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US4194051A Expired / Lapsed US ⏱️ 0.0 years remaining

Asymmetric catalysis

Assignee: Monsanto Co
•
Filing: 1977-08-17
•
Granted: 1980-03-18
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Expires: 1997-08-17
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Abstract

Abstract Catalytic asymmetric hydrogenation of a compound of the formula ##STR1## wherein R, R 1 and R 2 each independently represent hydrogen, substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, and R 3 represents substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, provided that, if only one of R and R 1 is hydrogen the Z geometric isomer is hydrogenated, in the presence of a homogeneous, coordination complex catalyst comprising rhodium, iridium or ruthenium in combination with an optically active bis phosphine ligand provides an excellent level of optical purity.

Inventors

  • 👤 Gerald L. Bachman
  • 👤 Billy D. Vineyard

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-11-06 03:44
CPC Classifications
C; C07; C07C; C07C67/00; C07C67/30; C07C67/303

Claims Analysis

Total Claims: 35
Claim 1
Independent Claim 221 words
An asymmetric hydrogenation process affording an optical purity of enantiomorph of at least about 86 percent comprising hydrogenating a compound of the formula ##STR11## wherein R, R 1 and R 2 each independently represent hydrogen, substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, and R 3 represents substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, provided that, if only one of R and R 1 is hydrogen the Z geometric isomer is hydrogenated, in the presence of from about 0.001% to about 5% by weight, based on said compound, of a homogeneous, coordination complex of rhodium, iridium or ruthenium in combination with an optically active bis phosphine ligand represented by the formula ##STR12## wherein A and B each independently represent substituted or unsubstituted alkyl of from 1 to 12 carbon atoms, substituted or unsubstituted cyclo alkyl having from 4 to 7 carbon atoms, or substituted or unsubstituted aryl; provided that such substituents provide no significant interference with the steric requirements around the phosphorus atom and A and B are different, said process being conducted at a temperature of from about -20° C. to about 110° C. and said hydrogen concentration being equal to about 0.5 to about 5 times the mole quantity of said compound.
Claim 2
Dependent Claim 221 words
An asymmetric hydrogenation process affording an optical purity of enantiomorph of at least about 86 percent comprising hydrogenating a compound of the formula ##STR11## wherein R, R 1 and R 2 each independently represent hydrogen, substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, and R 3 represents substituted or unsubstituted alkyl having from 1 to 5 carbon atoms or substituted or unsubstituted aryl, provided that, if only one of R and R 1 is hydrogen the Z geometric isomer is hydrogenated, in the presence of from about 0.001% to about 5% by weight, based on said compound, of a homogeneous, coordination complex of rhodium, iridium or ruthenium in combination with an optically active bis phosphine ligand represented by the formula ##STR12## wherein A and B each independently represent substituted or unsubstituted alkyl of from 1 to 12 carbon atoms, substituted or unsubstituted cyclo alkyl having from 4 to 7 carbon atoms, or substituted or unsubstituted aryl; provided that such substituents provide no significant interference with the steric requirements around the phosphorus atom and A and B are different, said process being conducted at a temperature of from about -20° C. to about 110° C. and said hydrogen concentration being equal to about 0.5 to about 5 times the mole quantity of said compound.
Claim 3
Dependent Claim 62 words
A process according to claim 1 wherein the bis phosphine ligand is represented by the formula ##STR13## wherein X represents substituted or unsubstituted phenyl, Y represents substituted or unsubstituted 2-alkoxyphenyl wherein the alkoxy has from 1 to 6 carbon atoms; provided that such substituents provide no significant interference with the steric requirements around the phosphorus atom and X and Y are different.
Claim 4
Dependent Claim 67 words
A process according to claim 1 wherein the bis phosphine ligand is represented by the formula ##STR14## wherein M represents ##STR15## N represents ##STR16## R' and R" each independently represent hydrogen, halogen, alkyl having from 1 to 6 carbon atoms or alkoxy having from 1 to 6 carbon atoms, and R''' represents alkyl having from 1 to 6 carbon atoms; provided that M and N are different.
Claim 5
Dependent Claim 13 words
A process according to claim 1 wherein the bis phosphine ligand is 1,2-bis(o-anisylphenylphosphino)ethane.
Claim 6
Dependent Claim 16 words
A process according to claim 1 wherein the metal utilized in the catalyst complex is rhodium.
Claim 7
Dependent Claim 16 words
A process according to claim 2 wherein the metal utilized in the catalyst complex is rhodium.
Claim 8
Dependent Claim 16 words
A process according to claim 3 wherein the metal utilized in the catalyst complex is rhodium.
Claim 9
Dependent Claim 16 words
A process according to claim 4 wherein the metal utilized in the catalyst complex is rhodium.
Claim 10
Dependent Claim 31 words
A process according to claim 1 wherein the compound being hydrogenated is represented by the formula ##STR17## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 11
Dependent Claim 31 words
A process according to claim 2 wherein the compound being hydrogenated is represented by the formula ##STR18## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 12
Dependent Claim 31 words
A process according to claim 3 wherein the compound being hydrogenated is represented by the formula ##STR19## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 13
Dependent Claim 31 words
A process according to claim 4 wherein the compound being hydrogenated is represented by the formula ##STR20## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 14
Dependent Claim 31 words
A process according to claim 5 wherein the compound being hydrogenated is represented by the formula ##STR21## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 15
Dependent Claim 31 words
A process according to claim 6 wherein the compound being hydrogenated is represented by the formula ##STR22## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 16
Dependent Claim 31 words
A process according to claim 7 wherein the compound being hydrogenated is represented by the formula ##STR23## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 17
Dependent Claim 31 words
A process according to claim 8 wherein the compound being hydrogenated is represented by the formula ##STR24## provided that, if R 1 is not hydrogen the Z geometric isomer is hydrogenated.
Claim 18
Dependent Claim 14 words
A process according to claim 9 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 19
Dependent Claim 14 words
A process according to claim 9 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 20
Dependent Claim 14 words
A process according to claim 10 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 21
Dependent Claim 14 words
A process according to claim 10 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 22
Dependent Claim 14 words
A process according to claim 11 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 23
Dependent Claim 14 words
A process according to claim 11 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 24
Dependent Claim 14 words
A process according to claim 12 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 25
Dependent Claim 14 words
A process according to claim 12 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 26
Dependent Claim 14 words
A process according to claim 13 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 27
Dependent Claim 14 words
A process according to claim 13 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 28
Dependent Claim 14 words
A process according to claim 14 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 29
Dependent Claim 14 words
A process according to claim 14 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 30
Dependent Claim 14 words
A process according to claim 15 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 31
Dependent Claim 14 words
A process according to claim 15 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 32
Dependent Claim 14 words
A process according to claim 16 wherein the compound being hydrogenated is (Z)-ethyl 2-acetyloxy-3-phenyl-2-propenoate.
Claim 33
Dependent Claim 14 words
A process according to claim 16 wherein the compound being hydrogenated is ethyl 2-acetyloxy-2-propenoate.
Claim 34
Dependent Claim 27 words
A process according to claim 1 wherein the Z geometric isomer of the compound is hydrogenated if said compound exists as a Z and E geometric isomer.
Claim 35
Dependent Claim 14 words
A process according to claim 1 wherein R and R 1 are the same.

References Cited (Backward Citations)

DE2123063C3 Cited
DE2161200A1 Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1983-03-18 1983-09-17 1984-03-18 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1987-03-18 1987-09-17 1988-03-18 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1991-03-18 1991-09-17 1992-03-18 $7700.00 Window Closed / Lapsed

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