Claims
- 1. A process for preparing an organic carbonate: ##STR17## wherein R is a linear or branched C.sub.1 -C.sub.10 alkyl radical, or a C.sub.5 -C.sub.8 cycloalkyl radical;
- or a cyclic organic carbonate: ##STR18## wherein R' is a linear or branched C.sub.2 -C.sub.5 alkylene radical; by reacting an aliphatic or cycloaliphatic alcohol
- R--OH
- or, respectively, an aliphatic diol
- HO--R'--OH
- with carbon monoxide and oxygen;
- wherein said process is carried out in the presence of a catalyst comprising a divalent or trivalent cobalt ion and an organic ligand selected from the group consisting of:
- (i) a carboxylate ligand having the formula:
- R.sub.1 --COO.sup.- ; R.sub.2 --[COO.sup.- ].sub.2 ; R.sub.3 --[COO.sup.- ].sub.3 ; OR R.sub.4 --[COO.sup.- ].sub.4 ;
- wherein R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are independently selected from the group consisting of monovalent, divalent, trivalent and tetravelent radicals having up to 20 carbon atoms, and monovalent, divalent, trivalent and tetravalent organic radicals having up to 20 carbon atoms which additionally contain non-carbonyl oxygen atom(s), nitrogen atom(s), sulfur atom(s) and halogen atom(s),
- (ii) a beta-diketonate ligand having the formula: ##STR19## wherein each of R.sub.5, R.sub.6 and R.sub.7 independently is selected from the group consisting of a hydrogen atom, aliphatic, cycloaliphatic and aromatic radicals having up to 10 carbon atoms, and aliphatic cycloaliphatic and aromatic radicals having up to 10 carbon atoms which additionally contain non-carbonyl oxygen atom(s), nitrogen atom(s), sulfur atom(s) and halogen atom(s),
- (iii) a Schiff base having one or more oxygen functional groups selected from the group consisting of: ##STR20## wherein R.sub.2, R.sub.5 and R.sub.7 are as above defined, R.sub.8 is an aliphatic, cycloaliphatic or aromatic radical having up to 10 carbon atoms, R.sub.9 is a hydrogen atom or is the same as R.sub.8, and X is an alkyl, alkoxy, nitro, cyano, amino radical, or a halogen atom; and
- (iv) a ligand having the formula:
- P--OH
- wherein P is selected from those having the formula: ##STR21## in which formulae R'.sub.1 and R'.sub.2 are a hydrogen atom, a halogen atom selected from the group consisting of chlorine, bromine or iodine, a (C.sub.1 -C.sub.20)alkyl, or a (C.sub.1 -C.sub.20) alkoxy radical.
- 2. A process according to claim 1 wherein in said carboxylate ligands (i):
- R.sub.1 is selected from H; CH.sub.3 --; CH.sub.3 --CH.sub.2 ; CH.sub.3 (CH.sub.2).sub.2 --; CH.sub.3 (CH.sub.2).sub.3 ; CH.sub.2 .dbd.CH--; (CH.sub.3).sub.2 CH--; (CH.sub.3).sub.2 CH--CH.sub.2 --; ##STR22## a cyclohexyl radical; a phenyl radical; a phenyl radical substituted with an alkyl, halogen, alkoxy, nitro or cyano group;
- R.sub.2 is selected from --CH.sub.2 ; --CH.sub.2 --CH.sub.2 --; --CH.dbd.CH--; --CH.sub.2 --CH.sub.2 --CH.sub.2 --; CH.sub.2 --NH--CH.sub.2 --CH.sub.2 --NH--CH.sub.2 --; --CH.sub.2 --(CH.sub.2).sub.2 --NH--(CH.sub.2).sub.2 --CH.sub.2 --; --CH.sub.2 --(CH.sub.2).sub.2 --CH.sub.2 --; --CH(OH)--CH(OH)--; a phenylene radical; or a direct bond;
- R.sub.3 is selected from --CH.sub.2 --C(OH)--CH.sub.2 --; and
- R.sub.4 is selected from ##STR23##
- 3. A process according to claim 1, wherein said beta-diketonate ligand (ii) is ##STR24##
- 4. A process according to claim 1, wherein said catalyst additionally contains a nitrogen ligand selected from the group consisting of pyridine, bipyridil, phenanthroline, tetra-methyl ethylene-diamine, and an alkali or alkali-earth cation selected from the group consisting of sodium and barium.
- 5. A process according to claim 1, wherein said catalyst is selected from the group consisting of: ##STR25##
- 6. A process according to claim 1, wherein said aliphatic alcohol is selected from the group consisting of methanol, ethanol, n-propanol, iso-propanol, n-butanol, iso-butanol, 2-ethyl-hexanol and cyclohexanol, and the aliphatic diol is selected from the group consisting of ethylene glycol and propylene glycol.
- 7. A process according to claim 1, wherein said aliphatic alcohol is methanol, ethanol, and said aliphatic diol is ethylene glycol.
- 8. A process according to claim 1, wherein said process is carried out in the liquid phase, at a temperature of 25.degree. to 200.degree. C., under a carbon monoxide and oxygen total pressure of from atmospheric pressure up to 100 kg/cm.sup.2, with an oxygen to carbon monoxide partial response ratio of 0.005:1 to 50:1, and a reaction time of 1 to about 360 microns.
- 9. A process according to claim 1, wherein said temperature is in the range of from 50.degree. to 150.degree. C., said total pressure is in the range of from 2 to 100 kg/cm.sup.2, and said oxygen to carbon monoxide partial pressure ratio is in the range of from 0.01:1 to 0.5:1.
- 10. A process according to claim 1, wherein said process is carried out with the alcohol or diol being in excess over the stoichiometric amount, and with a catalyst concentration in the liquid reaction medium in the range of from 10.sup.-3 to 2 mol/liter.
- 11. A process according to claim 1, wherein said catalyst is selected from the group consisting of: Co(CH.sub.3 COO).sub.2 ; Co(CH.sub.3 COO).sub.3 ; Co(acetylacetonate).sub.2 ; Na; Co(acetylacetonate).sub.2 (bipyridil); Co(acetylacetonate).sub.2 (phenatroline); Na; Ba.sub.2 ; Co(citrate).sub.2 ; .sub.2.H.sub.2 O; Co(MeSALEN); Co(3-FSALEN), Co(SALPROPEN); Co(SALDPT); Co(ACACEN), Co(SALOPH), ##STR26## wherein: n is 1 to 3,
- m is 0 to 5,
- R'.sub.1 and R'.sub.2 are as above defined, and
- L is a secondary ligand selected from the group consisting of pyridine, phenanthroline, piperidine, quinoline, isoquinoline, H.sub.2 O, --OH, --OCH.sub.3, ##STR27## wherein R'.sub.3 is a C.sub.1 -C.sub.5 alkyl.
Priority Claims (2)
Number |
Date |
Country |
Kind |
20809/90 |
Jun 1990 |
ITX |
|
MI910374 |
Feb 1991 |
ITX |
|
Parent Case Info
This is a continuation, of application Ser. No. 07/718,236, filed Jun. 20, 1991, now abandoned.
US Referenced Citations (7)
Foreign Referenced Citations (1)
Number |
Date |
Country |
8707601 |
Dec 1987 |
WOX |
Continuations (1)
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Number |
Date |
Country |
Parent |
718236 |
Jun 1991 |
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