US4499027A
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Process for preparing optically active [(3-amino-3-carboxy)propyl-1]_phosphinic acid derivatives
Assignee: Meiji Seika Kaisha Ltd
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Filing: 1984-05-18
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Granted: 1985-02-12
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Expires: 2004-05-18
Abstract
Abstract Disclosed is a novel process for optically active [(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives, which comprises reacting a Shiff's base with a derivative of vinylphosphinate in the presence of a base, and subjecting the resulting compound to hydrolysis to form the optically active [(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives as either [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives or [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives.
Inventors
- 👤 Nobuto Minowa
- 👤 Shunzo Fukatsu
- 👤 Kunitaka Tachibana
- 👤 Taro Niida
- 👤 Sadaaki Mase
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-31 15:21
CPC Classifications
A; A01; A01N; A01N57/00; A01N57/18; A01N57/22; A01N57/20; C; C07; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/30; C07F9/301
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
216 words
A process for preparing optically active [(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives, which comprises reacting a compound represented by the formula (I)-1: ##STR10## wherein R 1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each S-form or a compound represented by the formula (I)-2: ##STR11## wherein R 1 have the same meaning as defined above; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each R-form with a compound represented by the formula (II): ##STR12## wherein R 2 and R 3 may be the same or different and each represent a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, in the presence of a base, and subjecting the resulting compound to hydrolysis to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1: ##STR13## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is L-form or [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2: ##STR14## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is D-form.
Claim 2
Dependent Claim
216 words
A process for preparing optically active [(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives, which comprises reacting a compound represented by the formula (I)-1: ##STR10## wherein R 1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each S-form or a compound represented by the formula (I)-2: ##STR11## wherein R 1 have the same meaning as defined above; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each R-form with a compound represented by the formula (II): ##STR12## wherein R 2 and R 3 may be the same or different and each represent a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, in the presence of a base, and subjecting the resulting compound to hydrolysis to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1: ##STR13## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is L-form or [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2: ##STR14## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is D-form.
Claim 3
Dependent Claim
33 words
The process according to claim 1, wherein the compound of the formula (I)-1 or (I)-2 and the compound of the formula (II) is reacted at a temperature ranging from -100° to 25° C.
Claim 4
Dependent Claim
56 words
The process according to claim 1, wherein the compound of the formula (II) is used in 1 to 2 moles per mole of the compound of the formula (I)-1 or (I)-2, and the base is used in 1 to 3 equivalent weights based on one equivalent weight of the compound of the formula (I)-1 or (I)-2.
Claim 5
Dependent Claim
45 words
The process according to claim 1, wherein the base is selected from the group consisting of n-butyl lithium, sec-butyl lithium, t-butyl lithium, lithium diisopropylamide, lithium isopropylcyclohexylamide, lithium di(trimethylsilyl)amide, sodium methylate, sodium ethylate, sodium hydride, potassium t-butoxide, calcium diisopropylamide, methylmagnesium chloride, methylmagnesium bromide and methylmagnesium iodide.
Claim 6
Dependent Claim
178 words
The process according to claim 1, which comprises reacting a compound represented by the formula (I)-1: ##STR15## wherein R 1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each S-form with a compound represented by the formula (II): ##STR16## wherein R 2 and R 3 may be the same or different and each represent a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, in the presence of a base, and subjecting the resulting compound to hydrolysis to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1: ##STR17## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is L-form or [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2: ##STR18## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is D-form.
Claim 7
Dependent Claim
31 words
The process according to claim 5, wherein the compound of the formula (I)-1 and the compound of the formula (II) is reacted at a temperature ranging from -100° to 25° C.
Claim 8
Dependent Claim
44 words
The process according to claim 6, wherein the compound of the formula (I)-1 and the compound of the formula (II) is reacted at a temperature ranging from -100° to -75° C. to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1.
Claim 9
Dependent Claim
44 words
The process according to claim 6, wherein the compound of the formula (I)-1 and the compound of the formula (II) is reacted at a temperature ranging from -60° to 25° C. to form the optically active [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2.
Claim 10
Dependent Claim
52 words
The process according to claim 5, wherein the compound of the formula (II) is used in 1 to 2 moles per mole of the compound of the formula (I)-1, and the base is used in 1 to 3 equivalent weights based on one equivalent weight of the compound of the formula (I)-1.
Claim 11
Dependent Claim
45 words
The process according to claim 5, wherein the base is selected from the group consisting of n-butyl lithium, sec-butyl lithium, t-butyl lithium, lithium diisopropylamide, lithium isopropylcyclohexylamide, lithium di(trimethylsilyl)amide, sodium methylate, sodium ethylate, sodium hydride, potassium t-butoxide, calcium diisopropylamide, methylmagnesium chloride, methylmagnesium bromide and methylmagnesium iodide.
Claim 12
Dependent Claim
178 words
The process according to claim 1, which comprises reacting a compound represented by the formula (I)-2: ##STR19## wherein R 1 represents a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group; and the absolute configurations of the three asymmetric carbon atoms indicated by * are each R-form with a compound represented by the formula (II): ##STR20## wherein R 2 and R 3 may be the same or different and each represent a straight or branched chain alkyl group having 1 to 5 carbon atoms, an aryl group or an aralkyl group, in the presence of a base, and subjecting the resulting compound to hydrolysis to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1: ##STR21## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is L-form or [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2: ##STR22## wherein R 2 have the same meaning as defined above; and the absolute configuration of the amino acid is D-form.
Claim 13
Dependent Claim
31 words
The process according to claim 11, wherein the compound of the formula (I)-2 and the compound of the formula (II) is reacted at a temperature ranging from -100° to 25° C.
Claim 14
Dependent Claim
44 words
The process according to claim 12, wherein the compound of the formula (I)-2 and the compound of the formula (II) is reacted at a temperature ranging from -100° to -75° C. to form the optically active [D-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-2.
Claim 15
Dependent Claim
44 words
The process according to claim 12, wherein the compound of the formula (I)-2 and the compound of the formula (II) is reacted at a temperature ranging from -60° to 25° C. to form the optically active [L-(3-amino-3-carboxy)propyl-1]phosphinic acid derivatives represented by the formula (III)-1.
Claim 16
Dependent Claim
52 words
The process according to claim 11, wherein the compound of the formula (II) is used in 1 to 2 moles per mole of the compound of the formula (I)-2, and the base is used in 1 to 3 equivalent weights based on one equivalent weight of the compound of the formula (I)-2.
Claim 17
Dependent Claim
45 words
The process according to claim 11, wherein the base is selected from the group consisting of n-butyl lithium, sec-butyl lithium, t-butyl lithium, lithium diisopropylamide, lithium isopropylcyclohexylamide, lithium di(trimethylsilyl)amide, sodium methylate, sodium ethylate, sodium hydride, potassium t-butoxide, calcium diisopropylamide, methylmagnesium chloride, methylmagnesium bromide and methylmagnesium iodide.
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) | 1988-02-12 | 1988-08-13 | 1989-02-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1992-02-12 | 1992-08-13 | 1993-02-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1996-02-12 | 1996-08-13 | 1997-02-12 | $7700.00 | Window Closed / Lapsed |