US4740332A
Expired / Lapsed
US
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Process for preparing phosphonous acids
Assignee: ER Squibb and Sons LLC
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Filing: 1987-01-20
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Granted: 1988-04-26
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Expires: 2007-01-20
Abstract
Abstract A process is provided for preparing phosphonous acids of the structure wherein R 1 is lower alkyl or arylalkyl ##STR1## which are useful in preparing phosphinic and phosphonic acid ACE inhibitors, which process includes the steps of treating an olefin of the structure R 1 --CH═CH 2 wherein R 2 is lower alkyl or arylalkyl with a phosphorus-containing reagent such as sodium hypophosphite or hypophosphorous acid in the presence of an organic alcohol solvent such as ethanol or methanol, and a radical initiator such as azobisisobutyronitrile, under acidic conditions, preferably at the reflux temperature of the organic solvent, to form the phosphonous acid without forming the alkyl ester.
Inventors
- 👤 John K. Thottathil
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 21:14
CPC Classifications
C; C07; C07F; C07F9/00; C07F9/02; C07F9/28; C07F9/48
Claims Analysis
Total Claims: 14
Claim 1
Independent Claim
134 words
A process for preparing phosphonous acids of the structure ##STR6## wherein R 1 is phenylalkyl, which comprises reacting an olefin of the structure R.sub.1 --CH═CH.sub.2 wherein R 1 is as defined above, with a phosphorus-containing reagent which is sodium hypophosphite or hypophosphorous acid, in the presence of an alcohol solvent which is ethanol or methanol and azobisisobutyronitrile as a radical initiator, at a temperature of within the range of from about 40° to about 120° C., under acidic conditions of pH of from about 0 to about 4, in an open vessel reactor, to form the phosphonous acid directly, without forming the alcohol ester, and recovering said phosphonous acid from the reaction mixture, wherein the phenyl is unsubstituted or substituted with halogen, alkyl, alkoxy, alkylthio, hydroxy, alkanoyl, nitro, amino, dialkylamino or CF 3 .
Claim 2
Dependent Claim
134 words
A process for preparing phosphonous acids of the structure ##STR6## wherein R 1 is phenylalkyl, which comprises reacting an olefin of the structure R.sub.1 --CH═CH.sub.2 wherein R 1 is as defined above, with a phosphorus-containing reagent which is sodium hypophosphite or hypophosphorous acid, in the presence of an alcohol solvent which is ethanol or methanol and azobisisobutyronitrile as a radical initiator, at a temperature of within the range of from about 40° to about 120° C., under acidic conditions of pH of from about 0 to about 4, in an open vessel reactor, to form the phosphonous acid directly, without forming the alcohol ester, and recovering said phosphonous acid from the reaction mixture, wherein the phenyl is unsubstituted or substituted with halogen, alkyl, alkoxy, alkylthio, hydroxy, alkanoyl, nitro, amino, dialkylamino or CF 3 .
Claim 3
Dependent Claim
14 words
The process as defined in claim 1 wherein the phosphorus-containing reagent is hypophosphorous acid.
Claim 4
Dependent Claim
23 words
The process as defined in claim 1 wherein the reaction is carried out at a pH of from about 0 to about 2.
Claim 5
Dependent Claim
30 words
The process as defined in claim 1 wherein the phosphorus-containing reagent is sodium hypophosphite and the olefin is treated with said sodium hypophosphite in the presence of a strong acid.
Claim 6
Dependent Claim
18 words
The process as defined in claim 4 wherein said strong acid is H 2 SO 4 or HCl.
Claim 7
Dependent Claim
16 words
The process as defined in claim 1 wherein the radical initiator is employed in catalytic amounts.
Claim 8
Dependent Claim
31 words
The process as defined in claim 1 wherein the phosphorus-containing reagent is employed in a molar ratio to the olefin of within the range of from about 0.5:1 to about 6:1.
Claim 9
Dependent Claim
31 words
The process as defined in claim 1 wherein the radical initiator is employed in a molar ratio to the olefin of within the range of from about 0.01:1 to about 0.3:1.
Claim 10
Dependent Claim
19 words
The process as defined in claim 1 wherein the olefin is ##STR7## wherein n is 2, 3 or 4.
Claim 11
Dependent Claim
28 words
The process as defined in claim 1 wherein the reaction is carried out at a temperature of within the range of from about 50° to about 100° C.
Claim 12
Dependent Claim
13 words
The process as defined in claim 1 wherein the alcohol solvent is methanol.
Claim 13
Dependent Claim
22 words
The process as defined in claim 10 wherein the reaction is carried out at about the reflux temperature of the organic solvent.
Claim 14
Dependent Claim
24 words
The process as defined in claim 1 wherein the reaction is carried out for a period of from about 3 to about 20 hours.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1991-04-26 | 1991-10-26 | 1992-04-26 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1995-04-26 | 1995-10-26 | 1996-04-26 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1999-04-26 | 1999-10-26 | 2000-04-26 | $7700.00 | Window Closed / Lapsed |