Manufacture of Dialkylised Meta-methoxy-meta-ethoxy and Meta- benzyloxy-para-amido-benzophenones.
Year: 1892

page_text: Date of Application, 2nd May, 1892
Complete Specification Left, 2nd Feb., 1893-Accepted. 11th Mar.. 1893
PROVISIONAL SPECIFICATION.
[Communicated from abroad by THE FARBWERKE VORMALS MEISTER LUCIUS
AND BRUNING, S C. of Hoechst */ Main, Germany, Chemical Manufacturers.]
Manufacture of Dialkylised Meta-methoxy-meta-ethoxy and Meta-
benzyloxy-para-amido-benzophenones.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered Patent Agent, do hereby declare the nature of this
invention to be as follows :-
In the same manner as dialkylamidobenzophenones are obtained from benzoic
acid, and tetra-alkyl-amido-benzophenones from dimethylamido benzoic acid
(German Letters Patents 41751 and 44077) can be produced dialkylamido-meta-
oxy-benzophenones or their ethers from meta oxybenzoic acid or their methyl,
ethyl and benzyl ethers.
For this purpose, according to the present invention, the substituted amides of
the respective acid are converted by heating them with phosphor-oxychloride and
a tertiary base, into coloured condensation products-those from dimethylamido-
benzoic acid are called "substituted auramines "and these easily decomposable
colouring matters are split up by boiling with diluted acids into benzophenone
and primary or secondary amine.
The manner of carrying out the invention is more fully described in the following
example relating to the production of tetramethyldiamido-benzophenone :

page_text: 1) Meta-methoxybenzanilide forms white needles of the melting point 120° C.
tolerably easily soluble in alcohol with difficulty in cold benzene, easier in hot
benzene.
2) Meta-ethoxybenzanilide forms white needles of the melting point 104° C.
easily soluble in alcohol, with some difficulty in benzene.
3) Meta benzyloxybenzanilide forms white needles of the melting point 112° C. ;
easily soluble in alcohol, with some difficulty in benzene.
Meta-methoxy-para-dimethylamido benzophenone;
10 parts by weight of meta-methoxybenzanilide
dimethylaniline
"phosphoroxychloride
14
"
"
"
99
7
"
"
وو
are mixed in an iron or copper vessel furnished with a stirrer, the mixture is
heated with care ou a water bath to about 90° C. and, while continually stirred,
is kept at this temperature for about 3 hours.
After some time the melt assumes a deep dark brown colour, in thin layers
yellow brown, with feeble metallic lustre, and later on it becomes viscous. It is
now well mixed with about 100 parts by weight of water and 5 parts by weight of
hydrochloric acid and is heated to about 70° C.; the melt which is viscous at the
beginning becomes quite thinly liquid, but without dissolving in the water to any
extent on the sides of the vessel are deposited separate flakes of the formed
benzophenone, until at a given moment the whole mass solidifies and afterwards
breaks up in crystalline powder; it is diluted with water until the whole quantity
(feebly basic) of meta methoxy-dimethyl-amido-benzophenone has become pre-
cipitated; the liquid is then separated from the sediment, the latter is washed, dried
and in order to purify the same it is recrystallised from 2 parts of alcohol. The
liquid contains the excess of dimethylaniline that had been added for the melting,
and the aniline split off from. the condensation product when heated with water.
The mixture of the two oils is regained in well known manner
\C.HOCH,
m. methoxy-p-dimethyl-
amidobenzophenone
+ Nigh s
85
aniline
The meta methoxy-para-dimethyl amido benzophenone is a feeble base; dissolves
in strong hydrochloric acid from which nearly the whole quantity is precipitated 40
on diluting with water. It crystallises in the form of yellowish white needles
melting at 67° C.; is easily soluble in water, very easily in benzene.
In a quite analogous manner are produced :
Meta-methoxy-para-diethylamidobenzophenone which is still less basic than the
above body, scarcely soluble in hydrochloric acid, very easily soluble in alcohol, 45

page_text: with greater difficulty in benzene; crystallising in form of tolerably white needles,
meltingpoint 120-121° C.
Meta-ethoxy-para-dimethylamidobenzophenone; a feeble base, soluble in strong
hydrochloric acid, re-precipitable by water; greenish white needles melting point
at 90° C., very easily soluble in benzene, with greater difficulty in alcohol.
Meta-ethoxy-para-diethylamidobenzophenone; not basic, very easily soluble in
benzene, easily in alcohol, crystallising in form of greenish white needles, melting
point 104° C.
Meta benzyloxy-paradimethyl amidobenzophonone; a feeble base, soluble in
strong hydrochloric acid re-precipitable by means of water, very easily soluble in
benzene, with some difficulty in cold alcohol, forming greenish white brilliant
needles or leaflets, melting point 86° C.
Dated this and
of Man 1800
ABEL & IMRAY,
Agents for the Applicant.
COMPLETE SPECIFICATION.
Manufacture of Dialkylised Meta-methoxy-meta-ethoxy and Meta-
benzyloxy-para-amido-benzophenones.
I, OLIVER IMRAY, of No. 28 Southampton Buildings, Chancery Lane, in the
County of London, Chartered 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 :-
In the same manner as dialkylamidobenzophenones are obtained from benzoic
acid, and tetra-alkyl amido benzophenones from dimethylamido benzoic acid
(German Letters Patents 41751 and 44077) can be produced dialkylamido-meta-
oxy-benzophenones or their ethers from meta oxybenzoic acid or their methyl, ethyl
and benzyl ethers.
For this purpose, according to the present invention, the substituted amides of
the respective acid are converted by heating them with phosphoroxychloride and a
tertiary base, into coloured condensation products-those from dimethylamido-
benzoic acid are called "substituted auramines "and these easily decomposable
colouring matters are split up by boiling with diluted acids into benzophenone and
primary or secondary amine."
The manner of carrying out the invention is more fully described in the following
example relating to the production of tetra methyldiamido-benzophenone :

page_text: TOUSTY TO state, that for aunime may be substituted any or
the other primary aromatic amines.
DESCRIPTION.
1) Meta-methoxybenzanilide forms white needles of the melting point 120° C.,
tolerably easily soluble in alcohol with difficulty in cold benzene, easier in hot
benzene.
2) Meta-ethoxybenzanilide forms white needles of the melting point 104° C.,
easily soluble in alcohol, with some difficulty in benzene.
3) Meta-benzyloxybenzanilide forms white needles of the melting point 112° C. ;
easily soluble in alcohol, with some difficulty in benzene.
Meta-methoxy-para-dimethylamido benzophenone
10 parts by weight of meta-methoxybenzanilide
14
"
"
"
7 "
"
"
"dimethylaniline
» phosphoroxychloride
"
are mixed in an iron or copper vessel furnished with a stirrer; the mixture is
heated with care on a water bath to about 90° C. and, while continually stirred, is
kept at this temperature for about 3 hours.
After some time the melt assumes a deep dark brown colour, in thin layers
yellow brown, with feeble metallic lustre, and later on it becomes viscous.
It is now well mixed with about 100 parts by weight of water and 5 parts by
weight of hydrochloric acid and is heated to about 70° C.; the melt which is
viscous at the beginning becomes quite thinly liquid, but without dissolving in the
water to any extent; on the sides of the vessel are deposited separate flakes of the
formed benzophenone, until at a given moment the whole mass solidifies and
afterwards breaks up in crystalline powder; it is diluted with water until the whole
quantity (feebly basic) of meta methoxy dimethyl-amido benzo-phenone has become
precipitated; the liquid is then separated from the sediment, the latter is washed,
dried and in order to purify the same it is recrystallised from 2 parts of alcohol.
The liquid contains the excess of dimethylaniline that had been added for the
melting, and the aniline split off from the condensation product when heated with 4
water.
The mixture of the two oils is regained in well known manner.

page_text: The meta methoxy-para-dimethyl-amido benzo phenone is a feeble base;
dissolves in strong hydrochloric acid from which nearly the whole quantity is
reprecipitated on diluting with water.
It crystallises in the form of yellowish white needles melting at 67° C.; is
easily soluble in water, very easily in benzene.
In a quite analogous manner are produced:
Meta-methoxy-para-diethylamidobenzophenone which is still less basic than the
above body, scarcely soluble in hydrochloric acid, very easily soluble in alcohol,
with greater difficulty in benzene; crystallising in form of tolerably white needles,
melting point 120-121° C.
Meta-ethoxy-para-dimethylamidobenzophenone; a feeble base, soluble in strong
hydrochloric acid, reprecipitable by water, greenish white needles melting point
at 90° C., very easily soluble in benzene, with greater difficulty in alcohol.
Meta-ethoxy-para-diethylamidobenzophenone; not basic, very easily soluble in
benzene, easily in alcohol, crystallising in form of greenish white needles, melting
point 104° C.
Meta-benzyloxy-paradimethyl amidobenzophenone a feeble base, soluble in strong
hydrochloric acid reprecipitable by means of water, very easily soluble in benzene,
with some difficulty in cold alcohol, forming greenish white brilliant needles or
leaflets, melting point 86° C.
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 herein described process for the manufacture of dialkylised meta-methoxy
and meta-ethoxy para dimethyl and diethyl-amido benzophenones, also meta-
benzyloxy para-dimethyl amidobenzophenone by treating respectively meta-
methoxy meta ethoxy and meta benzyloxy benzanilide with phosphoroxy chloride
and dimethyl or diethyl aniline and heating the coudensation product thus obtained
with diluted acids.
2. The dialkylised products obtained as above set forth.
Date L: 3