IMPROVEMENTS IN THE PREPARATION OF COMPOUNDS CAPABLE OF BEING EMPLOYED FOR THE PURPOSES OF DYEING AND PRINTING."
Year: 1881

page_text: LETTERS PATENT to Ralph Henry Christopher Nevile, of Wellingore Hall, in
the County of Lincoln, Esquire, for an Invention of "IMPROVEMENTS IN THE
PREPARATION OF COMPOUNDS CAPABLE OF BEING EMPLOYED FOR THE
PURPOSES OF DYEING AND PRINTING."
PROVISIONAL SPECIFICATION left by the said Ralph Henry Christopher
Nevile at the Office of the Commissioners of Patents on the 8th October
1881.
RALPH HENRY CHRISTOPHER NEVILE, of Wellingore Hall, in the County of
Lincoln, Esquire. " IMPROVEMENTS IN THE PREPARATION OF COMPOUNDS
CAPABLE OF BEING EMPLOYED FOR THE PURPOSES OF DYEING AND PRINTING."
This Invention relates to the artificial production of orcine from toluol, or from
such of its derivatives as have in the two positions meta to methyl groups, which
can by suitable methods be converted into hydroxyl groups.
Orcine being a compound in which the two hydroxyl groups are in meta position
to the methyl group, may therefore be obtained from those derivatives of toluol
which contain two groups in the meta position to methyl capable of being converted
into bydroxyl groups.
The following derivatives are given as examples :-
(1). Meta dinitro toluol. .
(2). Meta bromo-, meta toluol, sulphonic acid, meta chloro-, meta-toluol-, sulphonic
acid, meta-iodo, meta-toluol-, sulphonic acid.
(3). Meta-bromo-, meta-toluidine, meta-chloro-, meta-toluidine-, meta iodo, meta
toluidine.
(4). Toluol-, meta-disulphonic acid.
In carrying out any Invention I either take meta dinitro toluol, which may be
obtained from meta dinitro, para toluidine (the nitro groups being in the meta
position to methyl), or from any other source by the substitution of hydrogen for
the amido group.
For the purpose of obtaining dinitro toluol from meta dinitro, para toluidine,
nitrous acid is introduced into a mixture of meta dinitro para toluidine and
sulphuric acid diluted with an equal volume of water, and the resulting solution is
gradually poured into alcohol at an elevated temperature.
When the generation of gas has ceased the addition of water causes the dinitro-
toluol to separate, and it may then be purified by distillation with steam and
crystallization from alcohol,

page_text: The dinitrotoluol thus resulting or otherwise obtained is now reduced by an
alcoholic solution of ammonium sulphide or otherwise to meta nitro meta toluidine,
which may be separated by the addition of water.
It may then be dissolved in hydrochloric acid and reprecipitated by means of
ammonia.
The meta nitro meta toluidine thus or otherwise obtained is dissolved in a warm
mixture of equal volumes of sulphuric acid and water and allowed to cool, where-
upon the sulphate separates out and a solution of potassic nitrite is gradually
added, or nitrous acid may be introduced until the whole of the sulphate is
redissolved. The temperature of the solution of the diazo combination is after the
addition of water elevated, and the temperature is maintained until the desired
conversion into meta nitro metaoxyltoluol results. This partly separates
as an oily substance and may be purified by crystallization, and the remaining
portion may be extracted from the mother liquid by means of ether.
The meta-nitro-meta-oxytoluol thus or otherwise obtained may be reduced with
tin and hydrochloric acid. The tin existing in solution may be removed by means
of sulphuretted hydrogen, and the filtered liquid evaporated to dryness. The
chloride so obtained dissolved in water acidulated with sulphuric acid, cooled, and
then decomposed with a solution of potassic nitrite, then warmed until decom-
position takes place.
The resulting solution will then contain orcine, and may either be employed
direct for the production of coloring matters, or the orcine may be extracted there-
from by means of ether or otherwise.
I also prepare orcine from meta-bromo toluol, meta sulphoric acid, and from
analogous compounds by heating the same with caustic alkalies, as, for example,
caustic soda either in a solid form or in solution, which heating may be effected at
a temperature varying from 200° to 300° centigrade.
As an example, we take an alkaline salt of the meta-bromo meta toluol
sulphonic acid and mix it with about twice its weight of caustic potash or caustic
soda, in a solid condition or in a concentrated solution, and heat the mixture to
about from 250° to 300° centigrade, by preference with agitation.
The melted mass is dissolved in water and acidulated, and may then be either
used directly in the production of coloring matters, or the orcine may be obtained
therefrom by evaporation and subsequent extraction with ether.
I also obtain orcine from meta-bromo- meta-toluidine and analogous compounds
by conversion of the amido into an hydroxyl group by the usual methods, and the
subsequent conversion of the bromine group into an hydroxyl group by heating
with caustic alkalies. As an example, I take meta bromo meta toluidine and
dissolve the same in water acidulated with sulphuric or other acid. The
temperature is then reduced and a solution of potassic nitrite is gradually added
until the meta bromo meta toluidine is converted into a diazo compound. The
solution is then heated until meta bromo-meta kresol is produced, which may be
extracted from the solution by means of ether and subsequent evaporation or
otherwise, and may then be heated with caustic potash, either in the solid or liquid
form, to about from 250° to 300° centigrade in order that orcine may be obtained
therefrom, which may be extracted either by means of water or by means of
ether.
I further prepare orcine by the action of caustic alkalies at an elevated temperature
upon the disulphonic acid, which is obtained in effecting the substitution of
hydrogen for the amido group in toluidine-dimeta sulphonic acid, the latter being
obtained by the action of sulphuric acid upon the mixture of ortho and para
toluidine, known as commercial toluidine.
Orein thus obtained may be dissolved in an ammoniacal solution and may be
employed for the purposes of drying and printing, in a manner similar to that now
adopted when vegetable orcin is used, or may be otherwise employed.

page_text: SPECIFICATION in pursuance of the conditions of the Letters Patent filed by
the said Ralph Henry Christopher Nevile in the Great Seal Patent Office on
the 6th April 1882.
RALPH HENRY CHRISTOPHER NEVILE, of Willingore Hall, in the County of
Lincoln, Esquire. "IMPROVEMENTS IN THE PREPARATION OF COMPOUNDS CAPABLE
OF BEING EMPLOYED FOR THE PURPOSES OF DYEING AND PRINTING."
This Invention relates to the artificial production of orcin and substitution
products thereof, and of homologous substances from toluol and from such of its
derivatives as contain in the two positions meta to methyl groups which may by
suitable methods be changed into hydroxyl groups, and to the employment and use
of the orein and other substances so prepared for the purposes of preparing
colouring matters, and for the employment and use of the same for the purposes of
dyeing and printing.
According to this Invention I prepare orcin from any derivative of toluol which
contains in the two positions meta to methyl groups which can by suitable means
be changed into hydroxyl groups, as, for example, meta dinitro toluol; meta bromo
toluol-, meta sulphonic acid; toluol-meta-disulphonic acid; meta bromo, meta amido
toluol; meta diBromo toluol.
It will be understood that the above are given as examples, as the products
referred to can be prepared from any substance, as defined above, such as meta
nitro-meta kresol and others.
According to the substance from which it is prepared I proceed in different
ways, for example, in preparing it from meta-dinitro-toluol, I take this substance
and dissolve it in an alcoholic solution of ammonium sulphide, by which means it
is reduced and meta nitro meta amido toluol is formed. On diluting the alcoholic
solution with water this is precipitated, and it may then be purified by solution in
dilute acids, as, for example, bydrochloric acid, and reprecipitation with ammonia
or otherwise.
The meta nitro meta amido toluol thus or otherwise obtained may now be
dissolved in a mixture of equal volumes of sulphuric acid and water and allowed
to cool, whereupon the sulphate crystallizes out. A solution of potassium nitrite is
now added until the whole or nearly the whole of the sulphate is redissolved.
The temperature of the solution is now after the addition of water elevated
from about 60° to about 90° centigrade, and maintained at or about such
temperature until the desired conversion into meta-nitro-meta-kresol takes
place. This partly separates as an oily substance and may be purified by
crystallization, and the remaining portion may be extracted from the mother
liquid by means of ether or otherwise. The meta nitro-meta kresol thus or
otherwise obtained may be reduced by tin and hydrochloric acid. The tin existing
in solution may be removed by sulphuretted hydrogen gas or otherwise, and the
filtered liquid evaporated to dryness. The chloride of meta amido meta kresol thus
or otherwise obtained may be dissolved in water acidulated with sulphuric or other
suitable acid, cooled, and then decomposed with a solution of potassium nitrite, and
then warıned until the conversion into meta di oxy toluol or orcin take place. The
resulting solution contains the orein and may be employed directly for the
production of coloring matters, or the orcin may be extracted therefrom by means
of ether, evaporation, or otherwise.
I also prepare orein from meta bromo-toluol meta sulphonic acid and from
analogous compounds, such as metachlor toluol meta sulphonic acid, by heating the
same with caustic alkalies, as, for example, caustic soda either in a solid form or in
solution, which heating may be effected at a temperature varying from 250° to 300°
centigrade, preferably with agitation and in a closed vessel.

page_text: As an example I take an alkaline salt of meta bromo toluol meta sulphoric acid
and mix it with about twice its weight of caustic potash or caustic soda in a solid
condition or in a concentrated solution, and heat the mixture of about from 250°
to about 300° centigrade for some time, say, about from 1 to 9 hours by
preference, with agitation and in a closed vessel. The melted mass if solid potash
or soda be used is dissolved in water, and in either case the solution is acidulated
and may then be either used directly for the production of coloring matters, or
the orein may be obtained therefrom by evaporation or extraction with ether or
otherwise.
I also prepare orcin from meta dibromo toluol and analogous compounds in a
similar manner by heating them with caustic alkalies, preferably in closed vessels
and with agitation, the same being submitted to a temperature of from about 200°
to about 300° centigrade.
I also prepare orcin from meta bromo meta amido toluol and analogous com-
pounds by first converting the amido group into an bydroxyl group, and then
heating the resulting compound with caustic alkalies. For example, I take meta
bromo-meta amido toluol and dissolve the same in water acidulated with sulphuric
or other suitable acid. The temperature is then reduced and a solution of
potassium nitrite is gradually added until the meta bromo meta amido toluol is
converted into a diazo compound. This may be known by the smell of nitrous
acid being persistent. The solution is then heated until the diazo compound is
converted into meta bromo meta kresol. This partly separates as an oily substance,
and the remaining portion may be extracted from the solution by means of ether
and subsequent evaporation or otherwise. It may then be heated with caustic
potash, either in the solid or liquid form, to about from 200° to about 300°
centigrade, preferably with agitation in closed vessels, in order that orcin may be
obtained therefrom.
The melt or solution may then be acidulated and the orcin extracted therefrom
by means of ether or otherwise. I also prepare orein from ortho amido-toluol-
meta sulphonic acid, or from para amido-toluol-meta sulphonic acid, or from a
mixture of the two, by converting it first into a disulphonic acid and then removing
the amido group and then treating the resulting toluol meta disulphonic acid with
caustic alkalies.
For example, I take ortho amido-toluol meta sulphonic acid, or para amido
toluol meta sulphonic acid, or a mixture of the two, and heat it with about from 2
to 4 times its weight of fuming sulphuric acid to a temperature of about from
140° to about 200° centigrade until the mass dissolves easily in a small quantity of
water. The quantity of fuming sulphuric acid used and the exact temperature to
which the mixture must be heated in order to secure the best result depends upon
the strength of the acid. Ortho, or para toluidine, or a mixture of the two, known
as fluid toluidine, may be used instead of the sulphonic acids above described by
using a proportionately larger quantity of the fuming sulphuric acid.
The easily soluble mass obtained by the above process, or a similar compound
obtained in any other manner, is then dissolved in water and treated with caustic
lime or baryta or their carbonates, in order to remove the free sulphuric acid. The
liquid is filtered, and any lime or baryta remaining in the solution, either in a free
state or in combination with the disulphonic acids, is removed by a current of
carbonic acid or by the cautious addition of sulphuric acid.
The solution is now filtered and evaporated to dryness cautiously, and the dried
residue is mixed with a small quantity of strong alcohol or benzine, and a stream of
nitrous acid gas is introduced in order to form the diazo compound; strong alcoliol
is now added, and the whole is heated in a closed vessel under pressure to about
100° centigrade or thereabouts until the diazo compound is decomposed. The
resulting liquid is then saturated with an alkaline carbonate and the alcohol
distilled off. The alkaline salt so obtained is then heated with from one to four
times its weight of caustic potash or caustic soda, either in a solid form or in
solution, preferably at a temperature of from about 200° to about 320° centigrade with

page_text: agitation and in closed vessels. The resulting mass if solid alkali is used is
dissolved in water, and in either case the solution is acidified with sulphuric
or other suitable acid and the orcin extracted by evaporation or extraction with
ether or otherwise.
Having now described the nature of the Invention and the manner in which
the same may be carried into effect, I would observe in conclusion that I do not
confine myself to the use of those before mentioned substances which I have used
as examples, inasmuch as orcin may be prepared from meta chloro or meta-iodo
instead of from meta-bromo toluol meta-sulphonic acid, and from meta dichloro or
meta-di-iodo, instead of from meta di-bromotoluol, or from meta chloro or meta-
iodo, instead of from meta bromo-meta amido toluol; nor do I confine myself to
the precise details or proportions herein before mentioned, as the same may, fromn
the indications hereinbefore given, bo varied by any chemist conversant with the
ules of synthetical processes without departing from the principle of the Invention.
And I would also observe that for many purposes it is not necessary that the
processes for purification of the several products be carried out, but the resulting
substances may be used in their crude state and mixed with other substances
which, though not contributing to the production of orcin, yet do not prevent its
production. Therefore what I consider to be novel and original and therefore clairu
as the Invention is,―
First. The synthetical or artificial formation of orein from derivatives of toluol,
having in the two positions meta to methyl groups which are capable of being by
suitable methods replaced by hydroxyl groups.
Secondly. The synthetical or artificial formation of orein from meta-dinitro-
toluol, meta nitro meta amido toluol, meta nitro meta kresol, meta amido meta
kresol, or from one or more of the above products, substantially by the methods
herein beforo described.
Thirdly. The synthetical or artificial formation of orcin from meta dibromo
toluol and analogous substances, substantially as herein before described.
Fourthly. The synthetical or artificial formation of orein from meta bromo
toluol, meta-sulphonic acid, and analogous substances, substantially as hereinbefore
described.
Fifthly. The synthetical or artificial formation of orcin from meta bromo-, meta-
amido toluol, or from meta bromo, meta kresol, or from substances analogous to
either of them, or from one or more of them, substantially as herein before
described.
Sixthly. The synthetical or artificial formation of orcin from ortho toluidine or
para toluidine, or from ortho amido toluol meta sulphonic acid, or para amido
toluol-meta sulphonic acid, or ortho amido toluol meta-disulphonic acid, or para
amido toluol meta-disulphonic acid, or from toluol neta disulphonic acid, or
from any one or more of the above compounds, substantially as hereinbefore
described.
Seventhly. The synthetical or artificial formation of substituted compounds
similar to orcin from compounds similar to any of the above substances, but having
one or more of the other hydrogen atoms in the benzene ring substituted by
other groups by methods substantially similar to those herein before described.
In witness whereof, I, the said Ralph Henry Christopher Nevile, have to
this my Specification set my hand and seal, the Fifth day of April, One
thousand eight hundred and righty two.