US4254279A
Expired / Lapsed
US
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Ester resolution process
Assignee: FMC Corp
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Filing: 1979-09-24
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Granted: 1981-03-03
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Expires: 1999-09-24
Abstract
Abstract Optically active 1-Trichloromethyl-3-methyl-2-butenyl acetoacetate is prepared by resolving the racemic ester via a crystalline enamine derivative.
Inventors
- 👤 Charles E. Hatch, III
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-01 21:09
CPC Classifications
C; C07; C07C; C07C67/00; C07C67/30; C07C67/313; C07B; C07B2200/00; C07B2200/07
Claims Analysis
Total Claims: 4
Claim 1
Independent Claim
122 words
A process for resolving 1-trichloromethyl-3-methyl-2-butenyl acetoacetate which comprises (i) condensing 1-trichloromethyl-3-methyl-2-butenyl acetoacetate with optically active 1-(1-naphthyl)ethylamine in acetonitrile using a catalytic amount of protonic mineral acid or sulfonic acid, (ii) crystallizing or recrystallizing the resultant mixture of enamine diastereomers from acetonitrile, employing 2-4 g of said mixture per 100 ml of acetonitrile, recovering one diastereomer as the first crystalline precipitate and the other in the residual solution, and then (iii) hydrolyzing at least one of the recovered diastereomers in a mixture of tetrahydrofuran and aqueous mineral acid selected from HCl, HBr, HNO 3 , H 3 PO 4 , and H 2 SO 4 , about 1-20 equivalents of 0.1 to 4 N aqueous acid being employed for each equivalent of diastereomer.
Claim 2
Dependent Claim
122 words
A process for resolving 1-trichloromethyl-3-methyl-2-butenyl acetoacetate which comprises (i) condensing 1-trichloromethyl-3-methyl-2-butenyl acetoacetate with optically active 1-(1-naphthyl)ethylamine in acetonitrile using a catalytic amount of protonic mineral acid or sulfonic acid, (ii) crystallizing or recrystallizing the resultant mixture of enamine diastereomers from acetonitrile, employing 2-4 g of said mixture per 100 ml of acetonitrile, recovering one diastereomer as the first crystalline precipitate and the other in the residual solution, and then (iii) hydrolyzing at least one of the recovered diastereomers in a mixture of tetrahydrofuran and aqueous mineral acid selected from HCl, HBr, HNO 3 , H 3 PO 4 , and H 2 SO 4 , about 1-20 equivalents of 0.1 to 4 N aqueous acid being employed for each equivalent of diastereomer.
Claim 3
Dependent Claim
122 words
A process for preparing (R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetate substantially free of the (S)-optical isomer which comprises (i) condensing racemic 1-trichloromethyl-3-methyl-2-butenyl acetoacetate with (S)-1-(1-naphthyl)ethylamine in acetonitrile using a catalytic amount of protonic mineral acid or sulfonic acid, (ii) crystallizing or recrystallizing the resultant mixture of (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate and (S)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate from acetonitrile, employing 2-4 g of said mixture per 100 ml of acetonitrile, recovering (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate as the first crystalline precipitate, and then (iii) hydrolyzing the recovered (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate in a mixture of tetrahydrofuran and aqueous mineral acid selected from HCl, HBr, HNO 3 , H 3 PO 4 , and H 2 SO 4 , about 1-20 equivalents of 0.1 to 4 N aqueous mineral acid being employed for each equivalent of (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate.
Claim 4
Dependent Claim
122 words
A process for preparing (R)-1-trichloromethyl-3-methyl-2-butenyl acetoacetate substantially free of the (S)-optical isomer which comprises (i) condensing racemic 1-trichloromethyl-3-methyl-2-butenyl acetoacetate with (S)-1-(1-naphthyl)ethylamine in acetonitrile using a catalytic amount of protonic mineral acid or sulfonic acid, (ii) crystallizing or recrystallizing the resultant mixture of (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate and (S)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate from acetonitrile, employing 2-4 g of said mixture per 100 ml of acetonitrile, recovering (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate as the first crystalline precipitate, and then (iii) hydrolyzing the recovered (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate in a mixture of tetrahydrofuran and aqueous mineral acid selected from HCl, HBr, HNO 3 , H 3 PO 4 , and H 2 SO 4 , about 1-20 equivalents of 0.1 to 4 N aqueous mineral acid being employed for each equivalent of (R)-3-methyl-1-trichloromethylbut-2-en-1-yl (S)-3-[N-(1-(1-naphthyl)ethyl)amino]but-2-enoate.
References Cited (Backward Citations)
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| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
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| 3.5 Years (Year 4) | 1984-03-02 | 1984-09-01 | 1985-03-03 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-03-02 | 1988-09-01 | 1989-03-03 | $3760.00 | Window Closed / Lapsed |
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