The Production of Violet and Blue Coloring Matters of the Rose- aniline-series by Treating Aromatic Amines with Alkylised Amidodoxinating of Donzovlobloxide and of Ropeonhonore
Year: 1884

page_text: The Production of Violet and Blue Coloring Matters of the Rose-
aniline-series by Treating Aromatic Amines with Alkylised
Amidodoxinating of Donzovlobloxide and of Ropeonhonore
I, CHARLES DENTON ABEL of No 28 Southampton Buildings Chancery Lane in
the County of Middlesex, Consulting Engineer and Patent Agent, seek leave to
amend the Specification of Letters Patent N° 4961 of 1884 as shewn in red ink
in the Queen's Printers Copy of the original Specification hereunto annexed:—
From which it will appear that the amendment proposed consists essentially in
the excision of the second claim and of those parts of the title and description
which relate thereto.
My reasons for making this amendment are as follows :—
That since filing the said Specification I have been advised that the subject
matter of the invention has been too broadly stated and claimed therein.

page_text: In the matter of the application made by Charles Denton Abel for leave to amend
the Specification of Letters Patent N° 4961 of 1884.
I hereby grant leave to the said Charles Denton Abel to amend the said
Specification in the manner proposed.

page_text: I, CHARLES DENTON ABEL of N° 28 Southampton Buildings, Chancery Lane, in
the County of Middlesex, Consulting Engineer and Patent Agent, do hereby declare
the nature of the said invention for "THE PRODUCTION OF VIOLET AND BLUE
COLORING MATTERS OF THE ROSEANILINE-SERIES BY TREATING AROMATIC AMINES
WITH ALKYLISED AMIDODERIVATIVES OF BENZOYLCHLORIDE AND OF BENZOPHENONE
to be as follows:--
1. E & O Fischer (Berichte des Deutschen chem. Gesellschaft (1879) vol XII
p 797; v. also p 800 & 802) have shown that malachite green (bitter-almond-oil-
green) is formed by the action of benzoylchloride upon dimethylaniline in presence
of a condensing agent (zinc-chloride). In an analogous way, according to the
present invention, coloring matters of the roseaniline series are obtained when
C. H. N (Alk) 2
Ci
tertiary alkylised amidoderivatives of benzoylchloride CO-
are allowed to act upon tertiary aromatic amines in the presence of condensing
agents as shewn in the following example:-
Dimethylamidobenzoic acid (Michler Berichte d. D. ch. G (1876) vol IX p 401) is
by the aid of phosphorus pentachloride (1 molecule) converted into dimethylamido-
C¸ H¸ N (C H¸) 2
benzoylchloride CO-
Cl
(Michler, ibid). This is mixed with
an excess of diethylaniline and aluminium chloride and the mixture thus
obtained is gently heated. By this means a mixed ketone having the formula
C. H. N (CH) 2
CO
C, H, N (C, H.) 2 (Michler Ber. d. D. 'ch G (1876) vol IX p 716) is
formed in the first instance. The latter reacts upon a second molecule of diethyl-
aniline producing dimethyltetraethylroseaniline C
-C, H, N (C. H,) 2
-C, H. N (C, H.) 2
-C¸ H¸ N (CH) 2 Cl.
(Compare also the similar formation of dimethylamidotriphenylmethane from
benzophenonechloride and dimethylaniline O Fischer Ber d. D. ch. G (1879)
vol XII p 1690), a violet coloring matter of a more blueish shade than the
"Violet 6 B" of commerce.
:
On employing methyldiphenylamine in the place of diethylaniline in the reaction
just described tetramethyldiphenylpararosaniline is obtained which is a very blue
violet.
2. The ketones formed as intermediate products in the foregoing reaction, which
are tetraalkyldiamidobenzophenones, may be separated by a suitable method
(Michler & Dupertius Ber d. D. ch. G (1876) vol IX p 1899; Michler & Gradmann
Ber d D ch G (1876) vol IX p 1914).
When for instance dimethylamidobenzoylechloride is heated with an excess of
diethylaniline the mixed ketone dimethyldiethyldiamidobenzophenone of the
formula CO.
C. H. N (C H₂) 2 is formed, and may be separated in the
C. H. N (C₂ H) 2
shape of plates by distilling off the excess of diethylaniline with steam and
crystallising the residue from alcohol;
Such ketones react upon tertiary aromatic amines with formation of coloring
matters of the roseaniline series when any one or more of the following condensing

page_text: agents are present: aluminium chloride, carbonylchloride, phosphorus-tri-chloride,
phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide,
phosphorus oxychloride, phosphorus oxybromide. The same ketones react upon
secondary aromatic amines with formation of coloring matters in the presence of
sulphuric acid as condensing agent.
°
When for instance dimethyldiethyldiamidobenzophenone is allowed to act upon
an excess of methyldiphenylamine in the presence of one of the condensing agents
enumerated, a very blue violet is obtained having the formula:
-C HN (C H₁) 2
C. H. N (C, H) 2 Cl..
As is shown in this example coloring matters of the roseaniline series may
be obtained by this method which contain the radicals of three different tertiary
aromatic amines.
3. When it is intended to prepare coloring matters containing the radicals of one
and the same tertiary amine, it is not necessary to separate the benzoylchloride or
ketone formed in the first instance. For example:-a current of carbonylchloride
is passed into a mixture of methyldiphenylamine and aluminium chloride; after
being allowed to stand for several days, the excess of methyldiphenylamine is
removed by a current of steam and the residue is now found to consist of a mass of
coppery lustre soluble in alcohol with a blue color. By converting the new coloring
matter into its sulphonic acid and preparing the sodium salt of the latter, a blue
coloring matter of the shade known as 3 B is obtained which is soluble in water.
In place of aluminium chloride, anhydrous ferric chloride can be used in these
reactions.
4. The amines, chlorides of acid radicals and ketones employed in the foregoing
syntheses are the following:-
Secondary amines:-Diphenylamine, alpha dinapthylamine.
.
Tertiary amines:-The tertiary methyl- ethyl isobutyl- amyl, and benzyl-
derivatives of aniline, orthotoluidine, ortho-anisidine, alpha-napthylamine, diphenyl-
amine, alpha-dinapthylamine, phenyl-alpha-napthylamine and metaphenylendia-
mine. Phenyl alpha dinaphthylamine may also be employed.
Chlorides of acid radicals :-The chlorides of acid radicals which are obtained
from the tertiary amines just enumerated by the action of carbonylchloride in
the presence or absence of condensing agents or from dialkylamidobenzoic acids
C. H. N (Alk) 2
CO
by treatment with phosphorus pentachloride and
OH
similar bodies.
-
.
Ketones: The ketones which result from the tertiary amines above enumerated
by the action of the chlorides of acid radicals mentioned in the presence or absence
of condensing agents.
By alkyles I understand the hydro-carbon radicals methyl, ethyl, phenyl, tolyl,
benzyl etc etc.
Dated this 15th day of March 1884.

page_text: I, CHARLES DENTON ABEL of N° 28 Southampton Buildings, Chancery Lane,
in the county of Middlesex, Consulting Engineer and Patent Agent, do hereby
declare the nature of the said invention for "THE PRODUCTION OF VIOLET AND
BLUE COLORING MATTERS OF THE ROSEANILINE SERIES BY TREATING AROMATIC AMINES
WITH ALKYLISED AMIDODERIVATIVES OF BENZOYLCHLORIDE AND OF BENZOPHENONE"
and in what manner the same is to be performed to be particularly described
and ascertained in and by the following statement :—
1, E&O, Fischer (Berichte des Deutschen chem: Gesellschaft, 1879, vol. XII
p. 797; v: also p. 800 and 802) have shewn that malachite-green (bitter-almond-
oil-green is formed by the action of benzoyl-chloride upon dimethylaniline in.
presence of a condensing agent (zinc-chloride). In an analogous way, according to
the present invention, coloring matters of the roseaniline series are obtained when
tertiary alkylised amidoderivatives of benzoylchloride CO. C₁ H. N (Alk) 2
Cl
are allowed to act upon tertiary aromatic amines in the presence of condensing
agents as shewn in the following example.
Dimethylamidobenzoic acid (Michler Berichte d. D. ch. G (1876) vol. IX p. 401)
is, by the aid of phosphorus pentachloride (1 molecule) converted into dimethyl-
amidobenzoylchloride CO.
C. H. N (O H₁) 2
(Michler. ibid.). This is mixed
CI.
with an excess of diethylaniline. and aluminium chloride and the mixture thus
obtained is gently heated. By this means a mixed ketone having the formula
co
C, H, N (C H₁) 2
C, H, N (C, H) 2 (Michler. Ber. d. D. ch. G (1876) vol. IX p. 716) is
formed in the first instance. The latter reäcts upon a second molecule of diethyl-
aniline, producing dimethyl-tetraethyl-roseaniline C
-C HN (C H₁) 2
-C. H. N (C, H.) 2
-C H. N (C₂ H.) 2 Cl.
>
(compare also the similar formation of dimethylamidotriphenylmethane from
benzophenonechloride and dimethylaniline: 0, Fischer, Ber. d. D. ch. G (1879);
vol. XII p. 1690) a violet coloring matter of a more bluish shade than the
"Violet 6 B" of commerce.
On employing methyldiphenylamine in the place of diethylaniline in the reaction
just described, tetramethyldiphenylpararosaniline is obtained which is a very blue
violet.
2, The ketones formed as intermediate products in the foregoing reaction, which
are tetra-alkyldiamidobenzophenones may be separated by a suitable method

page_text: (Michler & Durpertius Ber: d: D. ch.-G.-(1876) vol IX p.-1899-;-Michler &
Gradmann, Ber. d. D. oh. G.-(+876) vol. IX, p. 1914).
When, for instance, dimethylamido benzoylechloride is heated with an excess
of diethylaniline, the mixed ketone dimethyldiethyl diamidobenzophenone of the
CHN(CH) is formed, and may be separated in the shape
formula CO
GHN(C,H)-
of plates by distilling off the excess of diethylaniline with steam, and erystallising
the residue from alcohol.
Such ketones reüet upon tertiary aromatic amines with formation of coloring
matters of the roseaniline-series when any one or more of the following condensing
agents are present: aluminium chloride, carbonylchloride, phosphorustrichloride,
phosphorus pentachloride, phosphorus tribromide, phosphorus-pentabromide,
phosphorus oxychloride, phosphorus oxybromide.
The same ketones reäet-upon-secondary aromatic amines with formation of
coloring matters in the presence of sulphuric acid as condensing agent.
When, for instance dimethyl diethyl diamidobenzophenone is allowed to not
upon an excess of methyldiphenylamine in the presence of one of the condensing
agents enumerated, a very blue violet is obtained, having the formula:
As is shewn in this exs ple, coloring matters of the roseanttime-series may be
obtained by this method which contain the radicals of three different tertiary
aromatio-amines.
:
23, When it is intended to prepare coloring matters.containing the radicals of
one and the same tertiary amine it is not necessary to separate the benzoylchloride
or ketone formed in the first instance. For example, a current of carbonylchloride
is passed into a mixture of methyldiphenylamine and aluminium chloride; after
being allowed to stand for several days, the excess of methyldiphenylamine is
removed by a current of steam and the residue is now found to consist of a mass
of coppery lustre, soluble in alcohol with a blue color. By converting the new
coloring matter into its sulphonic acid and preparing the sodium-salt of the latter,
a blue coloring matter of the shade known as 3 B is obtained which is soluble in
water. In place of aluminium chloride anhydrous ferric chloride can be used in
-these reactions.
34. The amines, and chlorides of acid radicals and-ketones employed in the
foregoing syntheses are the following:
Secondary amines :-Diphenylamine, Alpha-dinaphthylamine.
Tertiary amines :-The tertiary methyl,- ethyl- isobutyl-, amyl- and benzyl-
derivatives of aniline orthotoluidine, orthoanisidine, alpha-naphthylamine diphenyl-
amine, alpha-dinaphthylamine, phenyl-alpha-naphthylamine and metaphenylen-
diamine. Phenyl-alpha-dinaphthylamine may also be employed.
Chlorides of acid radicals: The chlorides of acid radicals which are obtained
from the tertiary amines just enumerated by the action of carbonylchloride in
the presence or absence of condensing agents or from dialkylamido-benzoic acids

page_text: Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
--
+, The preparation of violet and blue coloring matters, by condensing the
chlorides of acid radicals hereinbefore mentioned under paragraph 43, with the
tertiary amines there enumerated in the presence of aluminium chloride, of
anhydrous ferric chloride of zinc chloride or of the substances mentioned under
paragraph 2, and having a similar action; those violet coloring matters excepted
which are obtained by the action of dimethylamido-benzoyl-chloride upon dimethyl-
aniline, of diethylamidobenzoyl-chloride upon diethylaniline and of methylethyl-
amidobenzoylchloride upon methylethylaniline in the presence of aluminium
chloride, of di-isobutylamidobenzoylchloride upon di-isobutylaniline, and of diamyl-
amidobenzoylchloride upon diamylaniline.
2, The preparation of violet and blue coloring matters by condensing the ketones
hereinbefore mentioned under-paragraph 4, with the tertiary amines there-enume-
rated in the presence of aluminium chloride, anhydrous ferrie chloride, carbonyl-
chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide,
phosphorus-pentabromide, phosphorus oxychloride phosphorus oxybromide or by
condensing the ketones mentioned under paragraph 4 with the secondary-amines
there enumerated in the presence of concentrated sulphurio-neid.
ABEL & IMRAY,
Agents for the Applicant,
28, Southampton Buildings,
London, W.C.
Dated this 29th day of July 1884.
ABEL & IMRAY,
Agents for the Applicant,
28, Southampton Buildings,
London, W.C.

page_text: I, CHARLES DENTON ABEL, of N° 28 Southampton Buildings, Chancery Lane, in
the County of Middlesex, Consulting Engineer and Patent Agent, do hereby declare
the nature of the said invention for. "THE PRODUCTION OF VIOLET AND BLUE
COLORING MATTERS OF THE ROSEANILINE-SERIES BY TREATING AROMATIC AMINES
WITH ALKYLISED AMIDODERIVATIVES OF BENZOYLCHLORIDE AND OF BENZOPHENONE
to be as follows:-
"
1. E & O Fischer (Berichte des Deutschen chem. Gesellschaft (1879) vol XII
p 797; v. also p 800 & 802) have shown that malachite green (bitter-almond-oil-
green) is formed by the action of benzoylchloride upon dimethylaniline in presence
of a condensing agent (zinc-chloride). In an analogous way, according to the
present invention, coloring matters of the roseaniline series are obtained when
tertiary alkylised amidoderivatives of benzoylchloride CO
C H. N (Alk) 2
ΟΙ
are allowed to act upon tertiary aromatic amines in the presence of condensing
agents as shewn in the following example :-
Dimethylamidobenzoic acid (Michler Berichte d. D. ch. G (1876) vol IX p 401) is
by the aid of phosphorus pentachloride (1 molecule) converted into dimethylamido-
benzoylchloride CO-
C. H. N (Ơ H₂) 2 (Michler, ibid). This is mixed with
01
an excess of diethylaniline and aluminium chloride and the mixture thus
obtained is gently heated. By this means a mixed ketone having the formula
CO
O HN (O, H 2
(Michler. Ber. d. D. ch G (1876), vol IX. p. 716) is.
°

page_text: '
formed in the first instance. The latter reacts upon a second molecule of diethyl-
aniline producing dimethyltetraethylroseaniline
-C HN (C H₁) 2
-C, H, N (C, H,) 2
-C, H. N (CH) 2 Cl.
(Compare also the similar formation of dimethylamidotriphenylmethane from
benzophenonechloride and dimethylaniline O Fischer Ber d. D. ch. G (1879)
vol XII p 1690), a violet coloring matter of a more blueish shade than the
"Violet 6 B" of commerce.
On employing methyldiphenylamine in the place of diethylaniline in the reaction
just described tetramethyldiphenylpararosaniline is obtained which is a very blue
violet.
2. The ketones formed as intermediate products in the foregoing reaction, which
are tetraalkyldiamidobenzophenones, may be separated by a suitable method
(Michler & Dupertius Ber d. D. ch. G (1876) vol IX p 1899; Michler & Gradmann
Ber d D ch G (1876) vol IX p 1914).
When for instance dimethylamidobenzoylechloride is heated with an excess of
diethylaniline the mixed ketone dimethyldiethyldiamidobenzophenone of the
formula CO-
is formed, and may be separated in the
"C. H. N (C H₂) 2
C HN (C, Hg) 2
shape of plates by distilling off the excess of diethylaniline with steam and
crystallising the residue from alcohol.
Such ketones react upon tertiary aromatic amines with formation of coloring
matters of the roseaniline series when any one or more of the following condensing
agents are present: aluminium chloride, carbonylchloride, phosphorus-tri-chloride,
phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide,
phosphorus oxychloride, phosphorus oxybromide. The same ketones react upon
secondary aromatic amines with formation of coloring matters in the presence of
sulphuric acid as condensing agent.
F
When for instance dimethyldiethyldiamidobenzophenone is allowed to act upon
an excess of methyldiphenylamine in the presence of one of the condensing agents
enumerated, a very blue violet is obtained having the formula:

page_text: amine, alpha-dinapthylamine, phenyl-alpha-napthylamine and metaphenylendia-
mine. Phenyl alpha dinaphthylamine may also be employed.
Chlorides of acid radicals -The chlorides of acid radicals which are obtained
from the tertiary amines just enuinerated by the action of carbonylchloride in the
presence or absence of condensing agents or from dialkylamidobenzoic acids
C, H, N (Alk) 2
by treatment with phosphorus pentachloride and
CO
о н
similar bodies.
Ketones-The ketones which result from the tertiary amines above enumerated
by the action of the chlorides of acid radicals mentioned in the presence or absence
of condensing agents.
By alkyles I understand the hydro-carbon radicals methyl, ethyl, phenyl, tolyl;
benzyl etc etc.

page_text: I, CHARLES DENTON ABEL of N° 28 Southampton Buildings, Chancery Lane,
in the county of Middlesex, Consulting Engineer and Patent Agent, do hereby
declare the nature of the said invention for "THE PRODUCTION OF VIOLET AND
BLUE COLORING MATTERS OF THE ROSEANILINE SERIES BY TREATING AROMATIC AMINES
WITH ALKYLISED AMIDODERIVATIVES OF BENZOYLCHLORIDE AND OF BENZOPHENONE
and in what manner the same is to be performed to be particularly described
and ascertained in and by the following statement :-
"
1, E & O, Fischer (Berichte des Deutschen chem: Gesellschaft, 1879, vol. XII
p. 797 v also p. 800 and 802) have shewn that malachite-green (bitter-almond-
oil-green is formed by the action of benzoyl-chloride upon dimethylaniline in
presence of a condensing agent (zinc-chloride). In an analogous way, according to
the present invention, coloring matters of the roseaniline series are obtained when
tertiary alkylised amidoderivatives of benzoylchloride CO
CÅ H₁ N (Alk) 2
'6
Ci
are allowed to act upon tertiary aromatic amines in the presence of condensing
agents as shewn in the following example.
Dimethylamidobenzoic acid (Michler Berichte d. D. ch. G (1876) vol. IX p. 401)
is, by the aid of phosphorus pentachloride (1 molecule) converted into dimethyl-
amidobenzoylchloride CO< ¨C H N (C H¸) 2.
CL
(Michler. ibid.).
This is mixed
with an excess of diethylaniline and aluminium chloride and the mixture thus
obtained is gently heated. By this means a mixed ketone having the formula
CH, N (C H₂) 2
CO
C, H, N (C, H) 2 (Michler. Ber. d. D. ch. G (1876) vol. IX p. 716) is
formed in the first instance. The latter reäcts upon a second molecule of diethyl-
aniline, producing dimethyl-tetraethyl-roseaniline C
-CÅ HÄN (Ơ H¸) 2
-C HN (C2 H.) 2
-C HN (C₂ H) 2 Cl.
(compare also the similar formation of dimethylamidotriphenylmethane from
benzophenonechloride and dimethylaniline: O, Fischer, Ber. d. D. ch. G (1879) :
vol. XII p. 1690) a violet coloring matter of a more bluish shade than the
"Violet 6 B" of commerce.
On employing methyldiphenylamine in the place of diethylaniline in the reaction
just described, tetramethyldiphenylpararosaniline is obtained which is a very blue
violet.
2, The ketones formed as intermediate products in the foregoing reaction, which
are tetra-alkyldiamidobenzophenones may be separated by a suitable method
(Michler & Durpertius Ber: d: D. ch. G. (1876) vol IX p. 1899; Michler &
Gradmann, Ber. d. D. ch. G. (1876) vol. IX, p. 1914).
When, for instance, dimethylamido-benzoylechloride is heated with an excess
of diethylaniline, the mixed ketone dimethyldiethyl-diamidobenzophenone of the
formula CO-
C. H. N (C H₂) 2
is formed, and may be separated in the shape
C HN (C H) 2
of plates by distilling off the excess of diethylaniline with steam, and crystallising
the residue from alcohol.
Such ketones reäct upon tertiary aromatic amines with formation of coloring
matters of the roseaniline-series when any one or more of the following condensing

page_text: agents are present: aluminium chloride, carbonylchloride, phosphorustrichloride,
phosphorus pentachloride, phosphorus tribromide, phosphorus pentabromide,
phosphorus oxychloride, phosphorus oxybromide.
The same ketones reäct upon secondary aromatic amines with formation of
coloring matters in the presence of sulphuric acid as condensing agent.
When, for instance dimethyl-diethyl-diamidobenzophenone is allowed to act
upon an excess of methyldiphenylamine in the presence of one of the condensing
agents enumerated, a very blue violet is obtained, having the formula:
Ketones: The ketones which result from the tertiary amines above enumerated
by the action of the chlorides of acid radicals mentioned, in the presence or absence
of condensing agents.
By alkyles are understood the hydrocarbon-radicals, methyl, ethyl, phenyl, tolyl,
benzyl, &c., &c.
Having now particularly described and ascertained the nature of the said
invention and in what manner the same is to be performed, I declare that what
I claim is:-
1. The preparation of violet and blue coloring matters, by condensing the
chlorides of acid radicals hereinbefore mentioned under paragraph 4, with the
tertiary amines there enumerated in the presence of aluminium chloride, of
anhydrous ferric chloride of zinc chloride or of the substances mentioned under
paragraph 2, and having a similar action; those violet coloring matters excepted
which are obtained by the action of dimethylamido-benzoyl-chloride upon dimethyl-
aniline, of diethylamidobenzoyl-chloride upon diethylaniline and of methylethyl-
amidobenzoylchloride upon methylethylaniline in the presence of aluminium

page_text: chloride, of di-isobutylamidobenzoylchloride upon di-isobutylaniline, and of diamyl-
amidobenzoylchloride upon diamylaniline.
2, The preparation of violet and blue coloring matters by condensing the ketones
herein before mentioned under paragraph 4, with the tertiary amines there enume-
rated in the presence of aluminium chloride, anhydrous ferric chloride, carbonyl-
chloride, phosphorus trichloride, phosphorus pentachloride, phosphorus tribromide,
phosphorus pentabromide, phosphorus oxychloride phosphorus oxybromide or by
condensing the ketones mentioned under paragraph 4 with the secondary amines
there enumerated in the presence of concentrated sulphuric acid.