US4014895A
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US
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Method for synthesis of optically active thiolactones
Assignee: Sumitomo Chemical Co Ltd
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Filing: 1974-12-13
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Granted: 1977-03-29
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Expires: 1994-12-13
Abstract
Abstract A new method for the production of intermediates in the synthesis of an optically active biotin, which comprises reacting a dicarboxylic acid of the formula: ##SPC1## Or its reactive derivative with an optically active primary amine, reducing the resulting trione with a metal hydride, hydrolyzing the resultant amide-alcohol and treating the thus produced lactone with a thiolactonating agent to give a thiolactone of the formula: ##SPC2## , the said trione and amide-alcohol being respectively novel and representable by the formulae: ##SPC3##
Inventors
- 👤 Yasuhiko Aoki
- 👤 Hiroyuki Suzuki
- 👤 Hisao Akiyama
- 👤 Shigeru Okano
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-28 07:31
CPC Classifications
C; C07; C07D; C07D487/00; C07D487/02; C07D487/04
Claims Analysis
Total Claims: 11
Claim 1
Independent Claim
128 words
A process for producing an optically active (+)-thiolactone of the formula: ##SPC8## wherein R is a benzyl group, which comprises reacting a dicarboxylic acid of the formula: ##SPC9## wherein R is as defined above or the acid anhydride, ester or halide thereof with an optically active primary amine of the formula: R.sup.1 -- NH.sub.2 where R 1 is an optically active primary amine residue, reducing the resultant trione of the formula: ##SPC10## wherein R and R 1 are each as defined above, hydrolyzing the resulting amide-alcohol of the formula: ##SPC11## wherein R and R 1 are each defined above and treating the thus obtained lactone of the formula: ##SPC12## wherein R is as defined above with an alkali metal hydrosulfide and carbon disulfide or phosphorus pentasulfide and imidazole.
Claim 2
Dependent Claim
128 words
A process for producing an optically active (+)-thiolactone of the formula: ##SPC8## wherein R is a benzyl group, which comprises reacting a dicarboxylic acid of the formula: ##SPC9## wherein R is as defined above or the acid anhydride, ester or halide thereof with an optically active primary amine of the formula: R.sup.1 -- NH.sub.2 where R 1 is an optically active primary amine residue, reducing the resultant trione of the formula: ##SPC10## wherein R and R 1 are each as defined above, hydrolyzing the resulting amide-alcohol of the formula: ##SPC11## wherein R and R 1 are each defined above and treating the thus obtained lactone of the formula: ##SPC12## wherein R is as defined above with an alkali metal hydrosulfide and carbon disulfide or phosphorus pentasulfide and imidazole.
Claim 3
Dependent Claim
20 words
The process according to claim 1, wherein the thiolactonation is carried out using an alkali metal hydrosulfide and carbon disulfide.
Claim 4
Dependent Claim
17 words
The process according to claim 1, wherein the thiolactonation is carried out using phosphorus pentasulfide and imidazole.
Claim 5
Dependent Claim
28 words
The process according to claim 1, wherein the optically active primary amine is selected from the group consisting of (R)-1-phenethylamine, (1S,2S)-(+)-threo-1-(p-nitrophenyl)-2-amino-1,3-propanediol, (1S,2S)-(+)-threo-1-(p-methylsulfonylphenyl)-2-amino-1,3-propanediol, (+)-1-phenyl-2-(p-tolyl)ethylamine, (+)-1-(2-naphthyl)ethylamine, (+)-1-(2-thienyl)ethylamine, (S)-phenylalaninol and (S)-phenylalanine.
Claim 6
Dependent Claim
22 words
A compound of the formula: ##SPC13## wherein R is a benzyl group and R 1 is an optically active primary amine residue.
Claim 7
Dependent Claim
22 words
A compound of the formula: ##SPC13## wherein R is a benzyl group and R 1 is an optically active primary amine residue.
Claim 8
Dependent Claim
27 words
The compound of claim 5, wherein the optically active primary amine is selected from the group consisting of (R)-1-phenethylamine, (1S,2S)-(+)-threo-1-(p-nitrophenyl)-2-amino-1,3-propanediol, (1S,2S)-(+)-threo-1-(p-methylsulfonylphenyl)-2-amino-1,3-propanediol, (+)-1-phenyl-2-(p-tolyl)ethylamine, (+)-1-(2-naphthyl)ethylamine, (+)-1-(2-thienyl)ethylamine, (S)-phenylalaninol and (S)-phenylalanine.
Claim 9
Dependent Claim
22 words
A compound of the formula: ##SPC14## wherein R is a benzyl group and R 1 is an optically active primary amine residue.
Claim 10
Dependent Claim
22 words
A compound of the formula: ##SPC14## wherein R is a benzyl group and R 1 is an optically active primary amine residue.
Claim 11
Dependent Claim
27 words
The compound of claim 7, wherein the optically active primary amine is selected from the group consisting of (R)-1-phenethylamine, (1S,2S)-(+)-threo-1-(p-nitrophenyl)-2-amino-1,3-propanediol, (1S,2S)-(+)-threo-1-(p-methylsulfonylphenyl)-2-amino-1,3-propanediol, (+)-1-phenyl-2-(p-tolyl)ethylamine, (+)-1-(2-naphthyl)ethylamine, (+)-1-(2-thienyl)ethylamine, (S)-phenylalaninol and (S)-phenylalanine.
References Cited (Backward Citations)
US2489232A
Cited
US2417326A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1980-03-28 | 1980-09-27 | 1981-03-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1984-03-28 | 1984-09-27 | 1985-03-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1988-03-28 | 1988-09-27 | 1989-03-29 | $7700.00 | Window Closed / Lapsed |