PROCESS FOR THE PREPARATION OF TRI-ESTERS AND PRODUCTS SO OBTAINED

PROCEDE POUR LA PREPARATION DE TRIESTERS ET PRODUITS OBTENUS PAR CE PROCEDE

English Abstract

ABSTRACT OF THE DISCLOSURE:

A process for the preparation of a triester of the
formula:

Image

wherein R is an alkyl radical of from 1 to 5 carbon atoms
consisting of reacting a ?-halo-epoxide of the formula

Image

wherein Y is an halogen atom, with an anhydride of a carboxylic
acid RCOOH, wherein R has the above meaning, in the presence of
Lewis acids, and with an alkaline or alkaline earth metal salt
of that RCOOH acid, and the so obtained products. These products
are useful as intermediates for organic synthesis, such as the
preparation of ?-hydroxy-aldehydes or -ketones, ?-acyloxy
(or aroyloxy)-aldehydes or -ketones, or ?-hydroxy-aminoacids.

Claims

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:

1. Triesters of the formula:


Image

wherein R is an alkyl radical of 1 to 5 carbon atoms.

2. A process for the preparation of a triester of
the formula:



Image

wherein R is an alkyl radical of 1 to 5 carbon atoms
consisting of reacting a ?-halo-epoxide of the formula

Image

wherein Y is an halogen atom, with an anhydride of a carboxylic
acid RCOOH, wherein R has the above meaning, in the presence of
Lewis acids, and with an alkaline or alkaline earth metal salt
of that RCOOH acid.


3. A process according to claim 2 characterized
in that the reaction is carried out in two stages, the
first one consisting in reacting the ?-halo-epoxyde with the
anhydride of the RCOOH acid, the second one in reacting
the product thus obtained with an alkaline or alkaline-earth
metal salt of the RCOOH acid.

4. A process according to claim 3 characterized
in that the reaction of the first stage is carried out at
a temperature ranging from -30 to +70°C.

5. A process according to claim 3 characterized
in that the reaction of the second stage is carried out
at a temperature ranging from +25 to +180°C.

6. A process according to claim 2 characterized
in that the reaction is carried out in the presence of a
solvent selected among the aromatic compounds.

7. A process according to claim 6 characterized
in that the solvent is selected among the nitro- or halo-
aromatic compounds.

8. A process according to claim 2 characterized
in that the reaction is carried out at such a pressure
as to maintain the reaction mixture in a liquid phase.

Description

1049036
The present invention relates to a process for
the preparation of tri-esters of formula:
OCOR OCOR
H ______\ \
C C H
H /
OCOR
wherein R is an alkyl radical of from 1 to 5 carbon atoms
and to the so obtained products !
The products according to the invention are useful
` 10 as intermediates for some organic synthesis, such as for
example the preparation of~ -hydroxy-aldehydes or -ketones,
-acyloxy (or aroyloxy)-aldehydes or -ketones, or ~-hydroxy-
aminoacids.
- The process according to the invention consists in
reacting q-halo-epoxides of the formula:
. H O Y
\~y
H H
wherein: .
Y i8 an halogen atom, with an anhydride of a carboxylic
acid RCOOH, wherein R has the above meaning, in the presence
of Lewis acids, and, preferably, in a second stage, with .
an alkaline or alkaline-earth metal salt of that RCOOH acid.
More particularly, the reaction of the halo-epoxide
with the anhydride is carried out at a temperature ranging
from -30 to ~70C at such a pressure as to maintain the
mixture in the liquid phase, possibly in the presence of a
suitable solvent, selected among the aroma~c'compounds
preferably among the nitro- or halo-aromatic compounds, and
-. the subsequent reaction with the salt is carried out at a
.




'~ '
` . ' : -' '1. ' ~ :- '

~0 49 03U6
temperature ranging from +25 to ~180C~ the other condltions
remaining unchanged. --
~ he ln~ention will be now better under~tood withreference to the following non-restrlctl~e e~ample.
EX~æ
Preparation o~ 1.1.2-triacetoxy-ethane from monochloroeth,~lene
oxide
To 5.27 g (67.2 mmoles) of monochloroethylene oside
were added 40 ml of acetic anh~dride and 0.22 g of anh~drous
rerric chloride. ~he mixture ~a8 stirred ior one hour at room
temperature under a nltrogen atmosphere. ~hen 5.51 g (67.2
mmoles) Or anhydrous sodium acetate were added, ana, ~tlll
under nitrogen, the reaction mi%ture stirred for a further
60 hour~ at room temperature and iinally was re n used ror
further 48 hours.
lhe rea¢tion misture, ¢ooled to room temperature,
was diluted with 100 ml of methylene chloride. ~he precipitated
salts were remo~ed b~ ~iltratinni the precipitate w w hed
~lth meth~lone ohloride and the collected riltrates were dried
unaer ~acuum on a rotating e~aporator. The residue diluted
~n methglene chloride was heated and treated wlth acti~e
carbo~. ~he aoti~e carbon was washea with a 8mall amount of
sol~ent. ~he sol~ent waa removed under ~acuum from the
gathered iiltrates and the residue puriiied by distillation.
Dhe 1,1,2-triacetosyethane wa~ distilled at 112-
114C under 2 mmHg (bath at 150C). 6.86 g of product pure
at the chromatography test (yield 50%) and with a melting
point Or 48-50C were obtalned.



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