US4345984A
Expired / Lapsed
US
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Novel prostaglandin analogues and process for making same
Assignee: Procter and Gamble Co
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Filing: 1981-03-02
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Granted: 1982-08-24
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Expires: 2001-03-02
Abstract
Abstract A novel process for the oxidation of olefins to the corresponding alpha-epoxy alcohols which can be incorporated in the total synthesis of members of a novel class of prostaglandin analogues. Olefins are reacted with singlet oxygen in the presence of a group IVB, VB or VIB transition metal catalyst, excluding chromium. The reaction is fast and highly selective to the alpha-epoxy alcohol. When cyclopentene is oxidized in the process of the invention, high yields of cis 2,3-epoxy-cyclopentan-1-ol are obtained. The latter compound is used as a starting material in the synthesis of prostaglandin analogues. The prostanoids of the invention are characterized by an oxa group replacing the methylene group at the 7-position, and the absence of a hydroxyl or other substituent at the 11-position. Members of this class of prostanoids show important cytoprotective properties in animal tests.
Inventors
- 👤 Edward D. Mihelich
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-03 09:40
CPC Classifications
C; C07; C07C; C07C405/00; C07C405/0008; C07C405/0016; A; A61; A61P; A61P43/00; C07C405/0025; C07D; C07D303/00; C07D303/02; C07D303/12; C07D303/14
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
64 words
A process for converting olefins to the corresponding alpha-epoxy alcohols comprising reacting an olefin with singlet oxygen in the 1 Δg state and converting the reaction product to an alpha-epoxy alcohol by in situ rearrangement in the presence of a catalytic amount of a heterogeneous or homogeneous catalyst containing a transition metal of group IVB, VB or VIB of the Periodic Table, excluding chromium.
Claim 2
Dependent Claim
64 words
A process for converting olefins to the corresponding alpha-epoxy alcohols comprising reacting an olefin with singlet oxygen in the 1 Δg state and converting the reaction product to an alpha-epoxy alcohol by in situ rearrangement in the presence of a catalytic amount of a heterogeneous or homogeneous catalyst containing a transition metal of group IVB, VB or VIB of the Periodic Table, excluding chromium.
Claim 3
Dependent Claim
19 words
A process according to claim 1 wherein the olefin is a mono-olefin, and the catalyst is a homogeneous catalyst.
Claim 4
Dependent Claim
27 words
A process according to claim 2 wherein the reaction mixture contains from about 5% to about 98% of an organic solvent which is miscible with the olefin.
Claim 5
Dependent Claim
65 words
A process for converting mono-olefins to the corresponding alpha-epoxy alcohols, whereby a reaction mixture comprising: a mono-olefin, from about 5% to about 98% of an organic solvent which is miscible with said mono-olefin; a catalytic amount of a soluble salt or metallo-organic complex of vanadium or molybdenum; and a catalytic amount of a photo-sensitizer; is purged with ground-state triplet oxygen and irradiated with visible light.
Claim 6
Dependent Claim
65 words
A process for converting mono-olefins to the corresponding alpha-epoxy alcohols, whereby a reaction mixture comprising: a mono-olefin, from about 5% to about 98% of an organic solvent which is miscible with said mono-olefin; a catalytic amount of a soluble salt or metallo-organic complex of vanadium or molybdenum; and a catalytic amount of a photo-sensitizer; is purged with ground-state triplet oxygen and irradiated with visible light.
Claim 7
Dependent Claim
41 words
A process according to claim 4 wherein the catalyst is a vanadium catalyst, and the photo-sensitizer is selected from the group consisting of tetraphenyl porphin, methylene blue, erythrosin B, eosin, fluorescein, hematoporphin, rubene, rose bengal and the phthalocyanines and mixtures thereof.
Claim 8
Dependent Claim
30 words
A process according to claim 5 wherein the amount of catalyst is from about 0.1% to about 2.5%, and the amount of photosensitizer is from about 0.01% to about 2.5%.
Claim 9
Dependent Claim
84 words
A process for converting an olefin selected from the group consisting of cyclopentene, cis 9-octadecenoic acid and esters and salts thereof, cis 4-octene, 2,3-dimethyl-2-butene, alpha-pinene and beta-pinene, to the corresponding alpha-epoxy alcohol, whereby a reaction mixture comprising: the olefin, from about 80% to about 95% of a solvent selected from the group consisting of toluene and dichloromethane, from about 0.7% to about 1.3% vanadium acetylacetonate, from about 0.05% to about 1.3% tetraphenyl porphin; is purged with ground-state triplet oxygen and irradiated with visible light.
Claim 10
Dependent Claim
84 words
A process for converting an olefin selected from the group consisting of cyclopentene, cis 9-octadecenoic acid and esters and salts thereof, cis 4-octene, 2,3-dimethyl-2-butene, alpha-pinene and beta-pinene, to the corresponding alpha-epoxy alcohol, whereby a reaction mixture comprising: the olefin, from about 80% to about 95% of a solvent selected from the group consisting of toluene and dichloromethane, from about 0.7% to about 1.3% vanadium acetylacetonate, from about 0.05% to about 1.3% tetraphenyl porphin; is purged with ground-state triplet oxygen and irradiated with visible light.
Claim 11
Dependent Claim
20 words
A process according to claim 7 wherein the olefin is cyclopentene and wherein the corresponding alpha-epoxy alchol is cis-2,3-epoxy cyclopentan-1-ol.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1985-08-23 | 1986-02-22 | 1986-08-24 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1989-08-23 | 1990-02-22 | 1990-08-24 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1993-08-23 | 1994-02-22 | 1994-08-24 | $7700.00 | Window Closed / Lapsed |