COMPOSES HETEROCYCLIQUES; PRODUITS QUI EN SONT TIRES

PROCESS FOR THE PRODUCTION OF HETEROCYCLIC COMPOUNDS AND PRODUCTS OBTAINED THEREBY

Abrégé anglais

ABSTRACT OF THE DISCLOSURE:
The present invention relates to a process for the
production of five membered ketonic heterocyclic compounds
of the general formula:
<IMG> (l)
wherein:
- R1, R2, R3, R4 and R6 are identical or different
and each represent n hydrogen atom or an alkyl radical
having from 1 to 3 carbon atoms, which may be substituted by
an hydroxy group or a radical of the formula -COOR5 in which
R5 represents an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and
- m is the valence of Y.
This process comprises reacting a difunctional compound
of the formula:
<IMG> (2)
wherein R1, R2, R3, R4, R6, X, Y and m have the above meanings;
with carbon monoxyde and oxygen in the presence of a ctalyst
selected among the soluble catalyst consisting of selenium or its
derivatives, and the unsoluble catalyst consisting of a copper
complex.

Revendications

The embodiments of the invention in which an exclusive
property or privilege is claimed are defined as follows:
1. Process for the production of five membered ketonic
heterocyclic compounds of the general formula:
<IMG> (1)
wherein:
- R1, R2, R3, R4 and R6 are identical or different
and each represent a hydrogen atom or an alkyl radical having
from 1 to 3 carbon atoms, which may be substituted by an hydroxy
group or a radical of the formula - COOR5 in which R5 represents
an alkyl radical having from 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and
- m is the valence of Y,
said process comprising reacting a difunctional compound
of the formula:
<IMG> (2)
wherein R1, R2, R3, R4 R6, X, Y and m have the above meanings
with carbon monoxyde and oxygen in the presence of a catalyst
selected among the soluble catalyst consisting of selenium
or its derivatives, and the unsoluble catalyst consisting of
a copper complex.
2. Process according to claim 1, characterized in
that the reaction is carried out in homogeneous phase, the
catalyst and the reagents being dissolved in a solvent.

3. Process according to claim 1, characterized in
that the reaction is carried out in heterogeneous phase.
4. Process according to claim 1, characterized in
that the reaction is carried out under a pressure ranging
from 1 to 100 atmospheres.
5. Process according to claim 4, characterized in
that the reaction is carried out under a pressure ranging from
1 to 10 atmospheres.
6. Process according to claim 1, characterized in
that the reaction is carried out at a temperature ranging from 0
to 100°C.
7. Process according to claim 6, characterized in
that the reaction is carried out at a temperature ranging
from the room temperature to 80°C.

Description

9~5
The present invention relates to a process or the
production of five membered ke-tonic heterocyclic compounds
having two heteroatoms in the ring.
More especially the present invention relates to a
process for the production of heterocyclic compounds of the
general formula:
R2 13
R - C C - R (1)
X ~ 6)m-2
, ~ '.
wherein:
- Rl, R2j R3, R4 and R6 are identical or different
and each represent a hydrogen atom or an alkyl radical having from
1 to 3 carbon atoms, wh.ich may be substituted by an hydroxy group
or a radical of the formula - COOR5 in which R5 represents
an alkyl radical having Erom 1 to 3 carbon atoms;
- X is an oxygen or sulfur atom;
- Y is a sulfur or nitrogen atom; and
~ m is the valence of Y,
Up to now, the above products have been prepared
through a reaction between a difunctional compound and phosgene
or through a more complex syntheses. The use o phosgene
involves several drawbacks because its toxicity and its reactivity
with other functional groups present in the molecule.
It has now been found a simple and cheap process for :
obtaining these heterocyclic compounds at very high yields.
The process according to the invention comprises
reacting a difunctional compound of the general ormula
~ 12 13
Rl - C . Y(R6)m_l (2)
in which Rl, R2, R3, R4, R6, X, Y and m have the above meanings,
with carbon monoxide and oxygen in presence ~

9~5
o~ a soluble or unsoluble catalyst, the former being selected
between selenium and derivatives thereof, the la-tt.er being a
copper complex.
The reaction may be carried out either in homogeneous
phase by dissolving the reagents and the catalyst into a sui-
table solvent or in heterogeneous phase by using an unsoluble
catalyst. Unrestrictive examples of compounds according to the
formula (2) may be ethanolamine, 2-aminopropano~ 3-aminopro-
pano], diethanblamine, 1,2-ethandithiole, 1,3-propandithiole,
1,2-propandithiole, 2-aminoethanthiole, 2-aminopropanthiole,
3-aminopropanthiole. The reaction may be carried out under a
pressure ranging from 1 to 100 atmospheres. For practical
reasons, it is preferable to operate ~nder a pressu~e rang~g between
l to 10 atmospheres.
As 2~resaid, the catalyst may be soluble into the
reagents or in suitable solvents, or it may be unsoluble.
Among the soluble catalysts, it is possible to mention metallic
selenium and the derivatives thereof whereas, as to the unso-
luble catalysts, an advantageous use can be made of complexes
containing Cu. The reaction may be carried out at temperatures
ranging from 0 to 100C, preferably from the room temperature
to 80C.
The Eollowing examples illustrate the invention,
but are not limitative thereof.
Example 1:
23.8 mmoles of 1-2 dimercaptoethane,~l mmole of triethylamine
and 0.5 mmole o Se were reacted ln 10 ml of T~F at 25C with
a CO:O2 mixture in the molar ratio 10:1 at 3.5 atmos~heres.
After 40 hours, selenium was recovered and the solvent was

1~50~9'~
evaporated from the resulting suspension. The residual was
distilled under vacuum. The IR analysis showed that the dis-
tilled product was ethylenedithiocarbonate. Yield=90%.
Example 2 :
lO moles of 2,3-dimercaptopropanol-l, l mole of triethylamine
and l mmole of Se were reacted in 10 ml of THF at 25C with
a CO:O2 mixture in the molar ratio lO: l at 3.5 atmospheres.
After 16 hours, selenium was recovered from the resulting
suspen5ion and the solvent was evaporated. The residual was
distilled under vacuum. The distilled product, at IR and
mass analysis, was 1-3 dithiolan-2-one-4-hydroxymethyl.
Yield = 90%.
20 mmoles of 2,3-dimercaptopropanol, l mmole of thiethylamine
and O.S mmole o~ Se were reacted with C0 and 2 in condi-tions
simllar to the precedi,ng ones. After 16 'hours the oolution
was yellowish and homogeneous. The solverit was evaporated
and the residual was distilled.
18 mmoles of 1-3 dithiolan-2-one-4-hydroxymethyl were obtained.
Yield = 90%~
Example 3:
14.8 mmoles of 2-mercaptoe-thylamine and 0.5 mmole of amorphous
Se, in lO mI of THF, were reacted at 60C with a C0:02 mixture
in the molar ratio lO:l at 3.5 atmospheres.
After 4 hours, the solution was filtered from selenium and the
solvent was evaporated. The residual was again crystallized
in CS2 (m.p.=50C). 1.4 g of 2-thiazolidinone were obtained,
' identified by IR and mass spectoscopy. Yield = 93%. ' ~ '
: .
- 3 -
.. . . . . . . . . . . . . . .. . .

105099~ -
Example 4:
82 mmoles of ethanolamine and 1 mmole of amorphous selenium
were reacted in 25 ml of THF with a CO:O2 mixture in the molar
ratio 4:1 at 4 atmospheres. After 3 hours at 70 C selenium
was filtered and the solvent was evaporated. The rèsidual
was crystalIized from chloroform (m.p. 87 C).
6.8 g of product was o~tained. The IR ana:Lysis showed that it
was 2-oxazolidone. Yield= 95%.
Example 5:
12.7 mmoles of 1-amino-2-propanol and 0.3 mmole of selenium
were reacted at 60 C under conditions similar to the preceeding
ones. After 3 hours selenium was filtered, the solvent was
evaporated and the residual product was distilled under vacuum.
1.2 g of an oily product were obtained. The IR and mass analysis
showed that it was 2-oxazolidone-5-methyl. Yield~ 95~.
Example 6:
10 mmoles of diethanolamine and 0.3 mmole of selenium were
reacted at 60 C under conditions similar to the preceeding ones.
After 10 hours selenium was filtered, the solvent was evapora-
ted and the residual was distilled under vacuum. 1.2 g of
liquid product were obtained. The IR and mass analysis showed
that it was 2-oxazolidone-3-hydroxyethyl~ Yield =91~.
Example 7:
: .
10.3 mmoles of trihydroxymethylaminomethane and 0.5 mmole of
selentum were reacted in 20 ml of ethyl alcohol at 70C with
a CO:O2 mixture in the molar ratio 4:1 at 4 atmospheres.
After 5 hours selenium was filtered and the solvent was eva-
porated. The residual was crystallized from chloroform (m.p.=
104C). 1.5 g of product were obtained. The IR analysis showed
that it was 2-oxazolidone-4, 4-bishydroxymethyl. Yield~ 99%.
,
4 _
L.~ , , ,
.. . . .: . . :. .. . ". .,. . .. ; , . . . . . . .. ..

995
Example_8:
16.~ mmoles of ethanolamine and 10 mmoles of CuCl in 10 ml
of pyridine were treated, in autoclave at 70C, with a CO:O2
mixture in the molar ratio 4:1. After 16 hours the solution
was filtered and the solvent evaporated under vacuum. The
residual was crystallized from chloroform. 0.78 g of 2-
oxazolidone was obtained. Yield = 55%.
.
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.... . . . . . - . . . . . . .
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