Manufa
Year: 1887

page_text: Date of Application, 9th Apr., 1887
Complete Left, 4th Jan., 1888
Complete Accepted, 23rd Mar., 1888
[Communicated from abroad by THE FARBWERKE VORMELS MEISTER. LUCIUS AND
BRUNING, of Hoechst-am-Maine, in the Empire of Germany, a Company carrying
on business as Chemical Manufacturers.]
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings Chancery Lane in
the County of Middlesex, Consulting Engineer and Patent Agent do hereby declare
the nature of this invention to be as follows:-
Two ways of producing the dialkyl-amido-benzophenones are known at present;
thus, the dimethylamidobenzophenone has been obtained by decomposing by means of
hydrochloric acid the coloring matter known as malachite green (Döbner, Berichte
der D. ch. Ges. XIII, 22) and the diaethylamidobenzophenone is produced by
aethylising the amidobenzophenone (Gerinan Patent 27789).
This invention has for its object a practical process for the production of such
dialkylamidobenzophenones. It starts from benzoic acid and substantially consists in,
that the anilides or naphthalides of benzoic acid are converted into the halogen
compounds by means of chloro-phosphorous and agents having similar action; these
compounds are condensed by means of dimethylaniline or any other tertiary aromatic
base and the products of the condensation are treated with diluted acids or alkalies.
In this process may be used any of the anilides or naphthalides, that are obtained
by the action of benzoic acid or its chloride on aniline, toluidines, Xylidines, cumidines,
dimethylparaphenylene-diamine, meta-phenylene-diamine, benzidine, alpha-naphthyl-
amine, beta-naphthylamine.
The conversion of these bodies into their halogen-compounds is carried out by
means of the chloro- bromo- and iodo- compounds of phosphorus in manner well known
to chemists; in practice it will be found advantageous to combine this conversion in
one operation with the subsequent condensation.
As agents of condensation may be employed any of the tertiary bases known at
present, viz.: The tertiary methyl- aethyl-butyl-anyl- and benzyl- derivatives of aniline,

page_text: orthotoluidine, orthoanisidine, alpha-naphthylamine, beta-naphthylamine, diphenyl-
amine, dinaphthylamine, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine and
meta-phenylene-diamine.
The bodies obtained in this way are colour-like compounds, soluble in water, and
dye mordanted cotton a vivid yellow-orange to red brown shade, but by contact with
acids and more readily by boiling, they are easily decomposed.
:
The decomposition is with all the bodies the same, viz. the primary amine separates
and the tertiary amine taken up in the last stage of the operation, remains in
conjunction with the benzoyl rest in form of a ketone.
Example. Into a mixture of 20 parts by weight of benzanilide and 40 parts by
weight of dimethylaniline are introduced 20 parts by weight of phosphoroxychloride
and while being kept in constant agitation the mixture is heated to water-bath
temperature. As soon as a more rapid rising the thermometer shows spontaneous
heating, the heating is interrupted and if necessary cooling is resorted to; in general
the operation is carried on in such a way that in the beginning of the reaction, the
temperature does not rise above from 105° to 110° C.
Later on, when spontaneous heating no longer occurs, the water bath is heated to
boiling point and is kept at that temperature for two hours. After this time the mass
is of syrupy consistency, yellow-brown color and feeble metallic lustre.
The newly formed body can be obtained in form of its base, by shaking the mass
together with a watery solution of ammonia (of about 10%) diluting afterwards
with the quintuple volume of water, neutralising cautiously with diluted hydrochloric
acid, until the oil is entirely dissolved, filtering and crystallising the residue from
alcohol.
A yellowish white crystalline powder is obtained whose melting point is 151°
to 152° C. The body dissolves in the cold, in diluted acids shewing an orange-red
tint; these solutions dye mordanted cotton a vivid yellow-orange shade, but they
decompose on being left standing for a longer space of time or on being heated.
In order to convert the body into the dimethylamidobenzophenone the above melt
is added to 40 parts by weight of hydrochloric acid and 200 parts by weight of water,
and subsequently heated until it is uniformly divided and a complete discolouring of
the liquid is effected.
In order to separate the benzanilide that might have been left unconverted, the
liquid is then filtered and the filtrate diluted by about 1000 parts by weight
of water.
A part of the formed ketone separates and in order to complete the precipitation,
the liquid is cautiously neutralised by means of sodium lye.
The precipitate is filtered off, washed and dried; the filtrate contains besides the
excess of dimethylaniline the reformed aniline; they are expelled together and are
afterwards separated by suitable means.
Dated this 9th day of April 1887
ABEL & IMRAY,
Agents for the Applicant.

page_text: Dialkylised Amidobenzophenones therefrom.
I, CHARLES DENTON ABEL of No. 28 Southampton Buildings, Chancery Lane, in
the County of Middlesex, Consulting Engineer, and 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
Two ways for producing the dialkyl-amido-benzophenones are known at present,
thus the dimethylamidobenzophenone has been obtained by decomposing by means of
hydrochloric acid the coloring matter known as malachite green (Döbner, Berichte
der D. ch. Ges. XIII, 22), and the diethylamidobenzophenone is produced by
ethylising the ainidobenzophenone (German Patent 27789).
This invention has for its object a practical process for the production of such
dialkyl-amido-benzophenones. It starts. for example, from benzoic acid and
substantially consists in that the anilides or naphthalides of benzoic acid are converted
into the halogen compounds by means of chloro-phosphorus and agents, having
similar action; these compounds are condensed by means of dimethylaniline or any
any other tertiary aromatic base and the products of the condensation are treated
with diluted acids.
In this process may be used any of the anilides or naphthalides that are obtained
by the action of benzoic acid, its homologues and substitution products further the
naphthoic acids or the chlorides of the said acids upon aniline, mono-methylaniline,
mono-ethylaniline, toluidines, xylidines, cumidines, dimethyl-paraphenylene-diamine,
meta-phenylene-diamine, benzidine, alpha naphthylamine, beta-naphthylamine.
The conversion of these bodies into their halogen compounds is carried out by
means of the chloro- and bromo- compounds of phosphorus in manner well known to
chemists, in practice it will be found advantageous to combine this conversion in one
operation with the subsequent condensation.
For the condensation may be employed any of the tertiary bases known at present
viz. the tertiary methyl- ethyl-butyl-amyl and benzyl- derivatives of aniline,
orthotoluidine, orthoanisidine, alpha-naphthylamine, beta-naphthylamine, diphenyl-
amine, dinaphthylamine, phenyl-alpha-naphthylamine, phenyl-beta-naphthylamine,
and meta-phenylene-diamine.
The bodies obtained in this way are colourlike compounds, soluble in water, and
dye mordanted cotton a vivid yellow-orange to red-brown shade, but by contact with
acids and more readily by boiling, they are easily decomposed.
The decomposition is with all the bodies the same viz. the primary or secondary
amine separates and the tertiary amine taken up in the last stage of the operation
remains in conjunction with the benzoyl rest in the form of a Ketone.
Example. Into a mixture of. 20 parts by weight of benzanilide, and 40 parts by
weight of dimethylaniline are introduced 20 parts by weight of phosphorus oxychloride

page_text: and while being kept in constant agitation the mixture is heated to water-bath
temperature. As soon as a more rapid rising of the thermometer shows spontaneous
heating the heating is interrupted and if necessary cooling is resorted to; in general
the operation is carried on in such a way that in the beginning of the reaction, the
temperature does not rise above from 105 to 110° C.
Later on, when spontaneous heating no longer occurs, the water bath is heated to
boiling point and kept at that temperature for two hours.
After this time the mass is of sirupy consistency, yellow-brown colour and feeble
metallic lustre.
The newly formed body can be obtained in form of its base, by shaking the mass
together with a watery solution of ammonia (of about 10%) diluting afterwards
with the quintuple volumen of water, neutralising cautiously with diluted hydrochloric
acid, until the oil is entirely dissolved, filtering and crystallising the residue from
alcohol.
A yellowish white crystalline powder is obtained whose melting point is about
152° C. The body dissolves in the cold in diluted acids, showing an orange red
tint; these solutions dye mordanted cotton a vivid yellow-orange shade, but they
decompose on being left standing for a longer space of time or on being heated.
In order to convert the body into the dimethylamidobenzophenone the above melt
is added to 40 parts by weight of hydrochloric acid and 200 parts by weight of water
and subsequently heated until it is uniformly divided and a complete discoloring of
the liquid is effected. In order to separate the bonzanilido that might have been left
unconverted, the liquid is then filtered and the filtrate diluted by about 1000 parts by
weight of water.
Instead of employing water with an admixture of acid as above described, water
alone may be used for the purpose.
A part of the formed Ketone separates and in order to complete the precipitation
the liquid is carefully neutralised by means of sodium lye.
The precipitate is filtered off, washed, and dried; the filtrate contains besides the
excess of dimethylaniline the reformed aniline, they are expelled together and are
afterwards separated by suitable known means.
Having now particularly described and ascertained the nature of this inven-
tion and in what manner the same is to be performed, I declare that what I
claim is :-
1. The process for producing colour-like bodies wherein the halogen compounds
of the anilides or naphthalides, which are obtained by the action of benzoic acid or the
naphthoic acids, their homologues or substitution products or the chlorides and
bromides of the said acids upon aniline, mono-methylaniline, mono-ethylaniline,
toluidines, xylidines, cumidines, dimethyl-para-phenylene-diamine, meta-phenylene-
diamine, benzidine, alpha-naphthylamine, beta-naphthylamine, are condensed with
tertiary amines, namely the tertiary methyl- ethyl- butyl- amyl- and benzyl derivatives
of aniline, ortho-toluidine, ortho-anisidine, alpha-naphthyl-amine, beta-naphthylamine,
diphenylamine, dinaphthylamine, phenyl-alpha-naphthylamine phenyl-beta-naphthyl-
amine, and meta-phenylene-diamine, in the presence of or without condensing agents,
and with any suitable dissolving or dividing agents.
2. The conversion of the colour-like bodies, produced as set forth in the preceding
claim, into Ketones by treatment with water or diluted acids.
Dated this 4th day of January 1888.
ABEL & IMRAY,
Agents for the Applicant.