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US4567265A Expired / Lapsed US ⏱️ 0.0 years remaining

Cyclopropanoid cyanoesters and method of making same

Assignee: Loyola University Chicago
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Filing: 1984-01-16
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Granted: 1986-01-28
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Expires: 2004-01-16
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Abstract

Abstract Cyclopropanoid cyanoesters of the formula: ##STR1## where R' is --CH 3 or --CH 2 CH 3 , and A is (a) --H, or (b) A, B represents an aliphatic group joined to a carbon atom on the cyclopropanoid ring, thereby forming a spiro group, A, B being selected from structures having the formula: (i) --(CH 2 ) n --, wherein n=3, 4, or 5, and (ii) --(CH 2 ) 2 --Y--(CH 2 ) 2 --, wherein Y is NCH 3 , O, or S); and, when A is --H, B is selected from the group consisting of: ##STR2## are disclosed. These compositions are useful in the synthesis of pyrethroids. A process for synthesis of cyclopropanoid cyanoesters by reacting 2-nitropropane with cyanoesters of the general formula: ##STR3## is also disclosed and claimed.

Inventors

  • 👤 James H. Babler

Bibliographic Details

Application Number —
Jurisdiction US
Data Source google_patents
Last Synchronized 2026-10-26 16:57
CPC Classifications
C; C07; C07D; C07D207/00; C07D207/02; C07D207/30; C07D207/32; C07D207/33; C07D207/337; C07D213/00; C07D213/02; C07D213/04; C07D213/24; C07D213/54; C07D213/57; C07D221/00; C07D221/02; C07D221/20; C07D307/00; C07D307/02; C07D307/34; C07D307/38; C07D307/54; C07D311/00; C07D311/96; C07D333/00; C07D333/02; C07D333/04; C07D333/06; C07D333/24; C07D335/00; C07D335/04

Claims Analysis

Total Claims: 10
Claim 1
Independent Claim 231 words
A process for synthesis of a cyclopropanoid cyanoester comprising the following steps: (A) forming a reaction mixture in a C 1 through C 4 monohydric alcohol solvent of (i) 2-nitropropane, (ii) a cyanoester selected from the group consisting of ##STR43## wherein R' is methyl or ethyl, A, B represents a group having the formula --(CH 2 ) n -- or --(CH 2 ) 2 --Y--(CH 2 ) 2 --, n=3, 4, or 5, Y being NCH 3 , O, or S, and R can be selected from the class consisting of: (1) alkyl, haloalkyl, alkenyl, haloalkenyl, cycloalkyl, carboalkoxy, and cycloalkenyl groups having up to ten carbons; (2) a heterocyclic residue selected from the group consisting of furan, thiophene, pyridine, pyrrole and indole; (3) phenyl and naphthyl groups; and, (4) monosubstituted phenyl groups and disubstituted phenyl groups wherein the substituents are selected from the group consisting of alkyl, halogen, nitro, alkoxy, and haloalkyl; provided that when R is alkenyl, R is not conjugated with the double bond between C 1 and C 2 and when R is a substituted phenyl group, at least one of the ortho carbons of said phenyl group is bonded to hydrogen; and (iii) a base selected from the group consisting of alkali metal alkoxides and alkali metal carbonates; (B) heating said reaction mixture in refluxing alcohol solvent; and (C) isolating a cyclopropanoid cyanoester from said reaction mixture.
Claim 2
Dependent Claim 231 words
A process for synthesis of a cyclopropanoid cyanoester comprising the following steps: (A) forming a reaction mixture in a C 1 through C 4 monohydric alcohol solvent of (i) 2-nitropropane, (ii) a cyanoester selected from the group consisting of ##STR43## wherein R' is methyl or ethyl, A, B represents a group having the formula --(CH 2 ) n -- or --(CH 2 ) 2 --Y--(CH 2 ) 2 --, n=3, 4, or 5, Y being NCH 3 , O, or S, and R can be selected from the class consisting of: (1) alkyl, haloalkyl, alkenyl, haloalkenyl, cycloalkyl, carboalkoxy, and cycloalkenyl groups having up to ten carbons; (2) a heterocyclic residue selected from the group consisting of furan, thiophene, pyridine, pyrrole and indole; (3) phenyl and naphthyl groups; and, (4) monosubstituted phenyl groups and disubstituted phenyl groups wherein the substituents are selected from the group consisting of alkyl, halogen, nitro, alkoxy, and haloalkyl; provided that when R is alkenyl, R is not conjugated with the double bond between C 1 and C 2 and when R is a substituted phenyl group, at least one of the ortho carbons of said phenyl group is bonded to hydrogen; and (iii) a base selected from the group consisting of alkali metal alkoxides and alkali metal carbonates; (B) heating said reaction mixture in refluxing alcohol solvent; and (C) isolating a cyclopropanoid cyanoester from said reaction mixture.
Claim 3
Dependent Claim 19 words
The process of claim 1 wherein said alcohol solvent is selected from the group consisting of methanol and ethanol.
Claim 4
Dependent Claim 44 words
The process of claim 1 wherein said step of isolating a cyclopropanoid cyanoester comprises: (A) cooling said reaction mixture; (B) diluting said reaction mixture with aqueous sodium chloride; (C) extracting the diluted reaction mixture with dichloromethane; and, (D) evaporating said dichloromethane at reduced pressure.
Claim 5
Dependent Claim 132 words
The process of claim 1 wherein said cyanoester has the formula: ##STR44## wherein R' is methyl or ethyl, and R can be selected from the class consisting of: (1) alkyl, haloalkyl, alkenyl, haloalkenyl, cycloalkyl, carboalkoxy, and cycloalkenyl groups having up to ten carbons; (2) a heterocyclic residue selected from the group consisting of furan, thiophene, pyridine, pyrrole and indole; (3) phenyl and naphthyl groups, and; (4) monosubstituted phenyl groups, and disubstituted phenyl groups wherein the substituents are selected from the group consisting of alkyl, halogen, nitro, alkoxy, and haloalkyl; provided that when R is alkenyl, R is not conjugated with the double bond between C 1 and C 2 and when R is a substituted phenyl group, at least one of the ortho carbons of said phenyl group is bonded to hydrogen.
Claim 6
Dependent Claim 10 words
The process of claim 1 wherein said cyanoester is ethyl(1-methyl-4-piperidylidene)-cyanoacetate.
Claim 7
Dependent Claim 11 words
The process of claim 1 wherein said cyanoester is (E)-ethyl 2-cyano-3-(o-chlorophenyl)-2-propenoate.
Claim 8
Dependent Claim 11 words
The process of claim 1 wherein said cyanoester is (E)-ethyl 2-cyano-3-(p-methylphenyl)-2-propenoate.
Claim 9
Dependent Claim 11 words
The process of claim 1 wherein said cyanoester is (E)-ethyl 2-cyano-3-(3'-pyridyl)-2-propenoate.
Claim 10
Dependent Claim 11 words
The process of claim 1 wherein said cyanoester is (E)-ethyl 2-cyano-5-methyl-2-hexenoate.

References Cited (Backward Citations)

US3962053A Cited
US4118412A Cited
US4276225A Cited
US4284582A Cited

USPTO Annuity & Maintenance Windows

Annuity Stage Window Opens Payment Deadline Surcharge Period Until Estimated Fee Status
3.5 Years (Year 4) 1989-01-27 1989-07-29 1990-01-28 $2000.00 Window Closed / Lapsed
7.5 Years (Year 8) 1993-01-27 1993-07-29 1994-01-28 $3760.00 Window Closed / Lapsed
11.5 Years (Year 12) 1997-01-27 1997-07-29 1998-01-28 $7700.00 Window Closed / Lapsed

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