Process for the hydroxylation of olefins using molecular oxygen, an osmium containing catalyst, a copper Co-catalyst, and an aromatic amine based promoter
AssigneeExxon Research & Engineering Co.
InventorsRichard S. Myers, Robert C. Michaelson, Richard G. Austin
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Abstract
A process directed to the hydroxylation of olefins by reacting said olefins in the presence of oxygen, water, and a catalyst composition comprising (i) a catalytically active osmium containing compound, (ii) a Co-catalyst I comprising a copper containing compound such as CuBr.sub.2, and (iii) a Co-catalyst II capable of increasing the rate and/or selectivity of the hydroxylation reaction, such as pyridine is disclosed.
Claims31
A process for hydroxylating at least one olefinic compound having at least one ethylenic unsaturation which comprises reacting said olefinic compound in the presence of oxygen, water and a catalyst composition, in a manner and under conditions sufficient to convert catalytically at least one of said ethylenic unsaturation directly to its corresponding diol, said catalyst composition comprising:
- (a) at least one catalytically active osmium containing compound;
- (b) at least one transition metal containing Co-catalyst I having an identity and in an amount effective to increase at least one of the rate and selectivity of the hydroxylation reaction relative to its absence, said transition metal being copper;
- and
- (c) at least one Co-catalyst II having an identity and in an amount effective to increase the rate of the hydroxylation reaction relative to its absence and represented by at least one of the structural formulae:
- ##STR22## wherein:
- (1) in structural formula (XIa):
- (a) Z.sub.2 to Z.sub.6 independently represent a member selected from the group consisting of a methylidyne group, a substituted methylidyne group represented, by the formula .tbd.CR.sub.11, and a tertiary nitrogen group;
- said R.sub.11 substituent being selected from the group consisting of hydroxy, alkyl, aryl, aralkyl and alkaryl;
- (b) any two of said R.sub.11 substituents located on adjacent carbons of said Z.sub.2 to Z.sub.5 groups of structural formula (XIa) together can constitute part of a monocyclic or fused bicyclic ring system, which partial ring systems are (i) aromatic, or heteroaromatic in nature, said heteroatom being nitrogen, and (ii) completed by, and fused with parent structure (XIa) through said adjacent carbons of Z.sub.2 to Z.sub.5 groups;
- and
- (2) in structural formula (XIb):
- (a) Z.sub.7 to Z.sub.9 independently represent a member selected from the group consisting of a methylidyne group, and a substituted methylidyne group represented by the formula .tbd.CR'.sub.11 wherein R'.sub.11 is independently selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl;
- and
- (b) R.sub.12 is selected from the group consisting of alkyl, aryl, aralkyl, and alkaryl.
A process for directly hydroxylating olefins which comprises admixing to form a liquid reaction mixture comprising:
- (1) at least one olefinic compound having at least one ethylenic unsaturation;
- (2) at least one catalytically active osmium containing compound;
- (3) at least one transition metal containing Co-catalyst I having an identity and in an amount effective to increase at least one of the rate and selectivity of said hydroxylation reaction relative to its absence, wherein said transition metal is copper;
- (4) at least one Co-catalyst II having an identity and in an amount effective to increase at least one of the rate and selectivity of the hydroxylation reaction relative to its absence, said Co-catalyst II comprising at least one member selected from the group consisting of pyridine, 3,5-dimethylpyridine, 2,4-dimethylpyridine, 4-methylpyridine, 4-phenylpyridine, 2-methylpyridine, 1-methylimidazole, and 1,2-dimethylimidizole;
- (5) an oxygen containing gas;
- and
- (6) water in at least a stoichiometric molar ratio with the molar amount of ethylenic unsaturation to be hydroxylated in the olefinic compound;
- said admixing being conducted in a manner and under conditions sufficient to catalytically convert at least one of said ethylenic unsaturation directly to its corresponding diol.
Dependencies are inferred from the claim text.