vessel from 374° to 392° Fahrenheit for three hours or upwards.
When cool the mixture is treated with boiling water, which dissolves out the
red colour, and the residue after filtration is treated with alcohol, which
dissolves out the violet colour. The red may also be produced by heating
hydrochlorate of aniline and aniline in a closed vessel, or by heating dry
hydrochlorate of aniline in 'an open or closed vessel with a thick layer of sand
at the top, or by heating a mixture of dry hydrochlorate of aniline with dry
sand in an open or closed vessel to a temperature from 212° to 392° Fahren-
heit. Instead of sand there may be mixed with the coloring substances, as
above described, gelatinous silicic acid or fluoride of calcium, or indeed many
other finely divided substances, which are not liable to act otherwise than
mechanically on the substances employed in the processes above described.
The effect of the sand or other finely divided substance when mixed with the
colouring matter as aforesaid "being to retain the tarry matters to a great
extent, and we find that the crude red made by the above process with the
admixture of sand or such other finely divided substance as aforesaid is
after extraction more easily purified than the crude red when made without
such admixture. A yellowish brown, known. as "cuir" or "havanne," may
be produced by heating to 482° Fahrenheit in a close vessel bydrochlorate of
aniline or its analogues, either dry or moistened with water. Different shades
of this colour may be produced by varying the length of time for the con-
tinuation of the heat. The brown colouring matter should be.treated with
benzine or coal naphtha till the tar is removed, and then be dissolved in
alcohol or acetic acid, when it will be ready for use.
All the above colours may be used for dying in the same way as the known
aniline dyes.
Since filing the Provisional Specification herein we have ascertained that
the formation of yellow, green, and blue from aniline or its analogues, as also

page_text: the producing of red by heating hydrochlorate or sulphate of aniline with
naphthaline are attended with such difficulties as to render the processes
practically useless, and we have therefore not proceeded to describe
.them.
We claim the production of red and violet colouring matters by the decom-
position of hydrochlorate or sulphate of aniline or its analogues by heat,
whether those substances are used by themselves or mixed with aniline or its
analogues, and whether either of the above mixtures is heated alone or after
it has been mixed with sand or any other finely divided substance, as before
'mentioned.
Also, the use of salts of ammonia for the purpose herein described.
Also, the admixture with the coloring substances, as above described, of
sand, gelatinous silicic acid, fluoride of calcium, or any other finely divided
substances not liable to act otherwise than mechanically upon the substances
employed in the processes above described.
And, also, the production of brown colours by the decomposition of salts of
aniline or its analogues by heat, as above described.
Whenever hydrochlorate of aniline or aniline is above mentioned the
hydrochlorate of aniline of commerce or aniline of commerce is intended.
In witness whereof, we, the said Robert Thomson Monteith and Robert
Monteith, have hereunto set our hands and seals, this Sixth day
of July, in the year of our Lord 1863.
ROBERT THOMSON MONTEITH. (L.B.)
ROBERT MONTEITH.
Signed, sealed, and delivered by Robert
Thomson Monteith, at St. Malo, in
presence of
PATRICK DUDGEON, Gentleman, St. Servan,
ANNE MARY MONTEITH, Spinster, St. Servan, } France.
(L.S.)