Roussel Uclaf

Andre Teche

Jean Tessier

Jacques Martel

Jean-Pierre Demoute

Jacques Perronnet

Pierre Girault

Daniel Hainaut

Laurent Taliani

Jacques Demassey

Claude Bonne

Pierre Pastre

An insecticidal composition comprising an insecticidally effective amount of (S) .alpha.-cyano-3-phenoxy-benzyl(1R, trans) 2,2-dimethyl-3-[(.DELTA.Z) 2-fluoro-3-oxo-3-methoxy-propenyl]-cyclopropane carboxylate and an inert carrier having excellent insecticidal activity and low mammal toxicity.

Method of combatting household insects

Novel substituted lactones of amino acids in all their possible stereoisomeric forms or mixtures thereof of the formula ##STR1## wherein A is a hydrocarbon chain of 1 to 10 chain members containing one or more heteroatoms and one or more unsaturations and the chain members being a mono- or polycyclic system or comprises a system of spiro or endo type and may contain one or more chiral atoms or the lactone copula can present a supplementary chirality due to the asymetric spatial configuration of the molecule make up and R is selected from the group consisting of ##STR2## wherein Z is the organic remainder of an amino acid of the formula ##STR3## Y is derived from a primary, secondary or tertiary alcohol of the formula Y-OH and B is the remainder of a heterocycle amino acid of 3 to 6 carbon atoms of the formula ##STR4## and their preparation and their use for the resolution of amino acids.

Process for resolving amino acids using substituted lactones

Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## wherein A' is selected from the group consisting of (1) alkyl of 1 to 18 carbon atoms, (2) benzyl optionally substituted with at least one member of the group consisting of alkyl of 1 to 4 carbon atoms, alkenyl of 2 to 6 carbon atoms, alkenyloxy of 2 to 6 carbon atoms, alkadienyl of 4 to 8 carbon atoms, methylenedioxy or halogen, ##STR2## wherein R.sub.1 is selected from the group consisting of hydrogen and methyl and R.sub.2 is selected from the group consisting of --CH.sub.2 --C.tbd.CH and monocyclic aryl, ##STR3## wherein a is selected from the group consisting of hydrogen and methyl and R.sub.3 is an aliphatic group of 2 to 6 carbon atoms containing at least one carbon-carbon unsaturation ##STR4## wherein a and and R.sub.3 have the above definition and R.sub.1 ' and R.sub.2 ' are individually selected from the group consisting of hydrogen, halogen, alkyl of 1 to 6 carbon atoms, aryl of 6 to 10 carbon atoms, cyano and alkoxy carbonyl of 2 to 5 carbon atoms, (6) ##STR5## wherein B is selected from the group consisting of ##STR6## --O-- and --S--, R.sub.4 is selected from the group consisting of hydrogen, --CH.sub.3, --C.tbd.N--CONH.sub.2, --CSNH.sub.2 and --C.tbd.CH, n is an integer form 0, 1 or 2 and R.sub.5 is selected from the group consisting of halogen and --CH.sub.3 ##STR7## wherein R.sub.6, R.sub.7 , R.sub.8 and R.sub.9 are selected from the group consisting of hydrogen, chlorine and methyl and S/I symbolizes an aromatic ring or dihydro or tetrahydro ring, ##STR8## wherein R.sub.10 is selected from the group consisting of hydrogen and --CN, R.sub.12 is selected from the group consisting of --CH.sub.2 -- and --O-- and R.sub.11 is selected from the group consisting of thiazolyl and thiadiazolyl with the bond the bond to ##STR9## being in anyone of the positions, R.sub.12 being bonded to R.sub.11 by the carbon atom included between a sulfur atom and a nitrogen atom, ##STR10## wherein R.sub.13 is selected from the group consisting of hydrogen and --CN ##STR11## wherein R.sub.13 has the above definition and the benzoyl is in the 3- or 4-position; ##STR12## wherein R.sub.14 is; selected from the group consisting of hydrogen, methyl, ethynyl and --CN and R.sub.15 and R.sub.16 are individually selected from the group consisting of hydrogen, bromine and fluorine and ##STR13## wherein R.sub.14 has the above definition, p is 0, 1 or 2, each R.sub.17 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, --CF.sub.3 3,4-methylenedioxy, chlorine, bromine and fluorine, B is selected from the group consisting of --O-- and --S-- and R is selected from the group consisting of alkyl of 1 to 18 carbon atoms substituted with one or more, optionally different functional groups, aryl of 6 to 14 carbon atoms optionally substituted with one or more optionally different functional groups, the double bond having Z or E geometry having insecticidal and nematocidal activity as well as plant and animal acaricidal activity and their preparation.

Certain cyclopropanedicarboxylates with an unsaturated side chain having

Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of Z geometry of the formula ##STR1## wherein A' is ##STR2## wherein R.sub.13 is selected from the group consisting of hydrogen and CN and R is an optionally unsaturated alkyl of 1 to 18 carbon atoms having insecticidal and nematocidal activity as well as plant and animal acaricidal activity and their preparation.

Novel cyclopropane carboxylic acid derivatives

Novel esters in all possible isomeric forms of the formula ##STR1## wherein R is selected from the group consisting of (a) optionally unsaturated alkyl of 1 to 8 carbon atoms and optionally unsaturated cycloalkyl or cycloalkyl-alkyl of 3 to 8 carbon atoms optionally substituted with at least one member of the group consisting of halogen, --OH, --SH, --OR', --SR', --NO.sub.2, ##STR2## --CN, --SO.sub.3 H, --PO.sub.4 H.sub.2, ##STR3## --SO.sub.2 AlK.sub.2, --SO.sub.3 AlK.sub.3, aryl optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3, --SCF.sub.3 and ##STR4## R' is alkyl of 1 to 8 carbon atoms, R' and R'' are individually selected from the group consisting of hydrogen and alkyl of 1 to 8 carbon atoms, AlK.sub.1, AlK.sub.2 and AlK.sub.3 are individually alkyl of 1 to 18 carbon atoms, (b) aryl of 6 to 14 carbon atoms optionally substituted with at least one substitutent selected from the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --OCF.sub.3, --CF.sub.3 and --SCF.sub.3 and (c) heterocycle optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3 and --SCF.sub.3, B is selected from the group consisting of optionally unsaturated alkyl of 1 to 18 carbon atoms, optionally unsaturated cycloalkyl of 3 to 18 carbon atoms and the remainder of an alcohol used in synthesis of pyrethrinoid esters, X is halogen and the ethylenic double bond may have Z or E geometry having parasitic activity, especially insecticidal acaricidal and nematocidal activity.

Cyclopropane carboxylic esters and acids

Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## wherein A' is selected from the group consisting of  wherein B is selected from the group consisting of --CH.sub.2 --, ##STR2## --O-- and --S--, R.sub.4 is selected from the group consisting of hydrogen, --CH.sub.3,--C.tbd.N--CONH.sub.2, --CSNH.sub.2 and --C.tbd.CH, n is an integer from 0, 1 or 2 and R.sub.5 is selected from the group consisting of halogen and --CH.sub.3 ##STR3## wherein R.sub.13 is selected from the group consisting of hydrogen and ##STR4## wherein R.sub.13 has the above definition and the benzoyl is in the 3- or 4-position, ##STR5## wherein R.sub.14 is selected from the group consisting of hydrogen, methyl, ethynyl and --CN and R.sub.15 and R.sub.16 are individually selected from the group consisting of hydrogen, bromine and fluorine and ##STR6## wherein R.sub.14 has the above definition, p is 0, 1 or 2, each R.sub.17 is selected from the group consisting of alkyl of 1 to 4 carbon atoms, alkoxy of 1 to 4 carbon atoms, alkylthio of 1 to 4 carbon atoms, alkylsulfonyl of 1 to 4 carbon atoms, --CF.sub.3, 3,4-methylenedioxy, chlorine, bromine and fluorine B' is selected from the group consisting of --O-- and --S-- and R is selected from the group consisting of alkyl of 1 to 18 carbon atoms substituted with one or more, optionally different functional groups, aryl of 6 to 14 carbon atoms optionally substituted with one or more optionally different functional groups, the double bond having Z or E geometry having insecticidal and nematocidal activity as well as plant and animal acaricidal activity and their preparation.

Certain cyclopropyl dicarboxylates having pesticidal and insecticidal

Novel ethers of organic compounds containing chiral atoms of the formula ##STR1## wherein A is a hydrocarbonated chain of 1 to 10 groups, the said chain containing one or more heteroatoms, one or more unsaturations, the assembly of the groups constituting the chain may represent a mono- or polycyclic system, including a system of the spiro or endo type, the chain A can contain one or more chiral atoms or the lactone moiety can present a chirality due to the dissymetric spatial configuration of the whole of the molecule and Z is selected from the group consisting of primary, secondary or tertiary alcohol moiety containing at least an asymetric carbon atom, a phenol moiety substituted comprising at least one asymetric carbon atom and an substituted alcohol or phenol moiety with a chirality due to the dissymetric spatial configuration of the whole of the molecule, with the proviso Z is not (R) or (S) .alpha.-cyano-3-phenoxy-benzyl when A is ##STR2## which are useful for the resolution of compounds of the formulae ##STR3## wherein A and Z have the above definitions and X is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms.

3-oxabicyclo-(3,1,0)-hexan-2-ones

Novel ethers of organic compounds containing chiral atoms of the formula ##STR1## wherein A is a hydrocarbonated chain of 1 to 10 groups, the said chain containing one or more heteroatoms, one or more unsaturations, the assembly of the groups constituting the chain may represent a mono- or polycyclic system, including a system of the spiro or endo type, the chain A can contain one or more chiral atoms or the lactone moiety can present a chirality due to the dissymetric spatial configuration of the whole of the molecule and Z is selected from the group consisting of primary, secondary or tertiary alcohol moiety containing at least an asymetric carbon atom, a phenol moiety substituted comprising at least one asymetric carbon atom and a substituted alcohol or phenol moiety with a chirality due to the dissymetric spatial configuration of the whole of the molecule, with the proviso Z is not (R) or (S) .alpha.-cyano-3-phenoxy-benzyl when A is ##STR2## which are useful for the resolution of compounds of the formulae ##STR3## wherein A and Z have the above definitions and X is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms.

Ethers of pantolactone

This invention relates to stereoisomeric forms and mixtures thereof of compounds of the formula ##STR1## having insecticidal, nematocidal, and acaricidal properties.

Cyclopropane thiocarboxylic esters and insecticidal and acaricidal use

Novel esters in all possible isomeric forms and mixtures thereof of the formula ##STR1## wherein R is selected from the group consisting of (a) optionally unsaturated alkyl of 1 to 18 carbon atoms and optionally unsaturated cycloalkyl or cycloalkylalkyl of 3 to 8 carbon atoms optionally substituted with at least one member of the group consisting of halogen, --OH, --SH, --OR', --SR', --NO.sub.2, ##STR2## --SO.sub.2 AlK.sub.2, --SO.sub.3 AlK.sub.3, aryl optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3, --SCF.sub.3 and ##STR3## R' is alkyl of 1 to 8 carbon atoms, R' and R'' are individually selected from the group consisting of hydrogen and alkyl of 1 to 8 carbon atoms, AlK.sub.1, AlK.sub.2 and AlK.sub.3 are individually alkyl of 1 to 18 carbon atoms (b) aryl of 6 to 14 carbon atoms optionally substituted with at least one substituent selected from the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --OCF.sub.3, --CF.sub.3 and --SCF.sub.3 and (c) heterocycle optionally substituted with at least one member of the group consisting of --OH, alkoxy of 1 to 8 carbon atoms, alkyl of 1 to 8 carbon atoms, halogen, --CF.sub.3, --OCF.sub.3 and --SCF.sub.3, A is selected from the group consisting of optionally unsaturated alkyl of 1 to 18 carbon atoms, optionally unsaturated cycloalkyl of 3 to 18 carbon atoms and the remainder of an alcohol used in synthesis of pyrethrinoid esters, X is halogen and the ethylenic double bond may have Z or E geometry having antiparasitic activity, especially insecticidal, acaricidal and nematocidal activity.

Anti-parasitic esters

Novel cyclopropanecarboxylates in all possible isomeric forms or mixtures thereof of the formula ##STR1## with a 1R,cis or 1R,trans structure and wherein X is a halogen, R is selected from the group consisting of (A) optionally unsaturated alkyl of 2 to 12 carbon atoms, (B) optionally unsaturated cycloalkyl of 3 to 12 carbon atoms, (c) ##STR2## Z is selected from the group consisting of --C.tbd.CH, --CH.sub.3 and --CN and Ar is selected from the group consisting of --C.sub.6 H.sub.5, --C.sub.6 F.sub.5, ##STR3## B is hydrogen or fluorine and X is fluorine, chlorine or bromine ##STR4## Y.sub.2 is selected from the group consisting of hydrogen, fluorine, chlorine bromine, --C.tbd.N and --C.tbd.CH, Y.sub.3, Y.sub.4, and Y.sub.5 are individually selected from the group consisting of hydrogen, fluorine, chlorine, bromine alkyl of 1 to 8 carbon atoms and cycloalkyl of 3 to 8 carbon atoms optionally substituted by one or more functional groups, alkenyl of 2 to 8 carbon atoms and alkynyl of 2 to 8 carbon atoms, and two of Y.sub.3, Y.sub.4 and Y.sub.5 can form rings between them with the proviso that if X is bromine and R is ##STR5## and Z is cyano or ethynyl and A.sub.r is ##STR6## the carbon carrying Z is in the (S) configuration and the double bond in the 3-side chain may have E or Z structure useful in combatting pests such as insects, nematodes acarids.

2-Fluoro-2-cyanoethenyl cyclopropane carboxylates as pesticides

Novel cyclopropane carboxylic acid derivatives of the formula ##STR1## wherein A is selected from the group consisting of --O--, --CH.sub.2 -- and ##STR2## R is selected from the group consisting of alkyl of 1 to 8 carbon atoms, alkenyl and alkynyl of 2 to 8 carbon atoms and optionally unsaturated cycloalkyl and cycloalkylalkyl of 3 to 8 carbon atoms optionally substituted with at least one alkyl group and the double bond in the 3-side chain has the Z geometry in all possible stereoisomeric forms and mixtures of stereoisomers having insecticidal, nematocidal and animal and vegetable acaricidal activities and their preparation.

Cyclopropane carboxylic acid derivatives

Novel isomers and mixtures thereof of cyclopropane carboxylic acid derivatives with a 3-unsaturated side chain of the formula ##STR1## The double bond having Z or E geometry and having insecticidal and nematocidal activity as well as plant and animal acaricidal activity.

Insecticidal cyclopropane carboxylic acid derivatives with

Novel ethers of organic compounds containing chiral atoms of the formula ##STR1## wherein A is a hydrocarbonated chain of 1 to 10 groups, the said chain containing one or more heteroatoms, one or more unsaturations, the assembly of the groups constituting the chain may represent a mono- or polycyclic system, including a system of the spiro or endo type, the chain A can contain one or more chiral atoms or the lactone moiety can present a chirality due to the dissymmetric spatial configuration of the whole of the molecule and Z is selected from the group consisting of primary, secondary or tertiary alcohol moiety containing at least an asymmetric carbon atom, a phenol moiety substituted comprising at least one asymmetric carbon atom and a substituted alcohol or phenol moiety with a chirality due to the dissymmetric spatial configuration of the whole of the molecule, with the proviso Z is not (R) or (S) .alpha.-cyano-3-phenoxy-benzyl when A is ##STR2## which are useful for the resolution of compounds of the formulae ##STR3## wherein A and Z have the above definitions and X is selected from the group consisting of hydrogen and alkyl of 1 to 4 carbon atoms.

Process for resolution of chiral alcohols or phenols or chiral lactonic

Novel imino derivatives of esters of 3-formyl-cyclopropane-1-carboxylic acids in their various isomeric forms and mixtures thereof of the formula ##STR1## wherein Z is an organic residue of a primary amine of the formula Z--NH.sub.2 and the acid moiety may have the cis or trans configuration and the alcohol moiety may have the R,S or RS configuration, novel intermediates therefore and a process for the preparation of the corresponding 3-substituted vinyl esters having insecticidal activity.

Growing community of inventors

Paris, France

Andre Teche