The Manufacture or Production of Colouring Matters, and Materials therefor.
Year: 1894

page_text: Date of Application, 19th Mar., 1894
Complete Specification Left, 19th Dec., 1894-Accepted, 19th Jan., 1895
[Communicated from abroad by THE FARBENFABRIKEN, vormals FRIEDRICH
BAYER & Co., of Elberfeld, Germany.]
The Manufacture or Production of Colouring Matters, and Materials
therefor.
I HENRY EDWARD NEWTON, of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the County of London, Patent Agent, do hereby declare the
nature of this invention to be as follows:-
This invention, which relates to the production of dye stuffs and materials
therefor, is based on the fact discovered by my foreign correspondents, that those
products which are derived from rosaniline dye-stuffs, or similar coloring matters
belonging to the triphenylmethane, diphenylnaphthylmethane series, or the like,
and which contain, in the relative position "ortho" to the methane carbon atom,
an amido group substituted by an acid radicle, possess great technical value
as dye-stuffs, particularly owing to their great clearness and high degree of
solubility.
My foreign correspondents have first prepared such rosaniline dye-stuffs, or similar
coloring matters, belonging to the triphenylmethane or diphenylnaphthylmethane
series, or the like, and the researches of my foreign correspondents have shown
that these dye-stuffs, containing in the said relative position " ortho" to the
methane carbon atom, an amido group substituted by an acid radicle, can be
obtained by several methods, for instance, by means of the following processes:-
1. Alkylised amidobenzhydrols (such as tetramethyldiamidobenzhydrol) are
condensed with acid derivatives of alkylated meta diamines (for instance, mono-
acetoinetaamidodiethylaniline), and the leuco compounds so formed are sub-
sequently oxidised, or the ketones corresponding to the afforesaid alkylated diamido-
benzhydrols are condensed in the presence of suitable condensing agents with the
acid derivatives of alkylated meta diamines, or the alkylated diamido benzhydrols
are first condensed with meta diamines alkylated in the one amido group, and then
acid radicles are introduced into the free amido groups contained in the
condensation products so formed, and the leuco products thus produced are
subsequently oxidised; or
2. Alkylated diamidobenzhydrols, which contain in the so-called position "ortho "
to the methane carbon atom, an amido group substituted by an acid radicle, are
condensed with amines, substituted amines, diamines, amido sulpho acids, or other
amido compounds of the benzene or naphthalene series, or with acid derivatives of
alkylated meta diamines, and the resulting leuco compounds are subsequently
oxidised; or
3. Alkylated leuco compounds of the triphenylmethane series, diphenylnaphthyl-
methane series, are nitrated; the resulting mononitro compounds are reduced, and
after introducing acid radicles into the amido groups contained in the first formed
amido products, the resulting leuco compounds are converted into dye-stuffs by
treatment with oxidising agents.
My foreign correspondents describe more fully hereinafter the production of these
dye stuffs and certain intermediate products, which either are obtained in these
processes, or are required for carrying out these processes.

page_text: As above mentioned, dye-stuffs distinguished for their clearness are obtained on
condensing alkylated diamido benzhydrols with acid derivatives of alkylated meta
phenylene diamine, or analogous acid derivatives of alkylated meta diamines of the
benzene or naphthalene series, and subsequently oxidising the so-formed leuco
products. Of the aforesaid "acid derivatives of alkylated meta diamines," for
instance, monoacetometaamidomonoethylaniline and monoacctometaamidodiethyl-
aniline, can be used, which possess the following respective formulæ :—
DYE-STUFF FROM TETRAMETHYLDIAMIDOBENZHYDROL AND MONO ACETOMETA-
AMIDODIETHYLANILINE.
The
20-6 parts of finely powdered aceto metaamidodiethylaniline are added to a
solution prepared by dissolving 27 parts of tetramethyldiamidobenzhydrol in
150 parts of acetic acid (10 per cent.). The mixture is heated by means of a water
bath. After heating during half an hour, the condensation is finished.
resulting liquid, which shows a moderately blue color, is, when cooled, poured into
soda lye, which is likewise cooled. The leuco base, which separates as a light grey
powder, is filtered off, washed, and dried.
In order to effect the oxidation, 45.8 parts of the said leuco base are dissolved in
200 parts of acetic acid (50 per cent.) and 30 parts of muriatic acid (36.5 per cent.),
and 160 parts of a lead dioxide paste (containing 15 per cent. of PbO2) are stirred,
at ordinary temperature, into the above solution. The liquid, which has assumed a
deep blue color, is mixed with 50 parts of sulphuric acid (20 per cent.), in order to
precipitate the lead dissolved, and after filtering off the lead sulphate, the new dyc-
stuff is precipitated by adding zinc chloride and common salt to the resulting
filtrate. It separates as a greenish-yellow colored lustrous mass.
The dye stuff thus produced dissolves very readily in cold water, affording a blue
colored solution, and produces brilliant blue shades on cotton prepared with tannic
acid or the like.
Other analogous dye-stuffs result in a manner similar to that described in the
above First Example, if, on the one hand, tetramethyldiamidobenzhydrol used in
the above example is replaced by the corresponding quantity of another alkylated
diamidobenzhydrol, or if the aceto metaamidodiethylaniline is replaced by the
equivalent quantity of other "acid derivatives of alkylated meta diamines."
My foreign correspondents mean by the above expression "acid derivatives of
alkylated meta diamines," not only the aceto derivatives, but in general all acid
derivatives which contain the radicles of fatty or aromatic acids in place of
hydrogen of the one amido group, and are derived from alkylated meta diamines,
or substituted meta diamines, for instance, meta diamines sulphonic acids of
the benzene or naphthalene series, these diamines being alkylated in the other
amido group.
According to the researches of my foreign correspondents, the same coloring
matters can be obtained by using the corresponding ketones in place of the
aforesaid alkylated diamindobenzhydrols, and condensing these ketones in the

page_text: presence of suitable condensing agents with the above defined "acid derivatives of
alkylated meta diamines."
The same result is also obtained if alkylated diamidobenzhydrols are first
condensed with alkylated meta diamines, or substituted diamines (for instance
meta diamine sulphonic acids) of the benzene or naphthalene series, if the radicles
of fatty or aromatic acids are subsequently introduced into the free amido
groups contained in the first formed condensation products, and if the resulting
products are finally oxidised.
The researches of my foreign correspondents have shown that the dye-stuffs
herein before defined can also be produced by first preparing alkylated diamido
benzhydrols which contain an amido group substituted by fatty or aromatic acid
radicles, condensing these products with amines, substituted amines, amido
sulphonic acids, diamines, or the like, of the benzene or naphthalene series, or with
"acid derivatives of alkylated meta diamines," or substituted meta diamines, of the
benzene or naphthalene series, and subsequently oxidising the leuco products so
formed.
The said alkylated diamidobenzhydrols containing an amido group substituted by
fatty or aromatic radicles, are obtained, for instance, by nitrating alkylated
diamidodiphenylmethanes, reducing the so-formed mononitro products, introducing
the radicle of a fatty or aromatic acid into the amido group contained in the
reduction products, and finally oxidising the resulting methane compounds.
One method of producing the last-named alkylated diamidobenzhydrols containing
an amido group substituted by fatty or acid radicles, is illustrated by the following
example The parts are by weight
PRODUCTION OF MONO ACETO AMIDO TETRAMETHYLDIAMIDOBENZHYDROL.
254 parts of tetramethyldiamido diphenylmethane are dissolved in 200 parts of
sulphuric acid (66 degrees Baumé). In order to effect the nitration, a liquid
prepared by mixing 10-8 parts of nitric acid (40 degrees Baumé) with 14-2 parts of
sulphuric acid (66 degrees Baumé) is added, on cooling, taking care that the
temperature does not rise above 10 degrees Centigrade. The resulting mixture is
poured into ice water, and the nitro compound is precipitated by adding alkalies or
sodium acetate.
The so-formed nitro product crystallises from hot alcohol in long, flat red spears
melting at 95 degrees Centigrade.
In order to reduce the nitro compound, 30 parts of the latter are dissolved in
100 parts of muriatic acid (20 degrees Baumé), and (after adding ice) 20 parts of
zinc dust are gradually introduced whilst the mass is kept cool and well agitated.
When the reduction is completed, the mixture is filtered, and the amido compound
is precipitated by adding soda lye in excess to the resulting filtrate. The amido
product, which, when exposed to the action of the air, gradually assumes a reddish
color, crystallises from a mixture of ligroine and ether in great crystals melting at
96 degrees Centigrade. It can, by heating, for instance, with glacial acetic acid
and acetic anhydride, easily be converted into the aceto compound. In order to
effect the acetylating, 27 parts of the amido product are mixed with 100 parts of
glacial acetic acid, and 20 parts of acetic anhydride, and the resulting mixture is
boiled during from 1 to 3 hours. After distilling off the most part of the glacial
acetic acid in excess, the residue is dissolved in 20 parts of muriatic acid (20 degrees
Baumé) and 20 parts of water. On adding alkali to the resulting solution, the
acetylated amido compound separates, which, being crystallised from benzene and
ligroine, yields silky, lustrous white needles melting at 136 degrees Centigrade.
The oxidation of the acetylated amido product is effected by dissolving 31·1 parts
of the said acetylated product (which is chemically aceto-amido tetramethyldiamido

page_text: diphenylmethane) in 35 parts of muriatic acid (20 degrees Baumé), and about
100 parts of acetic acid (30 per cent.), and gradually stirring in 160 parts of a lead
dioxide paste (containing 15 per cent. of PbO2). The formation of the aceto
amido tetramethyldiamidobenzhydrol immediately takes place, the liquid assuming
an intense blue color. The lead dissolved is precipitated by means of 50 parts of
sulphuric acid (20 degrees Baumé), and after filtering off the lead sulphate, the said
hydrol is separated by adding alkali to the filtrate so formed. The hydrol thus
obtained forms a greyish powder.
Other aceto amido alkyldiamidobenzhydrols are obtained in a manner analogous
to that described in the above Second Example, if the tetramethyldiamidodiphenyl-
methane is replaced by the equivalent quantities of its analogues, for instance,
tetraethyldiamidodiphenylmethane or the like. Other acid radicles derived from
fatty or aromatic acids can likewise be introduced into the amido compounds first
formed, viz., on using the corresponding acids, acid anhydrides, acid chlorides, or
the like, or mixtures thereof.
As herein before mentioned, the aforesaid aceto-amido alkyldiamidobenzhydrols,
or analogues thereof, can be easily condensed with amines, substituted amines,
amido-sulphonic acids, diamines, or the like, of the benzene or naphthalene series,
leuco products being thus obtained which are, by a subsequent oxidation, converted
into valuable dye-stuffs. For instance, sulphonic acids of alkylated or benzylated
aniline, toluidine, or a-naphthyl-amine-ortho-monosulpho acid, or the polysulpho
acids derived from the last named monosulphonic can be used.
One method of producing the last mentioned leuco products and dye stuffs, is
illustrated by the following example: the parts are by weight.
+
า
LEUCO PRODUCT AND COLOURING MATTER FROM ACETOAMIDOTETRA-METHYL-
DIAMIDOBENZHYDROL AND METHYLDIPHENYLAMINE SULPHONIC ACID..
627 parts of meta-aceto amidotetramethyldiamidobenzhydrol are dissolved in
150 parts of acetic acid (50 per cent.), and the resulting liquid is mixed with a
solution prepared by dissolving 285 parts of methyldiphenylamine sulphonate of
sodium in a small quantity of dilute acetic acid. The resulting mixture is heated
by means of a water bath, until the blue colour of the hydrol used is no longer
distinguishable.
In order to effect the oxidation, 160 parts of a lead dioxide paste (containing
15 per cent. of PbO2) are added to the aforesaid liquid, when cold. When the
oxidation is finished, the lead dissolved is precipitated by means of 50 parts of
sulphuric acid (20 per cent.), and, after filtering off the lead sulphate precipitated,
the colouring matter is separated by adding common salt to the resulting filtrate.
The dye-stuff thus obtained produces beautiful blue shades on wool in an acid
bath.
Other lecuo products and colouring-matters are obtained in an manner analogous
to that described in the last example, if, on the one hand, meta-aceto amido-tetra-
methyldiamidobenzhydrol is replaced by the corresponding quantities of analogous
monoaceto amido products derived from alkylated amido benzhydrols, or the like,
or by analogous acid derivatives containing radicles of fatty or aromatic acids in
place of the hydrogen atoms of the amido groups contained in the amido alkyl-
diamidobenzhydrols, or if the methyldiphenylamine sulphonic acid is replaced by
the equivalent quantities of other sulphonic acids derived from alkylated or
benzylated aniline, toluidine, or the like, or, in general, by amines, substituted
amines, amidosulphonic acids, diamines of the benzene or naphthalene series, and if
the leuco products so formed are subsequently converted into the corresponding
dyestuffs by oxidation.
"
My foreign correspondents have also found, that on condensing the aforesaid

page_text: alkylated diamido benzhydrols containing an amido group substituted by fatty
or acid radicles (such as acetoamidotetramethyldiamidobenzhydrol) with the acid
derivatives of alkylated meta-diamines (such as monoacetometa amidodiethylaniline),
leuco products are obtained which contain two amido groups substituted by a
fatty or aromatic acid radicle. These products also possess technical value, as
they are, by a subsequent oxidation, converted into valuable dyestuffs, which
likewise contain two amido groups substituted by fatty or aromatic acid radicles.
Leuco products and dyestuff's identical with, or similar to those hereinbefore
defired, are obtained according to the researches of my foreign correspondents, if
certain leuco bases of the triphenylmethane series, diphenylnaphthylmethane series,
or analogous leuco products, are nitrated, subsequently reduced, and if a fatty or
aromatic acid radicle is introduced into the amido group, and if, finally the leuco
bases so formed are oxidised.
For instance, the leuco base of "crystal violet," having the formula :
This dyestuff is identical with that obtainable as described in the above first
20 example by condensing tetramethyldiamidobenzhydrol with aceto-meta-amido-
dimethylaniline, and subsequently oxidising the so-formed leuco product.

page_text: COLOURING MATTER FROM HEXAMETHYLLEUCANILINE.
37.3 parts of hexamethylleucaniline are dissolved in 350 parts of sulphuric acid
(66 degrees Baumé), and this liquid is mixed at about 10 degrees Centigrade with a
solution containing 10.8 parts of nitric acid (40 degrees Baumé) and 15 parts of
sulphuric acid (66 degrees Baumé). When the nitration is finished, the liquid is
poured into ice water, and the watery solution so formed is rendered alkaline. The
nitro product is thus separated as a yellowish-green crystalline mass, which, when
crystallised from toluene, forms greenish-yellow coloured needles melting at
207 degrees Centigrade.
In order to effect the reduction, 41.8 parts of the said nitro product are dissolved
in 100 parts of muriatic acid (20 degrees Baumé), and after adding ice, from 20 to
30 parts of zinc dust are gradually stirred into the cooled liquid. When the
reduction is finished, the resulting mixture is filtered, and the leuco base is
precipitated by adding alkalies to the filtrate obtained. The amido leucɔ base so
formed is a slightly coloured solid mass, which crystallises from alcohol in scales
melting at 190 degrees Centigrade. It is converted into the aceto compound by
treating with acetic anhydride. The acetylated amido leuco- base, when dissolved
in ligroine, separates in colourless crystal buttons.
The oxidation of the aceto amido-leuco compounds is effected by dissolving
43 parts of this base (aceto-meta-amido-hexa-methylleucaniline) in 160 parts of
acetic acid (50 per cent.), and 30 parts of muriatic acid (36.5 per cent.), and
gradually adding, at ordinary temperature, 160 parts of a lead dioxide paste
(containing 15 per cent. of PbO2). When the oxidation is finished, the lead
dissolved is precipitated by means of dilute sulphuric acid, and after filtering off
the lead sulphate, the colouring-matter is isolated in the usual manner from the
resulting filtrate.
Other dyestuffs result in a manner analogous to that described in the foregoing
example, if the hexamethylleucaniline used replaced by the equivalent quantities
of analogous substituted leucoanilines, or, in general, by leuco products of the
triphenylmethane series, diphenylnaphthylmethane series, for instance, those leuco
products which result from condensing secondary or tertiary amines of the benzene
or naphthalene series, with amidobenzhydrols substituted in the amido groups by
any alkyl-radicle, either the same or different ones; or if in place of forming the
aceto amido leuco products, the corresponding amido leuco products substituted by
other fatty or aromatic acid radicles, are prepared, and these products are
subsequently oxidised.
The dye-stuffs thus obtainable, in general, are similar to that obtainable as
described in the preceding fourth example.
In the production of the dye-stuffs and intermediate products hereinbefore defined
my foreign correspondents do not limit themselves to the methods herein before
nientioned, as all methods known and in use for the production of analogous
dyestuffs, or intermediate products, can also be used on carrying the invention
herein before described into practical effect.
Dated this 19th day of March 1894.
NEWTON & SON,
Agents for the Applicant.

page_text: The Manufacture or Production of Colouring Matters, and Materials
therefor.
1 HENRY EDWARD NEWTON of The Office for Patents, 6 Bream's Buildings,
Chancery Lane in the City of London, Patent Agent, do hereby declare the
nature of this invention and in what manner the same is to be performed, to be
particularly described and ascertained in and by the following statement :-
This invention, which relates to the production of dye-stuffs and materials
therefor, is based on the fact discovered by my foreign correspondents, that the
products derived from triphenylmethane dyes, or the like, containing, in one of
the nuclei, an amido-group in the ortho position relatively to the methane carbon
atom, into which an acid radicle has been introduced, possess great technical value
as dye-stuffs, particularly on account of their great clearness and solubility.
My foreign correspondents have first prepared such dye-stuffs with an amido
group containing an acid radicle in the said position, and the researches of my
foreign correspondents have shewn, that these dye-stuff's can be obtained by several
methods, for instance, by means of the following processes:
a) Alkylated diamido benzhydrols (such as tetramethyldiamidobenzhydrol) are
condensed with acid derivatives of di-alkylated metadiamines (for instance,
monaceto metaamido diethylaniline), and the leuco compounds so formed are
subsequently oxidised (see Example A).
b) Ketones (such as tetramethyldiamidobenzophenone), corresponding to the
aforesaid alkylated diamidobenzhydrols, are condensed in the presence of suitable
condensing agents with mono acid derivatives of meta diamines, dialkylated in the
one amido-group (this process being effected in the manner generally known and in
use for analogous purposes);
c) Alkylated diamidobenzhydrols are first condensed with meta-diamines di-
alkylated in the one amido group, and then any acid radicle is substituted for a
hydrogen atom in the other amido group, and the leuco products thus produced are
subsequently oxidised (see Example B).
d) Alkylated diamido benzhydrols, which contain in one nucleus, in the ortho
position relatively to the methane carbon atom, an amido group into which an acid
radicle has been introduced (such as monoaceto metamido tetramethyldiamido-
benzhydrol, see Example C), are condensed with tertiary aromatic amines (such as
dimethylaniline, diethylaniline), or acid derivatives of meta diamines, dialkylated
in the one amido group, and the leuco compounds thus formed are finally oxidised
(see the Examples D and E respectively);
e) Alkylated leuco compounds of the triphenylmethane series are nitrated, the
mononitro derivatives are reduced, and, after introducing any acid radicle into the
free amido group, the leuco compounds thus obtained are converted into dye-stuffs
by oxidation (see Example F).
My foreign correspondents describe more fully hereinafter the production of
these dye-stuff's, and certain intermediate products, which either are obtained in
these processes, or are required for carrying out these processes.
As above mentioned, dye-stuffs distinguished by their clearness are obtained on
condensing alkylated diamidobenzhydrols with acid derivatives of metadiamines,
dialkylated in the one amido group, and subsequently oxidising the so-formed leuco
products. Of the aforesaid "acid derivatives of metadiamines," dialkylated in the

page_text: one amido group, for instance, the monaceto meta-amido diethylaniline possessing
the following formula, can be used:-
One method of producing the last-mentioned leuco compounds and dye-stuffs
from acid derivatives of meta diamines, dialkylated in the one amido group, is
illustrated by the following example. The parts are by weight.
DYE-STUFF FROM TETRAMETHYLDIAMIDO BENZHYDROL AND MONACETO
METAMIDO DIETHYLANILINE.
20-6 parts of finely powdered monaceto metamidodiethylaniline are added to a
solution prepared by dissolving 27 parts of tetramethyldiamido benzhydrol in
150 parts of acetic acid (10 per cent.). The mixture is heated by means of a
water bath, during about half an hour, when the condensation is finished. The
liquid, which is of a blue colour, is cooled, and then poured into cooled soda lye.
The leuco base, which separates as a light gray powder, is filtered off, washed, and
dried.
In order to effect the oxidation, 45'8 parts of the said leuco base are dissolved
in 200 parts of acetic acid (50 per cent.), and 30 parts of muriatic acid (36.5 per cent),
and 160 parts of a lead dioxide paste (containing 15 per cent. of PbO₁) are
stirred into the solution at the ordinary temperature. A deep blue coloured
liquid is thus obtained, which is mixed with 50 parts of sulphuric acid (20 per
cent.), in order to precipitate the dissolved lead, and, after filtering off the lead
sulphate, the new dye-stuff is precipitated by adding zinc chloride and common
salt to the filtrate. It separates as a greenish-yellow coloured lustrous mass, and
is isolated by filtration.
The dye-stuff thus produced dissolves very readily, even in cold water, affording
a blue coloured solution, and produces brilliant blue shades on cotton prepared
with tannic acid or the like.
Other analogous dye-stuffs are formed in a manner similar to that described in
the above Example A, if, instead of the tetramethyldiamido benzhydrol used in
the above example, the corresponding quantity of another alkylated diamido-
benzhydrol be used, or if the equivalent quantity of another acid derivative of
meta diamines, dialkylated in the one amido group, be substituted for the aceto
meta amidodiethylaniline.
My foreign correspondents mean by the above expression, acid derivatives of
meta diamines, dialkylated in the one amido group, not only the aceto derivatives,
but, in general, acid derivatives of dialkyl meta diamines, containing a fatty or
aromatic acid radicle in the one amido group, and two alkyl groups in the other
amido group.
The following acid derivatives of meta diamines, dialkylated in the one amido
group, for instance, can be used in place of the monaceto metamido diethylaniline
prescribed in the preceding Example A, viz. :-Monacetometamido-dimethylaniline,

page_text: monobenzoyl-metamido dimethylaniline, and monobenzoylmetamido diethyl-
aniline (which can be produced by benzoylating metamido dimethylaniline, or
metamido diethylaniline respectively), or monaceto metamidodibenzylaniline
(obtainable by benzylating metanitraniline, reducing the metanitrodibenzyl
aniline thus formed, and subsequently acetylating the metamidodibenzylaniline).
According to the researches of my foreign correspondents, the same colouring
matters can be obtained by using the corresponding ketones in place of the
aforesaid alkylated diamido benzhydrols, and condensing these ketones in the
presence of suitable condensing agents, with the "acid derivatives of meta-
diamines dialkylated in the one amido group" hereinbefore defined. This process
is carried out in the manner generally known and in use for producing analogous
dye-stuffs.
The same result is also obtained, if alkylated diamido benzhydrols are first
condensed with metadiamines, dialkylated in the one amido group, and if a fatty
or aromatic acid radicle is subsequently substituted for a hydrogen atom in the
free amido group contained in the first-formed condensation products, and if the
products are finally oxidised.
In order to illustrate the last named process, the following example is given ;
the parts are by weight.
COLOURING-MATTER
OBTAINED BY CONDENSING
TETRAMETHYLDIAMIDO
BENZHYDROL WITH METAMIDO DIMETHYLANILINE, ACETYLATing the
SO-FORMED LEUCO BASE, AND SUBSEQUENTLY OXIDISING THE RESULTING
ACETYLATED LEUCO PRODUCT.
27 parts of tetramethyldiamido benzhydrol are dissolved in 300 parts of water,
and 30 parts of muriatic acid (36-5 per cent.), and 13-6 parts of metamidodimethyl-
aniline are then added to the solution. The liquid is heated by means of a water
bath until the hydrol is no longer distinguishable. The leuco base, which is
precipitated by adding alkalies or sodium acetate to the greenish coloured
liquid, forms a crystalline mass having a slight blue colour. When crystallised
froin toluene, it forms small flat needles melting at from 190 to 191 degrees
Centigrade.
By a suitable treatment with acetylating agents (such as acetic anhydride),
this leuco base is converted into the acetylated leuco product, and the latter
is finally oxidised by means of lead dioxide.
The analogous colouring-matters are obtained, if, instead of the tetra methyl-
diamido benzhydrol used in the last example, corresponding quantities of other
alkylated diamidobenzhydrols, or other meta diamines, dialkylated in the one
amido group, are used in place of the meta dimethylaniline prescribed in the said
example.
The researches of my foreign correspondents have shewn, that dye-stuff's
similar to those hereinbefore defined, can also be produced by first preparing
alkylated diamido benzhydrols containing an amido group into which a fatty or
aromatic acid radicle has been introduced, condensing these products with tertiary
amines, or with acid derivatives of metadiamines dialkylated in the one amido
group, and subsequently oxidising the leuco products so formed.
The said alkylated diamido benzhydrols containing an amido group into which
B

page_text: a fatty or aromatic acid radicle has been introduced, are obtained, for instance, by
nitrating alkylated diamido diphenylmethanes, reducing the mononitro products,
introducing the fatty or aromatic acid radicle into the amido group contained in
the reduction products, and finally oxidising the methane compounds thus
formed.
One method of producing the last-named alkylated diamido benzhydrols
containing an amido group into which a fatty or acid radicle has been introduced,
is illustrated by the following Example C. The parts are by weight.
PRODUCTION OF MONACETO-METAMIDO-TETRAMETHYLDIAMIDO BENZHYDROL.
25-4 parts of tetramethyldiamido diphenylmethane are dissolved in 200 parts of
sulphuric acid (66 degrees Baumé). In order to effect the nitration, a liquid
prepared by mixing 10.8 parts of nitric acid (40 degrees Baumé), with 14-2 parts
of sulphuric acid (66 degrees Baumé) is added, care being taken to cool, so that
the temperature does not rise above 10 degrees Centigrade. The mixture is
poured into ice water, and the nitro compound, which is precipitated by adding
alkalies or sodium acetate, is isolated by filtration.
The nitro product crystallises from hot alcohol in long, flat, red, spear-shaped
crystals melting at 95 degrees Centigrade.
In order to reduce this nitro compound, 30 parts of the latter are dissolved in
100 parts of muriatic acid (20 degrees Baumé), and (after adding ice) 20 parts of
zinc dust are gradually introduced, the mass being kept cool and well agitated.
When the reduction is completed, the mixture is filtered, and the amido compound
is precipitated by adding soda-lye in excess to the filtrate. The amido product,
which gradually assumes a reddish colour in contact with the air, crystallises from
a mixture of ligroine and ether in large crystals melting at 96 degrees Centigrade.
It can easily be converted into the acetyl compound, for instance, by heating with
acetic anhydride.
To effect the acetylation, 27 parts of the amido compound are dissolved in
50 parts of benzene, and 11 parts of acetic anhydride are gradually added. After
heating during a short time by means of a water bath, the mixture is rendered
alkaline by sodium carbonate. On distilling off the benzene, the acetylated
product remains as a slightly yellowish coloured crystalline mass, which, on being
crystallized from benzene and ligroine, yields silky lustrous white needles melting
at 136 degrees Centigrade.
The oxidation of the acetylated amido product is effected by dissolving 31.1 parts
of the said acetylated product, acetamido tetramethyldiamido diphenyl methane,
in 15 parts of mono-hydrated sulphuric acid, and 100 parts of acetic acid
(containing 30 per cent. of pure acetic acid), and gradually stirring in 160 parts of
a lead dioxide paste (containing 15 per cent. of PbO,). The formation of the
aceto amido tetramethyl diamidobenzhydrol immediately takes place, the liquid
assuming an intense blue colour. The dissolved lead is precipitated by means of
50 parts of sulphuric acid (20 degrees Baumé). After filtering off the lead
sulphate, the hydrol is separated by adding alkali to the filtrate, and by filtration.
The hydrol thus obtained forms a greyish powder, which, after crystallization from
alcohol, melts at 162 degrees Centigrade.
My foreign correspondents have ascertained that the mononitrotetramethyl-

page_text: This formula is established by the fact discovered by my foreign correspondents,'
5 that the said mononitro compound, when further treated with nitrating agents,
yields a dinitro derivative which, on reduction and further suitable treatment, is
converted into a derivative of acridine. Of course, a derivative of acridine can
only be produced, in this case, from a diamido compound corresponding to a
-dinitro compound having the formula :-

page_text: My foreign correspondents therefore ascribe the following formula to the mon-
acetamidotetramethyldiamido benzhydrol produced by the process illustrated by
the foregoing Example C, viz. :—
Other aceto-amidoalkyldiamidobenzhydrols are obtained in a manner analogous
to that described in the preceding Example C, if, instead of the tetramethyldiamido-
diphenylmethane used therein, equivalent quantities of its analogues, for instance,
tetraethyldiamido diphenylmethane, or the like, are used. Other acid radicles,
derived from fatty or aromatic acids, can also be introduced into the amido
compounds which are first formed, viz., by using the corresponding acids, acid
anhydrides, acid chlorides, or the like, or mixtures thereof.
For instance, benzoylmetamidotetramethyldiamidodiphenylmethane (which is
obtained from metamidotetramethyldiamido diphenylmethane by benzoylating),
melting at from 156 to 157 degrees Centigrade, can be easily oxidised and
converted into benzoyl metamidotetramethyldiamido benzhydrol. Tetraethyldi-
amidodiphenylmethane yields a mononitro compound forming ruby-colored prismatic
crystals melting at from 79 to 80 degrees Centigrade, which, by subsequent
reduction, acetylation, and oxidation, is converted into acetamidotetraethyldiamido-
benzhydrol.
All these hydrols are slightly-colored powders, which readily dissolve in mineral
acids, and, when heated with glacial acetic acid, yield an intense blue solution.
They can be obtained in a pure state by crystallisation from alcohol.
As herein before mentioned, the monacetamidotetralkyldiamidobenzhydrol, or its
analogues, can be condensed with tertiary aromatic amines, leuco products being
thus obtained, which, on oxidation, afford valuable dye-stuffs. For instance,
dialkylated or dibenzylated aniline or toluidine, or the like, can be used.
The process for producing these coloring matters is illustrated by the following
Example D. The parts are by weight.
DYE-STUFF PRODUCED BY OXIDISING THE CONDENSATION PRODUCT FROM 3
ACETOMETAMIDOTETRAMETHYLDIAMIDO
BENZHYDROL
AND DIMETHYL-
ANILINE.
10.1

page_text: 32-7 parts of acetometamidotetramethyldiamido benzhydrol in 300 parts of acetic
neid (containing 50 per cent. of pure acetic acid). The bluish color of the solution
disappears on heating during a short time in a water bath. The liquid having
been cooled, 160 parts of a lead dioxide paste (containing 15 per cent. of lead
dioxide) are quickly stirred in, and the mixture is kept stirred during an hour.
The dissolved lead is then precipitated by adding sodium sulphate, and, after
filtering off the lead sulphate, the dye-stuff is precipitated by adding 10 parts of
fuming muriatic acid, and a proper quantity of zinc chloride and common salt, to
the filtrate. The coloring matter thus obtained is the zinc chloride double salt,
and forms a bronze colored powder which readily dissolves even in cold water. It
produces clear blue shades on cotton prepared with tannic acid or the like.
Similar dye-stuffs are formed if corresponding quantities of other dialkylamines,
such as diethylaniline or the like, are used in place of dimethylaniline, or on
substituting for the monacetometamidotetramethyldiamido benzhydrol, equivalent
quantities of monacetometamidotetraethyldiamido benzhydrol, or analogous monaccto
or monobenzoylated compounds.
My foreign correspondents have also found, that on condensing the aforesaid
alkylated diamidobenzhydrols containing an amido group into which a fatty or
aromatic acid radicle has been introduced (such as aceto amidotetramethyldiamido
benzhydrol), with the acid derivatives of dialkylated meta-diamines (such as mono-
acetometaamidodiethylaniline), leuco products are obtained in which there are
two amido groups containing a fatty or aromatic acid radicle. These products are
also of technical value, as, by subsequent oxidation, they are converted into
valuable dye-stuff's, also containing two amido groups into which a fatty or aromatic
acid radicle has been introduced.
The following example is given, in order to illustrate this new process. The
parts are by weight.
COLORING MATTER PRODUCED BY OXIDISING THE LEUCO PRODUCT OBTAINED
FROM ACETOMONAMIDOTETRAMETHYLDIAMIDO BENZHYDROL AND ACETO
METAMIDO DIMETHYLANILINE.
32.7 parts of acetometamidotetramethyldiamido benzhydrol, and 17-8 parts of
acetometamidodimethylaniline, are dissolved in 250 parts of acetic acid (50 per cent.),
and 30 parts of muriatic acid (36-5 per cent.). The solution is heated by means of
a water bath, until the hydrol is no longer distinguishable. After cooling,
160 parts of a lead dioxide paste (containing 15 per cent. of lead dioxide) are
stirred into the liquid, in order to effect the oxidation. When the oxidation is
complete, the dissolved lead is precipitated in a suitable manner, and the solution
is mixed with zinc chloride and common salt. The dye stuff thus precipitated
forms a violet or bronze colored powder, which readily dissolves in water, and
produces, on cctton prepared with tannic acid or the like, clear greenish-blue
shades.
Other dye stuffs are formed in an analogous manner, if, instead of monaceto-
metamidotetramethyldiamidobenzhydrol, corresponding quantities of monacetomet-
amidotetraethyldiamidobenzhydrol, or other acid derivatives (such as benzoyl
derivatives) of metamidotetralkyldiamnidobenzhydrols, or if other of the "acid
derivatives of dialkylated metadiamines" herein before referred to, are used in
place of the monacetometamido dimethylaniline prescribed in the last example.
Leuco products and dye-stuffs identical with, or similar to those hereinbefore
defined, are obtained according to the researches of my foreign correspondents, if
certain leuco bases of the triphenylmethane series are nitrated, then reduced, and
if a fatty or aromatic acid radicle is introduced into the amido group, and if the
leuco bases só formed are finally, oxidised.

page_text: For instance, the leuco base of "crystal-violet," having the formula
This dye-stuff is identical with that obtainable as described in the above
Example A, by condensing tetramethyldiamidobenzhydrol with aceto meta amido-
dimethylaniline, and subsequently oxidising the leuco product so formed.
In order to illustrate the last-named method of producing dye-stuffs, the following
example is given, the parts being by weight.
LEUCO PRODUCT. AND COLORING MATTER FROM HEXAMETHYLEUCANILINE.
31
37.3 parts of hexamethylleucaniline (leuco base of crystal-violet) are dissolved
in 350 parts of sulphuric acid (66 degrees Baumé), and this liquid is mixed, at

page_text: about 10 degrees Centigrade, with a solution containing 10.8 parts of nitric acid
(40 degrees Baumé), and 15 parts of sulphuric acid (66 degrees Baumé). When
the nitration is finished, the liquid is poured into ice water, and the solution is then
rendered alkaline. The nitro product separates as a yellowish-green crystalline
mass, which, when crystallised from toluene, forms greenish-yellow colored needles
melting at 207 degrees. Centigrade.
In order to effect the reduction, 41.8 parts of the said nitro product are
dissolved in 100 parts of muriatic acid (20 degrees Baumé), and, after adding ice,
from 20 to 30 parts of zinc dust are gradually stirred into the cooled liquid.
When the reduction is finished, the mixture is filtered, and the leuco base is
precipitated by adding alkalies to the filtrate. The amido leuco base so formed
is a slightly colored solid, which crystallises from alcohol in scales melting at
190 degrees Centigrade. It is converted into the aceto compound by treating
with acetic anhydride. The acetylated amido leuco base crystallises from ligroine
in colorless warty forms.
The oxidation of the aceto amido lenco compound is effected by dissolving
43 parts of this base (aceto meta amidohexamethylleucaniline) in 160 parts of
acetic acid (50 per cent.), and 30 parts of muriatic acid (36.5 per cent.), and
gradually adding, at ordinary temperature, 160 parts of a lead dioxide paste
(containing 15 per cent. of Pho₂). When the oxidation is finished, the dissolved
lead is precipitated by means of dilute sulphuric acid, and, after filtering off the
lead sulphate, the coloring matter is isolated in the usual manner from the filtrate.
Other leuco products and dye-stuffs are formed in a manner analogous to that
described in the foregoing Example F, if, instead of hexamethylleucaniline, the
equivalent quantities of hexethylleucaniline, or analogous leuco products of the
triphenylmethane series are used, or if, instead of forming the aceto amido leuco
compounds, the corresponding amido leuco compounds containing another fatty or
aromatic acid radicle are prepared, and these products are subsequently oxidised.
The dye stuffs thus obtainable in general are similar to that obtainable as
described in the preceding Example F.
In producing the dye-stuffs and intermediate products herein before defined, my
foreign correspondents do not limit themselves to the methods herein before
mentioned, as all methods known and in use for the production of analogous dye-
stuffs, or intermediate products, can also be used, on carrying the invention
hereinbefore described into practical effect.
Having now particularly described and ascertained the nature of the said inven-
tion and in what manner the same is to be performed (as communicated to be from
abroad), I declare that what I claim is :-
1. The production of leuco products and dye-stuffs from alkylated diamido
benzhydrols, and monacid derivatives of meta diamines, dialkylated in the one
amido group.
2. The process for producing leuco compounds, which process consists in
condensing molecular proportions of tetramethyl or tetrethyldiamido benzhydrol,
and monaceto metamido dimethylaniline, monacetometamido diethylaniline,
monobenzoylmetamido dimethylaniline, monobenzoylmetamido diethylaniline, or
monaceto metamido dibenzylaniline.
3. The production of coloring matters by suitably oxidising the leuco compounds
produced by the process claimed in the foregoing second claim.
4. The manufacture of dye-stuffs by condensing a molecular proportion of
tetralkyldiamido benzophenone (such as tetramethyldiamido benzophenone, or
tetrethyl diamidobenzophenone), in the presence of suitable condensing agents,
with a molecular proportion of monacetometamidodimethylaniline, monacetomet-
amido diethylaniline, monobenzoylmetamidodimethylaniline, monobenzoylmetamido-
diethylaniline, or monacetometamidobenzylaniline.
5. The process for producing leuco products, which process consists in condensing
a molecular proportion of tetralkyldiamido benzhydrol (such as tetramethyldiamido

page_text: benzhydrol, or tetrethyldiamido benzhydrol), with a molecular proportion of a
meta diamine, dialkylated in the one amido group, and in subsequently treating
the so-formed condensation products with suitable agents, in order to introduce
an acid radicle (such as acetic or benzoyl radicle), in place of a hydrogen atom of
the free amido group contained in the said condensation product.
6. The conversion of the leuco compounds produced according to the process
claimed in the foregoing fifth claim, into the corresponding coloring matters, by
oxidation.
7. The production of tetralkyldiamido benzhydrols containing an amido group,
into which a fatty or aromatic acid radicle has been introduced, by converting
tetralkylated diamido diphenylmethanes, or analogues thereof, into mononitro
derivatives, reducing the latter, treating the monamido products thus formed with
suitable agents, in order to introduce an acid radicle (such as the acetyl or benzoyl
radicle), in place of a hydrogen atom in the free amido group, and subsequently
oxidising the acid derivatives of metamonamido tetralkyldiamidodiphenylmethanes,
to form acid derivatives of metamonoamidotetralkyldiamido benzhydrols.
8. The manufacture of monacetometamidotetramethyldiamido benzhydrol,
monacetometamidotetraethyldiamido benzhydrol, monobenzoylmetamidotetramethy-
diamido benzhydrol, or monobenzoylinetamidotetraethyl diamido benzhydrol, from
tetramethyldiamido benzhydrol, or tetraethyldiamidobenzhydrol, respectively, by
means of the process claimed by the preceding seventh claim.
9. The process for producing leuco compounds, which process consists in
condensing a molecular proportion of monacetometamidotetramethyldiamido-
benzhydrol, monacetometamidotetraethyldiamidobenzhydrol, monobenzoylmet-
amidotetramethyldiamido benzhydrol, monobenzoylmetamidotetraethyl diamido
benzhydrol, or the like, with one molecular proportion of dialkylaniline (such as
dimethylaniline, diethylaniline), or the like, or acid derivative of metadiamines
dialkylated in the one amido group, such as monacetometamidodimethylaniline,
monacetometamidodiethylaniline,
mono-
monobenzoylmetamidodimethylaniline,
benzoylmetamidodiethylaniline, monacetometaniidodibenzylaniline, or the like.
10. The conversion of the leuco compounds produced according to the preceding
ninth claim, or by any other process, into the corresponding dye-stuffs, by
oxidation.
11. The production of leuco compounds by converting hexalkyltriamidotriphenyl-
methanes (such as hexamethyl or hexacthyl triamidotriphenylmethane), or analogues
thereof, into mononitro products, reducing the latter, and subsequently treating
the monamido hexalkyltriamido triphenyl-methanes, or the like, in a suitable
manner, in order to introduce an acid radicle (such as the acetyl or benzoyl
radicle), in place of a hydrogen atom in the free amido group of these monamido-
hexalkyltriamido triphenylmethanes, or the like.
12. The conversion of the acid derivatives of monamidohexalkyltriamido
triphenylmethanes (such as monacetamido hexamethyltriamidotriphenylmethane,
monacetamidohexaethyltriamidotriphenylmethane, monobenzoylamidohexamethyl
triamido triphenylmethane), or the like, into the corresponding dye-stuffs, by
oxidation.
13. As new products of manufacture, the new leuco compounds, and the new
intermediate products, and the new dye-stuffs produced by the processes herein-
before defined, or by any process affording the same result.
Dated this 19th dow of Domb 1904
NEWTON & SON,
Agents for the Applicant.