MXPA00000969A

MXPA00000969A - Aryl and heteroarylcyclopropyl oxime ethers and their use as fungicides and insecticides

Info

Publication number: MXPA00000969A
Application number: MXPA/A/2000/000969A
Authority: MX
Inventors: Ross Ronald; Vuong Nguyen Duyan; Howard Shaber Steven
Original assignee: Rohm And Haas Company
Priority date: 1999-01-27
Filing date: 2000-01-27
Publication date: 2001-06-26

Abstract

Compounds with fungicidal and insecticidal properties having formula wherein X is N or CH;Z is O, S or NR8;A is hydrogen, halo, cyano, (C1-C12)alkyl, or (C1-C12)alkoxy;R1 and R8 are independently hydrogen or (C1-C4)alkyl;R2 is hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C3-C7)cycloalkyl, halo(C3-C7)cycloalkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, aryl, aralkyl, hererocyclic, hererocyclic(C1-C4)alkyl or C(R10)=N-OR9;R3 is hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C3-C7)cycloalkyl, halo(C3-C7)cycloalkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, aryl, aralkyl, aryl(C3-C7)cycloalkyl, heterocyclic or heterocyclic(C1-C4)alkyl;R4 and R5 are independently hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C3-C7)cycloalkyl, halo(C3-C7)cycloalkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, halo, cyano, (C1-C4)alkoxycarbonyl, aryl, aralkyl, aryl(C3-C7)cycloalkyl, heterocyclic or hererocyclic(C1-C4)alkyl;R6 is hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C3-C7)cycloalkyl, halo(C3-C7)cycloalkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, halo, cyano, (C1-C4)alkoxycarbonyl, aryl, aralkyl, aryl(C3-C7)cycloalkyl, heterocyclic or hererocyclic(C1-C4)alkyl;R7 is aryl, aralkyl, heterocyclic or heterocyclic(C1-C4)alkyl;R9 is hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, (C1-C4)alkylcarbonyl, (C1-C4)alkoxycarbonyl, aryl, or aralkyl;and R10 is hydrogen, (C1-C12)alkyl, halo(C1-C12)alkyl, (C3-C7)cycloalkyl, halo(C3-C7)cycloalkyl, (C2-C8)alkenyl, halo(C2-C8)alkenyl, (C2-C8)alkynyl, halo(C2-C8)alkynyl, aryl, aralkyl, heterocyclic, or heterocyclic(C1-C4)alkyl.

Description

OXYMES OF ARILO AND HETEROARILCICLOPROPILO AND THEIR UTILIZATION AS FUNGYCIDES AND INSECTICIDES The present invention relates to certain aryl cyclopropyl oxime ether structures, compositions containing these compounds and methods for controlling fungi and insects by using a fungitoxic or insecticidal amount of these compounds. It is known that compounds having certain oxime ether structures have been presented in the patents of the United States Numbers 5,194,662 and 5,292,759. We have discovered certain new cyclopropyl oxime ethers that possess a substituted aryl and heterocyclic moieties.

These novel derivatives have fungicide and broad spectrum insecticidal properties. The novel cyclopropyloxy ethers of the present invention have Formula (I) (I) where X is N or CH; Z is 0, S, or NR8; A is hydrogen, halo, cyano, alkyl (C? -C? 2), or alkoxy (C? ~ C12); Ri and R8 are independently hydrogen or alkyl (C? -C? 4); R2 is selected from a group consisting of hydrogen, (C1-C12) alkyl, haloalkyl (U-C12), cycloalkyl (C3-C7), cycloalkyl halo (C3-C7), alkenyl (C2-C8), haloalkenyl (C2-C8), alkynyl (C2-Cs), haloalkynyl (C2-C8), aryl, aralkyl, alkyl (C? -C) heterocyclic and C (Ri0) = N-0R9; R3 is selected from a group consisting of hydrogen, alkyl (U-C12), halo alkyl (C? -C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2-C8) ), (C2-C8) alkenyl halo, (C2-C8) alkynyl, (C2-C8) haloalkynyl, aryl, aralkyl, aryl (C3-C7) cycloalkyl, heterocyclic and heterocyclic alkyl (C? -C4); R4 and R5 independently selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? -C12), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2-? C8), halo alkenyl (C2-C8), alkynyl (C2-C8), halo alkynyl (C2-C8), halo, cyanoalkoxycarbonyl (C? -C4), aryl, aralkyl, aryl cycloalkyl (C3-C7), aryl (C2-C8) alkenyl, heterocyclic and heterocyclic alkyl (C? -C); Rβ, is selected from the group consisting of hydrogen, alkyl (C? -C12), halo alkyl (C? -C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2-C8) ), (C2-C8) alkenyl halo, (C2-C8) alkynyl, (C2-C8) halo alkynyl, halo, cyano, alkoxycarbonyl (C? -C), aryl, aralkyl, aryl (C3-C7) cycloalkyl, aryl (C2-C8) alkenyl, heterocyclics and heterocyclic alkyl (C? -C4); R7 is selected from the group consisting of aryl, aralkyl, heterocyclics and heterocyclic alkyl (C? -C4); R9 is selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? -C? 2), alkenyl (C2-C8), halo alkenyl (C2-C8), alkynyl (C2) -C8), halo alkynyl (C2-C8), alkylcarbonyl, (C? -C), alkoxycarbonyl (C? -C), aryl, and aralkyl; Rio, is selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? -C12), cycloalkyl (C3? C7), halo cycloalkyl (C3-C7), alkenyl (C2-C8) ), (C2-C8) alkenyl halo, (C2-C8) alkynyl, (C2-C8) halo alkynyl, aryl, aralkyl, heterocyclic and heterocyclic alkyl (C? -C); The aforementioned alkyl group (C? -C? 2), (C2-C8) alkenyl, (C2-C8) alkynyl and (C3-C7) cycloalkyl can be optionally substituted with up to three substitutes selected from the group consisting of nitro, ethyl, alkoxycarbonyl (C? -C), and cyano. The term "alkyl" includes both branched chain and straight chain alkyl groups of one to 12 carbon atoms. Typical alkyl groups are methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, osooctyl, nonyl, decyl , undecyl, dodecyl and the like. The term "haloalkyl" refers to an alkyl group substituted with 1 to 3 halogens. The term "alkenyl" refers to an unsaturated, straight or branched hetilenglycol hydrocarbon group with a chain length of 2 to 8 carbon atoms and 1 or 2 ethylenic bonds. The term "haloalkenyl" refers to an alkenyl group substituted with 1 to 3 allogeneic atoms. The term alkynyl refers to an unsaturated hydrocarbon group, straight or branched, having a chain length of 2 to 12 carbon atoms and 1 or 2 acetylenic bonds. The term "aryl" includes phenyl or naphthyl, which may be substituted with up to three substitutes independently selected from the group consisting of allogen, cyano, triallyl, phenyl, phenoxy, alkyl (C? -C4), alkoxy (C? -C4), alkylthio ( C? -C4), alkylsulfoxide (C? -C4), haloalkyl (C? ~ C4) and haloalkoxy (C? -C). Typical substitutes for aryl include, but are not limited to, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2,4-dibromophenyl, 3,5-difluorophenyl, 2,4,6-trichlorophenyl, 2-chloronaphthyl, 3- (trifluoromethyl) phenyl, 4- (trifluoromethyl) phenyl and 2-iodo-4-methylphenyl. The term heterocyclic refers to an unsaturated or unsubstituted 6-membered unsaturated closed chain, two or three heteroatoms, preferably one, two or three heteroatoms independently selected from oxygen, nitrogen and sulfur or a bicyclic unsaturated closed chain system containing up to 10 atoms includes a heteroatom selected from oxygen, nitrogen and sulfur. The term "heterocyclic" also refers to an unsaturated five-member closed chain containing one, two or three heteroatoms, preferably one or two heteroatoms, independently selected from oxygen, nitrogen or sulfur. Highlights among the examples of heterocycles, but are not limited to, 2-, 3- or 4-pyridinyl, pyrazinyl, 2-, 4-, or 5-pyridimidinyl, pyridazinyl, pyr-azole, triazolyl, imidazolyl, 2 or 3- thienyl, 2 or 3-furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, quinolyl and isoquinolyl. The heterocyclic enclosed chain can optionally be substituted with up to two substitutes independently selected from (C? -C4) alkyl, halogen, cyano, nitro and trialomethyl. The term "aralkyl" is used to describe a group in which the alkyl chain has from 1 to 10 carbon atoms and can be a branched or straight chain7 preferably a straight chain, the aryl portion forming, as defined above, a terminal portion of the aralkyl moiety. Typical aralkyl moieties are benzyl, phenethyl, phenpropyl and phenbutyl moieties optionally substituted. Typical benzyl moieties are 2-chlorobenzyl, 3-chlorobenzyl, 4-chlorobenzyl, 2-fluorobenzyl, 3-fluorobenzyl, 4-fluorobenzyl, 4-trifluoromethylbenzyl, 2,4-dichlorobenzyl, 2,4-dibromobenzyl, 2-methylbenzyl, 3 -methylbenzyl and 4-methylbenzyl. Typical phenethyl moieties are 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2-fluorofyl) ethyl, 2- (3-fluorophenyl) ethyl, 2- (4-fluorophenyl) ethyl, 2- (2-methylphenyl) ethyl, 2- (3-methyl-phenyl) ethyl, 2- (4-methylphenyl) ethyl, 2- (4-trifluoromethylphenyl) ethyl, - (2, -dichlorophenyl) -ethyl, 2- (3,5-dimethoxyphenyl) ethyl. Typical phenpropyl moieties are 3-phenylpropyl, 3- (2-chlorophenyl) propyl, 3- (3-chlorophenyl) propyl, 3- (4-chlorophenyl) propyl, 3- (2,4-dichloro-phenyl) propyl, 3- (2-fluorophenyl) propyl, 3- (3-fluorophenyl) propyl, 3- (4-fluorophenyl) propyl, 3- (2-methylphenyl) propyl, 3- (3-methylphenyl) propyl, 3- (4- methylphenyl) ethyl, 3- (4-trifluoromethylphenyl) propyl, 3- (2,4-dichlorophenyl) propyl and 3- (3,5-dimethylphenyl) propyl. Typical phenbutyl moieties include 4-phenylbutyl, 4- (2-chlorophenyl) butyl, 4- (3-chlorophenyl) butyl, 4- (4-chlorophenyl) butyl, 4- (2-fluorophenyl) butyl, 4- (3 -fluorophenyl) butyl, 4- (4-fluorophenyl) butyl, 4- (2-methylphenyl) butyl, 4- (3-methylphenyl) butyl, 4- (4-methylphenyl). butyl and 4- (2,4-dichlorophenyl) butyl.

Halogens or halo include the halides iodine, fluoro, bromo and chloro. Due to the double bonds C = C or C = N, the novel compounds of the general Formula I can be obtained in preparation as isometric mixtures E / Z. These isomers can be separated into individual elements by conventional methods. The arylcyclopropanes of Formula I can be obtained in preparation as cis and trans isometric mixtures which can be separated into individual elements by conventional methods. Both individual isomeric compounds and mixtures thereof are subject of the invention and can be used as fungicides and insecticides. The present invention also includes the enantiomorphs, salts and complexes of Formula (I). A preferred embodiment of the present invention are the compounds, enantiomorphs, salts and complexes of the Formula (I ') wherein A is hydrogen, Rx and R2 are hydrogen or alkyl (C? -C4), R3, R, R5 and are hydrogen and R7 is aryl, aralkyl or heterocyclic.

(D A more preferred form of the present invention are the compounds, enantiomorphs, salts and complexes of Formula (I ") wherein X is N, Z is NH, R 2 is methyl and R 7 is aryl. d ") Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 1 of Formula IV (X = CH and Z is 0) wherein R2, R3 and R7 are defined in Table 1.

Formula IV Table 1 fifteen Table 1 (continued) 15 Table 1 (continued) Table 1 (continued) Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 2 of Formula V (X = N and Z is 0) wherein R2, R3 and R7 are defined in Table 2.

Formula V Table 2 (continued) Table 2 (continued) Table 2 (continued) THE Table 2 (continued) Table 2 (continued) Typical compounds encompassed by the present invention with Formula I (wherein A = R = R 5 = R 6 = H) include those compounds presented in Table 3 of Formula VII (X = N and Z is NH) wherein R 2, R 3 and R7 are defined in Table 3.

Formula VII Table 3 Table 3 (continued) 10 Table 3 (continued) Table 3 (continued) Go. 0 10 Table 3 (continued) fifteen Table 3 (continued). twenty The typical covers are included by the present invention with Formula I (wherein A = R = R5 = R6 = H) include those compounds presented in Table 4- of Formula IV (X = CH and Z is 0) wherein R2, R3 and R are defined in Table 4.

Formula IV Table 4 Table 4 (continued) Table 4 (continued) 10 fifteen twenty Table 4 (continued) Table 5: Compounds 5.1 to 5.196 are compounds of Formula V (X = N and Z = 0) wherein the substitutes R2, R3 and R7 are defined in Table 4. Table 6; The compounds 6.1 to 6.196 are compounds of Formula VII (X = N and Z = NH) wherein the substitutes R2, R3 and R7 are defined in Table 4. Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 4 of Formula IV (X = CH and Z is O) wherein R2 / R3 and R? they are defined in Table 7.

Formula IV Table 7 twenty Table 7 (continued) fifteen Table 7 (continued) Table 7 (continued) 10 fifteen twenty Table 7 (continued) Table 8: Compounds 8.001 to 8.197 are compounds of Formula V (X = N and Z = 0) wherein the substitutes R2, R3 and R are defined in the Table 7. Table 9: Compounds 8.001 to 8.197 are compounds of Formula VII (X = N and Z = NH) where the substitutes RZf R3 and R7 are defined in Table 7.

Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 10 of Formula IV (X = CH and Z is O) wherein R2 / R3 and R7 are defined in Table 10.

Formula IV Table 10 Table 10 (continued) Table 10 (continued) 15 twenty Table 10 (continued) THE twenty Table 10 (continued) Table 10 (continued) Typical compounds encompassed by the present invention with Formula I '(wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 11 of Formula V (X = N and Z is O) wherein R2 / R3 and R7 are defined in Table 11 '.

Formula V Table 11 Table 11 (continued) Table 11 (continued) LO Table 11 (continued) Table 11 (continued) 10 10 fifteen Table 11 (continued) Typical compounds encompassed by the present invention with Formula I (wherein A = R 4 = R 5 = R 6 = H). they include those compounds presented in Table 12 of Formula V (X = N and Z is O) wherein R2 / R3 and R7 are defined in Table 12.

Formula VII Table 12 Table 12 (continued) 91 Table 12 (continued) Table 12 (continued) Z.184 H quinolin-4-yl Table 12 (continued) Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6: = H) include those compounds presented in Table 13 of Formula V (X = CH and Z is O) wherein R2 / R3 and R7 are defined in Table 13.

Formula IV Table 13 ? .- > 0 !!) fifteen twenty Table 13 (continued) fifteen :or Table 13 (continued) Table 13 (continued) twenty Table 13 (continued) Table 14: Compounds 14.1 to 14.196 are compounds of Formula V (X = N and Z = 0) wherein the substitutes R2 / R3 and R7 are defined in Table 15: Table 15: Compounds 15.1 to 15.196 are compounds of Formula VII (X = N and Z = NH) wherein the substitutes R2, R3 and R7 are defined in Table 13. Typical compounds encompassed by the present invention with Formula I (wherein A = R4 = R5 = R6 = H) include those compounds presented in Table 16 of Formula IV (X = CH and Z is 0) wherein R2, R3 and R7 are defined in Table 16.

Formula IV Picture THE fifteen 0 ! S Table 16 (continued) i 0 Table 16 (continued) Table 16 (continued ') Table 16 (continued) Table 16 (continued) 20 Table 16 (continued) 1 fifteen Table 16 (continued) twenty Table 16 (continued) OR Table 17: Compounds 17.1 to 17.396 are compounds of Formula V (X = N and Z = 0) wherein the substitutes R2 R3 and R7 are defined in Table 16. Table 18: Compounds 18.1 to 8.396 are compounds of Formula VII (X = N and Z = NH) where the substitutes R2, R3 and R, are defined in Table 16. As used in tables 1 to 8 Ph is understood as phenyl. Scheme A describes the preparation of the compounds of Formula (I). Where X is CH or N, and Z is O (compounds of formula IV and V). The cyclopropyl oximes (III) are reacted with the suitably substituted benzyl derivatives (II) wherein Z eg an allogen, for example, bromine, chlorine or iodine, preferably a benzyl bromide. A substituted cyclopropyl oxime represented by the general formula (III) is treated at room temperature with a suitable base to form an anion, followed by the addition of benzyl bromide (II). Typical bases used are metal hydrides, for example sodium hydride, alkoxides, for example sodium methoxide and hydroxide bases, for example, sodium or potassium hydroxide and alkaline bases, for example sodium or potassium carbonate. Typical solvents employed with hydride bases are N, N-dimethylformamide (DMF) and tetrahydrofuran (THF); with hydroxide bases DMF, THF, methyl ethyl ketone (MEK) and acetone and with alkaline base solvents, for example DMF, acetone, and MEK. As shown in scheme A, the N-O bond in C (R2) = N-0-, appears in position E (assuming it is the largest substitute). It should be recognized that the Z-isomer can also be produced as well as mixtures thereof. When the isomers are produced they are called isomer A (higher Rf in thin layer chromatography) and isomer B (lower Rf thin layer chromatography). The determination of which isomer A or B, possesses the E or Z geometry can be done through conventional techniques, for example, X-ray crystallography or through spectroscopic means, for example, nuclear magnetic resonance spectroscopy. For the compounds of the present invention, isomer A has been assigned the iminoxy E configuration and isomer B the imoxi Z configuration. Scheme A The compounds of formula IV (X is CH) are prepared by alkylation with methyl E-a- (2-bromomethylphenyl) -β-methoxyacrylate in the presence of a base, preferably NaOH or KOH, in a solvent, preferably acetone or methyl ethyl ketone. Methyl E-a- (2-bromomethylphenyl) -β-methoxyacrylate, as an individual E isomer, can be prepared in two steps from 2-methylphenylacetate as described above in U.S. Patent No. 4,914,128, columns 3-4. compounds of formula V X = N) are prepared by reaction with methyl E-2- (bromomethyl) phenylglyoxylate O-methyloxime in the presence of a base, preferably NaOH or KOH, in a solvent, preferably acetone or methyl ethyl ketone . Methyl 2- (bromomethyl) phenylglyoxylate O-methyloxime can be prepared as described in U.S. Patent Nos. 4,999,042, columns 17-18 and 5,157,144 columns 17-18. methyl 2- (bromomethyl) phenylglyoxylate O-methyl-oxime is prepared from methyl 2-methylphenyl-acetate by treatment with an alkyl nitrite under basic conditions to provide after the subsequent methylation, methyl 2-methyl-phenyl-glyoxalate O-methyl oxime which can also be prepared from methyl 2-methyl-phenylglyoxalate by treatment with 2-hydroxylamine hydrochloride and methylation or by treatment with methoxylamine hydrochloride.

Scheme B As shown in scheme B the compounds of formula VII (X is N) can be prepared by the aminolysis of oximinoacetate (V). The aminolysis of oximinoacetate in oxynoacetamides has been described in U.S. Patent Nos. 5,185,342, columns 22,48 and 57, 5,221,691, columns 26-27 and 5,407,902, column 8. For example, the compounds of Table 2 of formula V wherein x is N and Z is O are treated with an aqueous solution of 40% methylamine in methanol to provide the compounds of Table 3 of formula VII wherein Z is NH. Alternatively, as shown in scheme B, the intermediate unsaturated oximes (III) is reacted with N-methyl (E) -2-methoxyimino-2- [2- (bromomethyl) phenyl] -acetamide in the presence of a base, for example, a hydroxide base preferably in a solvent, for example, acetone or methyl ethyl ketone to provide the compounds of Table II of formula (VII). N-methyl (E) -2-methoxy-imino-2- [2- (bromomethyl) phenyl] -acetamide is described in U.S. Patent Number 5,387,714, column 13. Oximes of the general formula (III) they can be obtained, as shown in scheme C, by reacting the cyclopropyl aldehyde or ketone (VIII) with hydroxylamine hydrochloride from room temperature to reflux, preferably at room temperature, in a suitable solvent, for example methanol or ethanol, in the presence of a suitable alkali, for example sodium hydroxide, potassium carbonate or pyridine. In March, Advanced Organic Jhemistry, 4th Edition, pages 906-907 and in the references that appear therein presents a general description of the synthesis of oximes with hydroxylamine. The oximes of the general formula (III), when obtained as a mixture of syn or anti oxime isomers can be separated into individual and alkylated isomers, as described in Scheme A and B. When a mixture of Oximias of the formula is used General (III) in Scheme A and B, the compounds of formula IV, V and VII can be separated into their individual isomers through conventional chromatographic techniques. Scheme C (vpi) (Hl) The cyclopropyl aldehydes or ketones (VIII) can be prepared by conventional techniques. The unsaturated intermediate IX (scheme D) is reacted with a sulfur ylide, prepared from a salt of dimethylsulfoxonium in the presence of a base, which results in recrystallized acyl substituted cyclopropanes, VIII. The chemical composition of sulfur ylides is described in Trost and Melvin, Sulfur ILDIS, Academic Press, New York, NY 1975 and in Block, Reactions of Organousulfur Compounds, pp. 91-123, Academic Press, New York, NY 1978. Typical reaction conditions for the formation of sulfur ylide from a di-ethylsulfoxonium salt use bases, for example, hydroxides, metal hydrides and alkoxides in solvents, for example , dimethoxy-ethane, dimethylsulfoxide and water, depending on the base used. The reactions are carried out at 0 to 20 ° C, preferably at 10-15 ° C and preferably with alkali metal hydroxides in dimethylsulfoxide. Typically, dimethylsulfoxonium methylide is prepared from trimethylsulfoxonium iodide in dimethylsulfoxide in the presence of powdered sodium hydroxide at room temperature. The cyclopropyl aldehydes or ketones are added dropwise to the ylide and stirred at room temperature. Scheme D IX vm The oximes of the general formula (III ') wherein R2 is C (RIO) = N-OR9; can be obtained, as shown in scheme E. The ketones, X, wherein RIO is not H, or the aldehydes, wherein RIO is H, are reacted with alkyl nitrite, for example t-butylnitrite or isoamylnitrite under conditions basic to provide the corresponding a-oximinocyclopropyl ketones XI. Typically the ketone or cyclopropyl aldehydes in a solvent, for example, t-butanol and the alkyl nitrite, typically, t-butylnitrite, are added to a solution of t-butanol containing a base, for example, t-butoxide. potassium and stir at room temperature. The a-hydroxyimine cyclopropylketones XI are alkylated to form the a -. (Substituted) oxy in cyclopropyl ketones XII. Cyclopropyloxime keto XII is treated as in Scheme C to provide the bisoximes III 'Scheme E XI The α, β-unsaturated aldehydes or ketones IX can be prepared by conventional condensation techniques. A broad description of the synthesis of aldehydes or ketones (enonas) a, ß-unsaturated is described in March, Advanced Organic Chemistry, 4th Edition, pages. 937-955 and references therein included. For example, Qrganic Reactions, Volume 16 describes the general condensation of aldol of ketones and aldehydes. For the intermediate compounds of the formula IX of the present invention, in general the ketones or aldehydes can be R7COR6 wherein R7 and R6 are previously defined. When Re is hydrogen, the aldehydes are, for example, benzaldehydes or substituted heterocyclic aldehydes. Ketones may be R2COCH2R3 wherein R2 and R3 are described above. Typically, the ketone, R COCHR, is dissolved in a hydroxylic solvent, for example methanol or ethanol, to which the R7COR6 aldehyde followed by the base or, alternatively, an aldehyde solution in a basic solution is added dropwise. watery The typical bases used may be alkali metal hydroxides, for example, potassium or sodium, and the dropwise addition is carried out at 0 ° C to 35 ° C, preferably at room temperature. When the enone is derived from acetone (R2 is methyl and R3 is hydrogen) the solvent is preferably acetone to which RCOR is added followed by the aqueous hydroxide solution. Scheme F Alternatively, the α, β-unsaturated cyclopropyl ketones VIII can be prepared from cyclopropyl nitrile XIV which is prepared through the cyclopropanation of acrylonitriles XIII as described in Scheme F. The initial materials of acrylonitriles XIII , shown in Scheme F, can be prepared by conventional synthetic methods, as described in March, Advanced Organic Chemistry, 4th Edition, pages. 937-955 and in the references included therein. For example, the nitrile derivative R3CH2CN is condensed with the ketone or the aldehyde R7COR6 in the presence of a base to provide the acrylonitriles XIII. Preferably R3 in R3CH2CN is an aryl or heteroaryl group as defined above for R3. Typically, a nitrile is dissolved in a solvent, for example, ethanol and water to which the aldehyde or acetone is added followed by a base. Typical bases used may be hydroxides, alkali metals, for example, neighborhood, potassium or sodium and the mixture is typically stirred at room temperature.

The acrylonitrile XIII is treated as described in Scheme D with sulfur ylide to provide the cyclopropyl nitriles XIV. The cyclopropyl nitrite XIV is transformed into cyclopropyl ketones by the organometallic addition to the nitrile followed by hydrolysis. For example, normal Grignard R2MgX reagents or organolium reagents R2Li are added to the functionality of the nitrile to provide the ketones VIII '. The vision reaction to nitriles is described in March, Advanced Organic Chemistry, 4th Edition, pages 935-936 and references cited therein. The cyclopropyl nitrile XIV can be transformed into the cyclopropyl aldehyde VIII '(in doñee R2 is H) by normal reductive methods, for example with diisobutylaluminum hydride (DiBAL). The formation of aldehydes from the reduction of nitriles is described in March, Advanced Organic Chemistry, 4th Edition, pages 919-920 and references cited therein. In Scheme G a direct synthesis of the compounds of the formula V or VII is shown. The compounds of Formula V or VII can be prepared directly from functionalized cyclopropyl ketones or aldehydes, VIII, by condensation with the aminoxy compound XV. The preparation of the aminoxy intermediate compound XV is described in US Pat. No. 5,147,662. The aminoxy intermediate compound XV is prepared in a two step sequence by the alkylation of II (wherein X is N) with N-hydroxyphthalamide which is deal with hydrazine to provide XV. The aminoxy intermediate compound XV is condensed with ketones or aldehydes VIII to provide V and specifically with cyclopropane ketones XII to provide V. The compounds of formula V are treated as shown in Scheme B to provide VII. Scheme G XV xp v The compounds of the present invention can be manufactured according to the following procedures: Example 1 Preparation of Methyl (E) -3-methoxy-2- (2 - ((((cyclopropyl-trans- (2- (3'-chlorophenyl) cyclopropyl)) methylene) amin) oxy) methyl) phenylpropenoate Compound 1.102 of Table 1. Preparation of trans-3- (3'-chlorophenyl) -l-cyclopropyl-2-propen-1-one In a 250 ml round bottom flask equipped with A magnetic stirrer was charged 5.0 g (0.059 moles, 1 .eq.) of cyclopropyl methyl ketone, 50 ml of ethanol, and 50 ml of water. 3-Chlorobenzaldehyde (8.3 g, 0.059 mole, 1 Oeq) was added in one portion followed by 0.4 g of 85% potassium hydroxide. The stopper of the flask was placed and stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 100 ml of saturated aqueous sodium bisulfite solution, followed by 100 ml of water and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 11.4 g of the yellow liquid (94% isolated yield), which was congruent with the desired product, trans-3- (3'-chlorophenyl) -l-cyclopropyl-2-propen-1-one, after analysis by 300Mz 1H NMR. 1 H NMR: (300 MHz (1 H to 300 MHz nuclear magnetic resonance) X H, CDCL 3 / TMS = 0 ppm) 1.0 (m, 2 H), 1.2 (m, 2 H), 2.2 (m, 1 H), 6.9 (d, 1H), 7.3-7.6 (m, 5H). Preparation of rans ~ 2- (3? -chlorophenyl) clopropylcyclopropyl ketone In a 500 ml round bottom flask equipped with magnetic stirrer, nitrogen inlet, and equalization funnel with equalized pressure were charged 12.2 g (0.0553 mol, l.Oeq .) of trimethylsulfoxonium iodide, 2.2 g (0.0553 moles, 1 .Oeq.) of powdered sodium hydroxide, and 150 ml of dimethylsulfoxide. The solution was stirred at room temperature for 30 minutes, followed by the dropwise addition of trans-3- (3? -chlorophenyl) -l-cyclopropyl-2-propen-1-one in 100 ml of dimethylsulfoxide. The reaction was stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 9.3 g of a thick yellow liquid (isolated yield of 76%), which was congruent with the desired product, trans-2- (3-chlorophenyl) cyclopropylcyclopropyl ketone after analysis by 300Mz? E NMR. NMR (300 MHz, 1H / CDCL3 / TMS = 0 ppm) 0.9 (*? 2H), 1.1 (m, 2H), 1.3 (m, lH), 1.7 (m, 1H), 2.1 (, 1H), 2.3 (, 1H), 2.6 (, 1H), 6.9 (m, 1H), 7.1 (s, 1H), 7.2-7.3 (m, 2H) Preparation of trans-2- (3 * -chlorophenyl) cyclopropylcyclopropyl oxime In a 100 ml round bottom flask equipped with magnetic stirrer, 2.0 g (0.0091 mol, 1 .eq.) of trans-2- (3? -chlorophenyl) cyclopropylcyclopropyl ketone, 1.6 g (0.022 mol, 2.4 eq.) hydroxylamine hydrochloride, and 50 ml of anhydrous methanol. The solution was stirred at reflux for 90 minutes, then cooled and concentrated on a rotary evaporator. The residue was dissolved in 100 ml of ethyl ether, and the ether extract was washed with 2 x 50 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.4 g of a thick gummy semisolid. Chromatography of the crude product was carried out on silica gel with 50% ethyl acetate, 50% hexane. The pure fractions were combined and concentrated in a rotary evaporator to obtain 0.9 g of a white solid (42% isolated yield), which was congruent with the desired product, trans-2- (3'-chlorophenyl) cyclopropylcyclopropyl oxime as an E / Z mixture of oxime isomers after analysis with 300Mz? H NMR.

NMR (300 MHz, H, CDCL3, TMS = 0 ppm) 0.8 (m, 2H), 0.9 (m, 2H), 1.3 (m, 1H), 1.4-1.5 (m, 1H), 1.6 (m, 1H) , 2.0 (m, 1H), 2.6-2.8 (m, 1H), 6.9 (m, 1H), 7.1 (m, 1H), 7.2-7.3 (m, 2H) 9.0 (bs, 1H). Preparation of Methyl (E) -3-methoxy-2- [2- ((((cyclopropyl- (trans-2- (3-chlorophenyl) cyclopropyl) methylene) amin) oxy) methyl) phenyl] propenate To a glass bottle of 20 ml equipped with a magnetic stirrer, 0.9 g (0.00383 mol, l.Oeq.) Of trans-2- (3'-chlorophenyl) cyclopropylcyclopropyl oxime, 1.1 g (0.003 83 mol, l.Oeq.) Of t- were charged. potassium butoxide, and 10 ml of anhydrous dimethylformamide. The solution was stirred at room temperature for 10 minutes, followed by the addition of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in one portion. The flask was then capped, in the reaction it was stirred at room temperature overnight. The reaction mixture was then poured into 100 ml of water, and extracted with 2 x 50 ml of ethyl ether. The ether extract was washed with 2 x 50 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.2 g of a thick red acid. Chromatography of the crude product was carried out on silica gel with 20% ethyl acetate, 80% hexane. The pure fractions were combined and concentrated on a rotary evaporator to obtain 0.8 g of a clear colorless oil (45% isolated yield) which was congruent with the desired product, as a mixture of methyl and E imines of methyl (E) ) -3-methoxy-2- [2- ((((cyclopropyl-trans (2- (3'-chlorophenyl) cyclopropyl) methylene) amin) oxy) ethyl) phenyl] propenoate after analysis with 300Mz? H NMR. NMR (300 MHz, 1H / CDCL3, TMS = 0 ppm) 0.6-0.9 (m, 4H), 1.1 (m, 2H), 1.5 (m, 1H), 2.4 (m, 1H), 2.6 (m, 1H) , 3.6-3.7 (d, 3H), 3.8-4.0 (d, 3H), 4.9-5.0 (d, 2H), 6.9 (m, 1H), 7.0 (m, 1H), 7.2-7.4 (m, 6H) 7.6 (d, 1H). Example 2 Preparation of imines E and Z: (E, E) and (Z, E) methyl 2- [2- ((((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) ethillden) amin) oxy) methyl) phenyl] -2-methoxy-iminoacetate Compounds 2.23A and 2.23B of Table 2 Preparation of trans-4- (4-methoxyphenyl) -3-buten-2-one In a 250 ml round bottom flask equipped 12.8 g (0.22 mole) of acetone, 100 ml of ethanol, and 1 ml of water were charged with a magnetic stirrer. The p-anisaldehyde (3.0 g, 0.022 mol, 1 .eq.) Was added in one portion followed by 0.2 g of barium hydroxide monohydrate (catalyst). The flask was capped and stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 X 100 ml of ethyl ether. The ether extract was washed with 100 ml of saturated aqueous sodium bisulfite solution, followed by 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 3.2 g of a yellow oil (83% isolated yield) which was congruent with the desired product, trans-4- (4-methoxyphenyl) -3-buten-2-one after analysis with 300 MHz? H NMR. NMR (300 MHz, X H, CDCl 3, TMS = 0 ppm) 2.4 (s, 3 H), 3.85 (s, 3 H), 6.6 (d, 1 H), 6.9 (d, 2 H) 7.5 (m, 3 H). Preparation of trans-2- (4'-methoxyphenyl) cyclopropylmethyl ketone In a 250 ml round bottom flask equipped with a magnetic stirrer, nitrogen inlet and addition funnel with equalized pressure was charged 4.0 g (0.0182 mol, l. Oeq) of trimethylsulfoxonium iodide, 0.73 g (0.0182 moles, l.Oeq) of powdered sodium hydroxide, and 100 ml of dimethylsulfoxide. The solution was stirred at room temperature for 30 minutes, followed by the addition of trans-4- (4-methoxyphenyl) -3-buten-2-one in one portion. The dark red solution was then stirred for 15 minutes at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 X 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous solution of sodium chloride. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 2.6 g of the thick yellow liquid (isolated yield of 75%) which was congruent with the desired product, trans-2- (4). '-methoxyphenyl) cyclopropylmethyl ketone after analysis with 300 MHz? H NMR. NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.3 (m, 1H), 1.6 (m, 1H), 2.2 (, 1H), 2.3 (s, 3H), 2.6 (m, 1H), 6.8 ( d, 2H), 7.1 (d, 2H). Preparation of the imine isomers E and Z: (E, E) and (Z, E) -Methyl 2- [2- ((((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) ethylidene) amin ) _oxy) methyl) phenyl] -2-methoxyimino-acetate Trans-2- (4'-methoxyphenyl) cyclopropylmethyl ketone (0.7 g, 0.0037 mol, was charged to a 25 ml glass flask equipped with a magnetic stir bar). 1 .Oeq) 10 ml of anhydrous methanol, and 1.0 g (0.0041 mol, 1.1 eq.) Of methyl (E) -2- (aminooxymethyl) phenylglyoxylate O-methyloxime. The bottle was capped, and stirred overnight at room temperature. The solution was then poured into 100 ml of water, and extracted with 3 X 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.7 g of crude product E / Z methyl 2- [2- ((((trans-1- (2- (4 '-methoxyphenyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate as an amber colored oil. Chromatography of this product was carried out on silica gel with 30% EtOAc / 70% hexane to obtain, in order of elution from the 450 mg column, a yellow viscous liquid, isomer A, which is characterized as congruent with the desired product as imine E, (E, E) -methyl-2- [2- ((((trans-1- (2- (4-methoxyphenyl) cyclopropyl) ethylidene) amin; oxy) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1 H NMR, and 420 mg of a viscous yellow oil, isomer B, which is characterized as being congruent with the desired product such as imine Z, (Z, E) -methi 2- [2- ((((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) -ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1H NMR. Total yield of 60% after purification. Isomer A, imine E, NMR (300 MHz, XH, CDC13 TMS = 0 ppm) 1.1 (m, 1H), 1.3 (m, 1H), 1.7 (m, 1H), 1.75 (s, 3H), 2.1 (m , 1H), 3.8 (s, 3H), 3.9 (s, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 6.8-6.9 (m, 3H), ".0 (d, 1H), 7.2 (, 1H) 7.4-7.7 (m, 3H) Isomer B, imine Z, NMR (300 MHz, 2H, CDC13, TMS = 0 ppm) 1.1-1.4 (m, 2H), 1.6 (s, 3H), 2.2 (, 1H), 2.6 (m, 1H), 3.75 (s, 3H), 3.8 (s, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 6.8-6.9 (m, 3H), 7.0 (d, 1H), 7.2 (m, 1H) 7.4-7.7 (m, 3H) Preparation__d6 methyl (E) -2- (aminooxymethyl) phenyl glyoxylate 0-methyloxime _Methyl (E) -2- (O-phthalimidoxymethyl) phenyl glyoxylate 0-methyloxime In a 500 ml dry Round bottom flask equipped with magnetic stirrer and nitrogenous inlet were charged 5.1 g (0.03 15 mol) of N-hydroxyphthalimide, 1.3 g (0.0315 mol) of sodium hydroxide, and 300 ml of anhydrous dimethylformamide. The dark red solution was stirred at room temperature for 20 minutes, followed by the sight of methyl 2- (bromomethyl) phenylglyoxylate O-methyloxime (15 g, 60% purity, 0.0315 mol) in one portion. The reaction was stirred at room temperature over the weekend, then poured into 800 ml of water and stirred for 1 hour to obtain a white solid which was collected by vacuum filtration and washed with water, hexane, and dried under vacuum to 40 ° C during the night. 11.5g of a white solid was isolated (98% isolated yield) which was congruent with the desired product, methyl (E) -2- (O-phthalimidoxymethyl) phenyl glyoxylate 0-methyloxime, after analysis with 300 MHz 1H NMR. NMR (300 MHz,? E, CDC13, TMS = 0 ppm) 3.8 (s, 3H), 3.95 (s, 3H), 5.0 (s, 2H), 7.1 (d, 1H), 7.5 (m, 2H., 7.7-7.9 (, 5H) Preparation of methyl (E) -2- (aminooxymethyl) phenyl glyoxylate 0-methyloxime In a 250 ml round bottom flask equipped with a magnetic stirrer, 11.4 g (0.031 mole) of methyl (E) was charged. ) -2- (O-phthalimidoxymethyl) phenyl glyoxylate 0-methyloxime, 100 ml of anhydrous methanol, and 1.9 g (0.034 mole) of monohydrate hydrazine The flask was capped, and the reaction was stirred at room temperature for 2 hours. The resulting solid was removed by filtration and the filtrate was concentrated on a rotary evaporator, the residue was dissolved in 100 ml of ether, filtered, and washed to obtain 7.4 g of a thick yellow oil (100% isolated yield), which was congruent with the desired product methyl (E) -2- (aminooxymethyl) phenyl glyoxylate O-methyloxime after analysis with 300 MHz "" "H NMR was stored at -20 ° C until required for a synthesis NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 3.87 (s, 3H), 4.03 (s, 3H), 4.6 (s, 2H), 4.9-5.4 (bs, 2H), 7.2 (m, 1H), 7.4-7.5 (m, 3H). Example _3 Preparation of the imine isomers E and Z: (E, E) and (Z, E) -N-Methyl 2- [2- ((((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) ) ethylidene) amin) oxy) methyl) phenylj-2-methoxyiminoacetamide Compounds 3.23A and 3.23B of Table 3. In a 100 ml dry-bottomed round bottom flask equipped with a magnetic stirrer, 210 mg (0.5 12 mmol) of Compound 2.23 was charged. A, imine E, (E, E) -methyl 2- [2- ((((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) ethylidene) amin) oxy) metii) phenyl] -2-methoxyimino -acetate, 10 ml of anhydrous methanol, and 1.0 ml (12.9 mmoles) of 40% aqueous methyl amine. The bottle was capped and stirred during the weekend at room temperature. The solution was then poured into 100 ml of water, and extracted with 3 x 50 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 210 mg of a thick yellow oil (100% isolated yield) which was congruent with the desired proauct, (E, E ) -N-methyl 2- [2- ((((trans-l- (2- (4'-ethoxyphenyl) cyclopropyl) ethylidene) amin) oxy) ethyl) phenyl] -2-methoxyiminoacetamide after analysis with 300 MHz 1H NMR. Compound 3.23A, Isomer A, Imine E, NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.1 (m, 1H), 1.3 (m, 1H), 1.7 (m, 1H), 1.75 (s, 3H) ), 2.1 (m, 1H), 2.9 (d, 3H), 3.8 (s, 3H), 3.95 (s, 3H), 4.95 (s, 2H), 6.7 (bs, 1H), 6.8-6.9 (m, 3H), 7.0 (d, 1H), 7.2 (, 1H) 7.4-7.7 (m, 3H) The procedure was repeated for 0.23 g of compound 2.23B, imine Z, (Z, E) methyl 2- [2- ( (((trans-1- (2- (4'-methoxyphenyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate. and provided 0.23 g of (Z, E) -2- [2- ((((trans-1- (2- (4'-methoxyphenyl) -cyclopropyl) ethylidene) amin) oxy) ethyl) phenyl] -2-methoxyiminoacetamide, after analysis with 300 MHz 1H NMR, in an isolated yield of 100U Compound 3.23B, Isomer B, imine Z, NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.1-1.4 (m, 2H ), 1.6 (s, 3H), 2.2 (m, 1H), 2.7 (m, 1H) 2.75 (d, 3H), 3.8 (s, 3H), 3.95 (s, 3H), 4.95 (s, 2H), 6. 6 (bs, 1H), 6.8-6.9 (m, 3H), 7.0 (d, 1H), 7.2 (m, 1H) 7.4-7.7 (m, 3H). Example 4 Preparation of imines E and Z: (E, E) and (Z, E) -Methyl 2- [2- ((((transU- (2-phenylcyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2 -methoxyiminoacetate Compound 2.11, 2.11A and 2.11B Table 2 Preparation of trans-2-phenylcyclopropylmethyl ketone In a 2000 ml round bottom flask equipped with a magnetic stirrer were charged 150 g of trimethylsulfoxonium iodide (0.685 moles, l.Oeq. ), 28g of powdered sodium hydroxide (0.685 moles, l.Oeq.) And 1000 ml of DMSO. The bottle was capped and stirred at room temperature for 15 minutes, after which 1OOg of trans-4-phenyl-3-buten-2-one (0.685 moles) was added in one portion. The reaction was stirred at room temperature for 5 minutes, then poured into 500 ml of water and extracted with 3 x 200 ml of ethyl ether. The ether extract was washed successively with 2 x 200 ml of water and 200 ml of brine, dried over anhydrous MgSO 4, filtered and cleaned. 94 g yellow liquid (86% yield) was isolated which was congruent with the desired product trans-2-cyclopropylmethyl ketone after analysis with 300 MHz E NMR. 300 MHz, 1H / CDC13, TMS = 0 ppm): 1.3 (m, 1H), 1.7 (m, 1H), 2.2 (m, 1H), 2.3 (s, 3H), 2.6 (m, 1H), 7.1 (d, 2H), 7.2-7.4 (m, 3H) Preparation of imines E and Z: (E, E) and (Z, E) -Methyl 2- [2- ((((trans-1- (2-phenyl-cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate In a 250 ml round bottom flask equipped with a magnetic stir bar and reflux condenser was charged 7.3 g of trans-2-phenylcyclopropylmethyl ketone (0.045 mol, l.Oeq)) in 100 ml of methanol, and 16.2 g of methyl (E) -2- (aminooxymethyl) phenyl-glyoxylate O-methyloxime (0.0685, 1 .52eq.). The reaction was refluxed for 2 hours, after which an aliquot was analyzed by capillary GC. No initial material remained, and the two new products were observed at a rate of approximately 70% / 30%. The reaction was then cooled and poured into 200 ml of water, and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, 100 ml of 0.1 N HCl and 100 ml of saturated NaCl solution. The ether extract was then dried over anhydrous MgSO 4, filtered and washed to provide 17.2 g of crude product as a thick yellow oil (quantitative yield), characterized by 300 MHz 1 H NMR, and capillary GC congruent with (E, E) and (Z, E) -methyl 2- [2- ((((trans-1- (2-phenylcyclopropyl) ethylidene) aminopi) methyl) phenyl] -2-methoxyiminoacetate in a proportion of imines (-70% E at 30% Z). Chromatography of 1.0 g of compound 2.11 was performed (mixture of compounds 2.11A and 2.11B) on silica gel with % EtOAc / 75% hexane to obtain, in order of elution from the 500 mg column, a yellow viscous liquid, isomer A, which was characterized as congruent with the desired product as imine E, (E, E ) -methyl-2- [2- ((((trans-1- (2-phenylcyclopropyl) -ethylidene) min) oxy) ethyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1H NMR, and 250 mg of a viscous yellow oil, isomer B, was characterized as congruent with the desired product in the form of imine Z, (Z, E) -methyl 2- [2- ((((trans-1- (2-phenyl) cyclopropyl) ethylidene) -amin) oxij methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1H NMR. The recovery after purification was 75%. Compound 2. HA: Isomer A, imine E, NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1.4 (m, 1H), 1.75 (s, 3H), 1.8 (m, 1H), 2.2 (m, 1H), 3.8 (s, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 7.1 (d, 2H), 7.2 (m, 2H), 7.3 (m, 2H) ), 7.4-7.5 (m, 3H).

Compound 2.11B: Isomer B, irtrin Z, NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1.3 (m, 1H), 1.65 (s, 3H), 2.2 (m, 1H ), 2.7 (m, 1H), 3.7 (s, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 7.1-7.2 (m, 4H), 7.3 (m, 2H), 7.4-7.5 ( m, 3H) Example 5 Preparation_ of imines E and Z: (E, E) and (Z, E) -N-Methyl 2- [2- ((((trans-1- (2-phenylcyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetamide Compounds 3.11, 3 HA and 3.1IB of Table 3 In a 250ml dry Round bottom flask equipped with a magnetic stirrer, 17.2 g of compound 2.11 was charged as a 70:30 mixture of (E, E) and (Z, E) -N-Methyl. 2- [2- ((((trans-1- (2-phenylcyclopropyl) ethylidene) amin) ox) methyl) phenyl] -2-methoxyiminoacetate (0.0453 mol, 1.0 eq.) In 100 ml of methanol, and 5.3 g of 40% methyl amine (0.0679 moles, 1.5eq.) in water. The bottle was capped and stirred overnight at room temperature. An aliquot was analyzed by capillary gas chromatography. No initial material remained, and two new products were observed in a proportion of about 70% 130% - The reaction was then poured into 200 ml of water, and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, 100 ml of 0.1 N HCl and 100 ml of saturated NaCl solution. The ether extract was dried over anhydrous MgSO4, filtered and washed to give 15.1 g of crude product as a thick yellow oil which was characterized by 300 MHz 1 H NMR, and capillary GC with compound 3.11 as an iminoxy mixture. : 30 from (E, E) and (Z, E) -N-methyl 2- [2- ((((trans-1- (2-phenyl-cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2 -methoxyiminoacetamide in isolated yield of Chromatography of 1.5 g of compound 3.11 was performed on silica gel with 30% EtOAc / 70% hexane to obtain, in order of elution from the column 1100 mg of a viscous yellow liquid, isomer A, which is characterized as congruent with the desired product such as imine E, (E, E) -methyl-2- [2- ((((trans-1- (2-phenylcyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1 H NMR, and 350 mg of a viscous yellow oil, isomer B, which is characterized as congruent with the desired product as imine Z, (Z, E) methyl 2- [2- ((( (trans-1- (2-phenycyclopropyl) ethylidene) amin) oxy) -methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz? E NMR. The recovery after purification was 97%.

Compound 3. HA, Isomer A, Imine E, NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1. 4 (m, 1H), 1.75 (s, 3H), 1.8 (m, 1H), 1. 2 (m, 1H), 2.9 (d, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 6.7 (bs, 1H), 7.1 (d, 2H), 7.2 (, 2H), 7.3 ( m, 2H), 7.4-7.5 (m, 3H) Compound 3.11B, Isomer B, imine Z, NMR (300 MHz, XE, CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1.3 (m, 1H), 1.65 (s, 3H), 2.2 (, 1H) , 2.7 (m, 1H), 2.8 (d, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 6.6 (bs, 1H), 7.1-7.2 (, 4H), 7.3 (m, 2H) , 7.4-7.5 (m, 3H) Example 6 Preparation of imines E and Z: (E, E) and (Z, E) methyl 2- [2- ((((trans-1- (2- (2-thienyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoximinoacetate Compounds 11.50A and 11 .50B of Table 11 Preparation of trans-4- (2-thienyl) -3-buten-2-one In a 250 ml round bottom flask equipped with a magnetic stirrer 13.4 g (0.267 moles, l.Oeq.) of acetone, 100 ml of ethanol, and 1 ml of water were charged. 2-thiophenecarboxaldehyde (3.0 g, 0.0267 mol, 1 .eq) followed by 0.2 g of barium hydroxide monohydrate (catalyst) was added in one portion. The flask was capped and stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 100 ml of saturated aqueous sodium bisulfite solution, followed by 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 3.5 g of amber oil (isolated yield of 86%), which was congruent with the desired product, trans-4- ( 2-thienyl) -3-buten-2-one, after analysis with 300 MHz XH NMR. NMR (300 MHz, XH, CDC13, TMS = 0 ppm) 2.3 (s, 3H), 6.5 (d, 1H), 7.1 (, 1H) 7.3 (m, 1H), 7.4 (m, 1H), 7.6 (d , 1 HOUR) . Preparation of trans-2- (2-thienyl) cyclopropylmethyl ketone In a 250 ml round bottom flask equipped with magnetic stirrer, nitrogen inlet, and equalization funnel with equalized pressure were charged 5.1 g (0.023 mol, l.Oeq. ) of trimethylisulfoxonium iodide, 0.92 g (0.023 moles, 1 .Oeq.) of powdered sodium hydroxide, and 100 ml of dimethylsulfoxide. The solution was stirred at room temperature for 30 minutes, followed by the addition of trans-4- (2-thienyl) -3-buten-2-one in one portion. The dark red solution was then stirred for 15 minutes at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain the crude product, which chromatography was performed on silica gel with 90% hexane, and 10% ethyl acetate. The pure fractions were combined and concentrated on a rotary evaporator to obtain 1.1 g of a thick pale yellow liquid in an isolated yield of 29% which was congruent with the desired product, trans-2- (2-thienyl) cyclopropylmethyl ketone after analysis. with 300 MHz XH NMR. NMR (300 MHz, XH, CDC13 / TMS = 0 ppm) 1.4 (m, 1H), 1.7 (m, 1H), 2.2 (m, 1H), 2.3 (s, 3H), 2.7 (m, 1H), 6.8 (m, 1H) ), 6.9 (m, 1H), 7.1 (m, 1H). Preparation of (E, E) and (Z, E) -methyl 2- [2- ((((trans-1- (2- (2-thienyl) cyclopropyl) -ethylidene) amin) oxy) methyl) phenyl] - 2-methoxymethyl acetate In a 25 ml glass flask equipped with a magnetic stir bar, trans2- (2-thienyl) cyclopropylmethyl ketone (0.6 g, 0.0036 mol, l.Oeq.) Was charged with 10 ml of anhydrous methanol, and 0.95 g ( 0.0040 moles, 1.1 eq.) Of (E) -2- (aminooxymethyl) -phenylglyoxylate 0-methyloxime. The bottle was capped, and stirred overnight at room temperature. The solution was then poured into 100 ml of water, and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 6 g of the crude product as an amber oil. Chromatography of this product was carried out on silica gel with 30% EtOAc / 70% hexane to obtain, in order of elution of the column 580 mg of a viscous yellow liquid which was characterized as congruent with the desired product as imine E, in (E, E) -methyl 2- [2- ((((trans-1- (2- (2-thienyl) cisopropyl) ethylidene) aminopi) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1H NMR, and 300 mg of a viscous yellow oil which was characterized as congruent with the desired product as the imine Z, (Z, E) -methyl 2- [2- ((((trans- 1 - (2- ( 2-thienyl) cyclopropyl) ethylidene) amino) -oxy) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz 1H NMR. Total yield of 65% after purification.

Compound 11.50A, Isomer A, Imine E NMR (300 MHz, 1H, CDC13, TMS = 0 ppm) 1.1 (m, 1H), 1.3 (m, 1H), 1.76 (s, 3H), 1.8 (m, 1H) , 2.3 (m, 1H), 3.85 (s, 3H), 4.05 (s, 3H), 4.95 (s, 2H), 6.7 (m, 1H), 6.9 (m, 1H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3-7.5 (m, 3H) Compound 11.50B, Isomer B, imine Z NMR (300 MHz, XH, CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1.3 (m, 1H), 1.63 (s, 3H), 2.5 (m, 1H), 2.7 (m, 1H), 3.77 (s, 3H), 4.0 (s, 3H), 4.95 (s, 2H), 6.7 (m, 1H), 6.9 (m, 1H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3-7.5 (m, 3H). Example 7 Preparation of imines E and Z: (E, E) and (Z, E) -N-Methyl 2- [2- ((((trans-1-7 (2- (2-thienyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetamide Compounds. 12.50A and 12.50B of Table 12 In a 25 ml glass bottle equipped with a magnetic stirrer, 200 mg (0.544 mmol) of 11.50A (E, E) -methyl 2- [2- ((((trans -1- (2- (2-thienyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate in 10 ml of anhydrous methanol, and 1.0 ml (12.9 mmoles) of 40% aqueous methyl amine . The bottle was capped and stirred overnight at room temperature. The solution was then poured into 100 ml of water and extracted with 3 x 50 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 170 mg of a thick yellow oil in an isolated yield of 81% which was congruent with the desired product, (E, E ) -N-methyl 2- [2- ((((trans-1- (2- (2-thienyl) -cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetamide, after analysis with 300 MHc 1H NMR. Compound 12.50A, Isomer A, Imine E NMR (300 MHc, 1H, CDC13, TMS = 0 ppm) 1.1 (m, 1H), 1.3 (m, 1H), 1.75 (s, 3H), 1.8 (m, 1H) , 2.35 (, 1H), 2.95 (d, 3H), 3.95 (s, 3H), 4.95 (s, 2H), 6.65 (bs, 1H), 6.7 (m, 1H), 6.9 (m, 1H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3-7.5 (, 3H). The procedure was repeated for imine Z, (C, E) -methyl 2- [2- ((((trans-1- (2- (2-thienyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] - 2-methoxylminoacetate, with 150 mg and produced 150 mg of thick yellow oil in an isolated yield of 100% which was congruent with the desired product, (Z, E) -N-methyl 2- [2- ((((trans 1- (2- (2-thienyl) -cyclopropyl) ethylidene) amin) oxy) methyl) phenyl] -2-methoxy-laminoacetamide after analysis with 300 MHc XH NMR. Compound 12.50B, Isomer B, iipa Z NMR (300 MHz, 1H / CDC13, TMS = 0 ppm) 1.2 (m, 1H), 1.3 (m, 1H), 1.61 (s, 3H), 2.5 (m, 1H ), 2.7 (m, 1H), 2.8 (d, 3H), 3.9 (s, 3H), 4.97 (s, 2H), 6.65 (bs, 1H), 6.7 (m, 1H), 6.9 (, 1H), 7.1 (d, 1H), 7.2 (d, 1H), 7.3-7.5 (, 3H) Example 8 Preparation of (E) -Methyl 2- [2- (4-trans- (2-phenylcyclopropyl) -5-ethyl- 2,7-dioxa-3,6-diazaocta-3,5-dien-l-yl) phenyl] -2-methoxyiminoacetate Compound 2.144A of Table 2 Preparation of trans-1-phenyl-1-penten-3-one In a 250 ml round bottom flask equipped with a magnetic stirrer was charged 10.0 g (0.116 mol, l.Oeq.) of 2-pentanone, 100 ml of ethanol, and 10 ml of water. Benzaldehyde (12.3 g, 0.116 mol, l.Oeq.) Was added in one portion, followed by 0.4 g of 85% potassium hydroxide. The flask was capped and stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 100 ml of saturated aqueous sodium bisulfite solution, followed by 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 15.8 g of a reddish liquid (78% isolated) which was congruent with the desired product, trans-1-phenyl- 1-penten-3-one after analysis with 300 MHc 1HNMR. NMR (300 MHc XE NMR, CDC13, TMS = 0 ppm) 1.0 (t, 3H), 1.7 (q, 2H), 2.65 (t, 2H), 6.8 (d, 1H), 7.3-7.5 (m, 4H), 7.6 (m, 2H). Preparation of trans-2-phenylcyclopropyl-n-propyl ketone In a 500 ml round-bottomed flask equipped with magnetic stirrer, nitrogen inlet, and equalized addition funnel was charged 19.4 g (0.0879 moles, i.e.) of trimethylsulfoxonium iodide, 3.5 g (0.0879 moles, 1 .Oeq.) of powdered sodium hydroxide and 150 ml of dimethylsulfoxide. The solution was stirred at room temperature for 30 minutes, followed by the dropwise addition of the trans-1-phenyl-penten-3-one, (15.3 g 0.0879 moles) in 50 ml of dimethylsulfoxide. The reaction was then stirred overnight at room temperature, then poured into 200 ml of water and exted with 3 x 100 ml of ethyl ether. The ether ext was washed with 2 x 100 ml of water and 100 ml of saturated aqueous sodium chloride solution. The ether ext was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 14.2 g of a thick brown liquid (isolated yield of 86%) which was congruent with the desired product, trans-2- phenylcyclopropyl-n-propyl ketone after analysis with 300 MHc 1H NMR. NMR (300 MHc, H NMR, CDCl 3, TMS = 0 ppm) 0.95 (t, 3H), 1.3 (m, 1H), I7 (m, 3H), 2.2 (m, 1H), 2.45 (, 1H) ), 2.5 (m, 2H), 7.0 (d, 1H), 7.1-7.5 (, 4H) Preparation ^ of 2-hydroximin-l- (trans-2-phenylcyclopropyl) -1-butanone In a round bottom flask of 500 ml equipped with a magnetic stirrer, nitrogen inlet, and addition funnel with equalized pressure were charged 9.5 g (0.084 mol, l.leq) of potassium t-butoxide, and 150 ml of t-butanol. The solution was stirred at room temperature for 30 minutes, followed by rapid dropwise addition of a solution of trans-2-phenylcyclopropyl-n-propyl ketone (14 g, 0.075 mol, l.Oeq.), 26 g of t- 90% butylnitrite (0.231 moles, 3.08eq.) and 100 ml of t-butanol. The reaction was then stirred overnight at room temperature, then poured into a 500 ml round bottom flask and concentrated on a rotary evaporator. The residue was dissolved in 200 ml of water, acidified to a pH of 2 with 1 N of crude hydrochloric acid, and exted with 3 x 100 ml of ethyl ether. The ether ext was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether ext was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 8.4 g of a brown solid (isolated yield of 52%) which was congruent with the desired product, 2-hydroxyamin-1. - (trans-2-phenylcyclopropyl) -1-butanone after analysis with 300 MHc 1H NMR. NMR (300 MHc, XH, CDC13 / TMS = 0 ppm) 1.0 (t, 3H), 1.4 (m, 1H), 1.8 (m, 1H), 2.6 (m, 3H), 3.1 (m, 1H, 7.5 ( m, 2H), 7.1 (d, 2H), 7.2-7.4 (m, 4H) Preparation of 2-methoxyimin-l- (trans-2-phenylcyclopropyl) -1-butanone In a 100 ml round bottom flask equipped with a magnetic stirrer, and nitrogen inlet were charged 3.6 g (0.0166 moles, 1 .eq.) of 2-hydroxyimin-l- (trans-2-phenyl-cyclopropyl) -1-butanone, 2.3 g (0.0166 moles, 1. Oeq.) Of potassium carbonate and 100 ml of dimethylamine: dry ormamide The mixture was stirred at room temperature for 10 minutes, followed by the addition of 2.35 g (0.0166 moles) of iodomethane. overnight at room temperature, then poured into 100 ml of water, and exted with 3 x 100 ml of ethyl ether.The ether ext was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous solution of chloride The ether ext was dried over anhydrous magnesium sulfate, s = filtered and The mixture was concentrated on a rotary evaporator to obtain 3.4 g of a brown oil, which was chromatographed on silica gel with 15% ethyl acetate, 85 s of hexane. The pure fions were combined and concentrated in a rotary evaporator to obtain 2.5 g of a pale yellow oil (65% isolated yield) which was congruent with the desired product, 2-methoxyimin-l- (trans-2-phenylcyclopropyl) -1-butanone after analysis with 300 MHc XH NMR. NMR (300 MHc, 1H, CDCl3 / TMS = 0 ppm) 1.0 (t, 3H), 1.4 (m, 1H), 1.7 (m, 1H), 2.5 (q, 2H), 2.6 (m, 1H), 3 '.2 (m, 1H), 4.0 (s, 3H), 7.1 (d, 2H), 7.2-7.3 (m, 3H). Preparation of 2-methoxyimin-l- (trans-2-phenylcyclopropyl) -1-butanone_ oxime 2.3 g (0.010 mol, l.Oeq.) Were charged to a 200 ml round bottom flask equipped with magnetic stirrer and nitrogen inlet. of 2-methoxyimin-1- (trans-2-phenylcyclopropyl) -1-butanone, 3.5 g (0.05 moles, 5. Oeq.) of hydroxylamine hydrochloride, 4 g (0.05 moles) of pyridine and 70 ml of methanol. The reaction was stirred overnight at room temperature, then poured into 200 ml of water, and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.9 g of a yellow oil which was chromatographed on silica gel with 15% ethyl acetate, 85% of hexane. The pure fractions were combined and concentrated in a rotary evaporator to obtain (in order of elution) 1.1 g of a pale yellow solid which was congruent with the desired product, isomer A: 2-methoxyimin-1 oxime (trans 2-phenylcyclopropyl) -1-butanone after analysis with 300 MHc 1H NMR, and 0.25 g of a yellow solid which was congruent with the desired product, isomer B: 2-methoxyimin-1- (trans-2-phenylcyclopropyl) oxime ) -1-butanone after analysis with 300 MHc XH NMR, in a combined isolated yield of 57%. Isomer A: NMR (300 MHc, XH, CDC13, TMS = 0 ppm) 1.0 (t, 3H), 1.3 (m, 1H), 1.9 (m, 1H), 2.5 (m, 1H), 2.6 (q, 2H) ), 2.8 (m, 1H), 3.95 (s, 3H), 7.1-7.4 (m, 5H), 8.5 (bs, 1H). Isomer B: NMR (300 MHc, 1H, CDC13, TMS = 0 ppm) 1.0 (t, 3H), 1.2 (m, 1H), 1.6 (m, 1H), 1.95 (, 1H), 2.4 (, 1H), 2.7 (q, 2H), 3.95 (s, 3H), 7.1-7.4 (m, 5H), 9.5 (bs, 1H). Preparation of Isomer A of (E) -Methyl 2-J2- (4-trans- (2-phenynicitypropyl) -5-ethyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1-yl ) phenyl] -2-methoxyiminoacetate In a 100 ml round bottom flask equipped with a magnetic stirrer and nitrogen inlet were charged 0.8 g (0.00325 moles, 1 .eq.) Of oxime A, 2-methoxyimin-1- (trans-2-phenylcyclopropyl) -1-butanone oxime, 0.9 g (0.0065 moles, 2. Oeq.) Of potassium carbonate, and 100 my dry dimethylformamide. The mixture was stirred at room temperature for 10 minutes, followed by the addition of 1.25 g (0.00325 mole, 1 / Oeq.) Of 75% methyl 2- (bromomethyl) phenylglyoxylate 0-methyl oxime. The reaction was then stirred overnight at room temperature, then poured into 100 ml of water, and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution, the ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.4. g of a brown oil which was chromatographed on silica gel with 15% ethyl acetate, 85% hexane. The pure fractions were combined and concentrated on a rotary evaporator to obtain 0.4 g of a clear colorless oil (isolated yield of 27%) which was congruent with the desired product, isomer A, (E) -methyl 2- [2- (4-trans- (2-phenyl-cyclopropyl) -5-ethyl-2,7-dioxa-3,6-diazaocta-3,5-dien-l-yl) phenyl] -2-methoxyimino-acetate after analysis cdn 300 MHc 1H NMR. NMR (300 MHc, XH, CDC13, TMS = 0 ppm) 1.0 (t, 3H), 1.3 (m, 1H), 1.8 (m, 1H), 2.4 (m, 1H), 2.5 (q, 2H), 2.8 (m, 1H), 3.75 (s, 3H), 3.9 (s, 3H), 4.0 (s, 3H), 5.0 (s, 2H), 7.1 (m, 4H), 7.2 (, 2H), 7.4 (m , 3H). EXAMPLE 9 Preparation of (E) -N-Methyl 2- [2- (4-trans- (2-phenylcyclic propyl) -5-ethyl-2,7-dioxa-3,6-diazaocta-3,5-dien-1) -yl) phenyl] -2-metpxiiminoacetamide Compound 3.144A of Table 3 In a 100 ml round bottom flask equipped with a magnetic stirrer, 250 mg (0.55 mmoles) of isomer A of < E) -methyl2- [2- (4-trans- (2-phenylcytopropyl) -5-ethyl-2,7- dioxa-3,6-diazaocta-3,5-dien-l-yl) phenyl] -2 -methoxyiminoacetate and 50 ml of methanol. 1.0 ml of aqueous solution of 40% methyl amine (12.9 mmoles) were then added in one portion, and the flask was capped, and stirred overnight at room temperature. The reaction was then poured into 100 ml of water, and extracted with 3 x 50 ml of ethyl ether. The ether extract was washed with 2 x 50 ml of water and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 140 mg of a clear pale yellow oil (56% isolated yield) which was congruent with the title compound 3.144 after analysis with 300 MHz XH NMR. NMR (300 MHz, lE, CDC13, TMS = 0 ppm) 0.95 (t, 3H), 1.2 (m, 1H), 1.8 (m, 1H), 2.3 (m, 1H), 2.45 (q, 2H), 2.8 (m, 1H), 2.9 (d, 3H), 3.65 (s, 6H), 5.0 (s, 2H), 6.6 (bs, 1H), 7.0 (m, 4H), 7.2 (m, 2H), 7.4 ( m, 3H). Example 10 Preparation of (E) -Methyl 2- [2- ((((1- (1, 2-diphenylcyclopropyl) ethylidene) aminopi) methyl) phenyl] -2-methoxyiminoacetate Compound 5.39 of Table 5 Preparation of OA phenylcinnamonitrile In a 250 ml round bottom flask equipped with a magnetic stirrer were charged 3.0 g (0.0256 moles, 1.0 eq.) of benzylcyanide, 150 ml of ethanol, and 50 ml of water. Benzaldehyde (2.7 g, 0.0256 moles, 1.0 eq.) Was added in one portion followed by 0.2 g of 85% potassium hydroxide. The flask was capped and stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water. The resulting precipitate was collected by vacuum filtration, washed with water, hexane and dried under vacuum at 40 ° C overnight to obtain 4.4 g of a white solid (isolated yield of 84%) which was congruent with the product desired, α-phenylcinnamonitrile, after analysis with 300 MHz XH NMR. NMR (300 MHz, U, CDCl 3 TMS = 0 ppm) 7.1 (s, 1H), 7.2-7.4 (m, 6H), 7.6 (d, 2H), 7.8 (m, 2H). Preparation of 1, 2-diphenylcyclopropanecarbonitrile In a 250 ml round bottom flask equipped with a magnetic stirrer, nitrogen inlet, and equalized pressure anti- funnel were charged 4.8g (0.02 15 moles, l.Oeq.) of trimethylsulfoxonium iodide, 0.86 g (0.0215 moles, l.Oeq.) of powdered sodium hydroxide and 150 of dimethylsulfoxide. The solution was stirred at room temperature for 30 minutes, followed by the dropwise addition of phenyl cinnamonitrile in 100 ml of dimethylsulfoxide. The reaction was then stirred overnight at room temperature. The reaction mixture was then poured into 200 ml of water and extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water, and 100 ml of saturated aqueous sodium chloride solution. The ether extract was dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 4.1 g of a thick transparent colorless liquid which crystallized after standing (87% isolated yield) and was congruent with the product desired, 1,2-diphenylcyclopropanecarbonitrile, after analysis with 300 MHz XH NMR. NMR (300 MHz, 1H # CDC13, TMS = 0 ppm) 2.0 (m, 1H), 2.2 (m, 1H), 2.8 (m, 1H), 7.1 (m, lOH). Preparation of 1,2-diphenylcyclopropylmethyl ketone In a 500 ml dry-bottom round flask equipped with magnetic stirrer, nitrogen inlet, reflux condenser and side-arm addition funnel were charged 1.5 g (0.00685 moles, 1 .Oeq. ) of nitrile 1,2-diphenylcyclopropancarbonitrile and 150 ml of anhydrous toluene. Then, methylmagnesium bromide (0.0137 mol, 2.0 eq 4.6 mL of 3.0 M in ether) was added dropwise and the flow of the reaction was carried out for two hours. The reaction was cooled and carefully quenched with 100 ml of saturated aqueous ammonium chloride solution, then extracted with 3 x 100 ml of ethyl ether. The ether extract was washed with 2 x 100 ml of water and 100 ml of saturated aqueous sodium chloride solution, then dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.4 g of an oil. Thick transparent yellow (87% isolated yield) which was congruent with the desired product, 1,2-diphenylcyclopropylmethyl ketone after analysis with 300 MHz H NMR. NMR 300 MHz, 1H, CDC13, TMS = 0 ppm) 0.9-1.1 (m, 2H), 1.4 (m, 1H), 1.9 (s, 3H), 7.1-7.4 (m, lOH). Preparation of (E) -Methyl 2- [2- ((((1- (1, 2-diphenylcyclopropyl) ethylidene) amin) -oxi) methyl) phenyl] -2-methoxyiminoacetate In a 50 ml round bottom flask equipped with magnetic stirrer and reflux condenser, 0.8 g (0.0034 mol, 1 .eq.) of 1,2-diphenylcyclopropylmethyl ketone 50 ml of anhydrous toluene, approximately 20 molecular sieves size 4A, and 0.9 g (0.0037 mol, 1.1 cq. ) 0-Methyloxime of (E) -2- (aminooxymethyl) phenylglyoxylate. The reaction was refluxed for a total of 2.5 hours, then cooled and filtered through filter paper to remove the insoluble material. The filtrate was poured into 100 ml of water and extracted with 3 x 50 ml of ether. The ether extract was then washed with 2 x 100 ml of water, 100 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 1.4 g of a liquid. Thick amber color to which chromatography on silica gel was performed with 20% ethyl acetate, 80% hexane. The pure fractions were combined and concentrated in a rotary evaporator to obtain 460 mg of a clear, colorless, thick oil (30% isolated yield) congruent with the desired product, (E) -Methyl 2- [2- (((1- ( (1,2-diphenylcyclopropyl) ethylidene) amin) -oxi) methyl) phenyl] -2-methoxyiminoacetate after analysis with 300 MHz "" "H NMR, NMR (300 MHz, XH, CDC13, TMS = 0 ppm) 1.3 ( s, 3H), 1.35 (m, 1H), 2.2 (m, 1H), 2.8 (m, 1H), 3.75 (s, 3H), 4.0 (s, 3H), 5.0 (s, 2H), 7.1-7.4 (m, 14H) Example 11 Preparation of (E) -N-Methyl 2- [2- (((1- (1, 2-diphenylcyclopropyl) ethylidene) aminopi) methyl) phenyl] -2-ethoxyiminoacetamide Compounds 6.39 of Table 6 300 mg (0.66 mmol) of (E) -methyl 2- [2- ((((1- (1) was charged to a 100 ml dry-bottom flask equipped with a magnetic stirrer., 2-diphenylcyclopropyl) -etiidene) amin) oxy) methyl) phenyl] -2-methoxyiminoacetate, 10 ml of methanol, and 1.0 ml (12.9 mmoles) of 40% aqueous methyl amine. The flask was capped and stirred overnight at room temperature. The reaction was then poured into 100 ml of water and extracted with 3 x 50 ml of ethyl ether. The ether extract was washed with 2 x 50 ml of water, 50 ml of saturated aqueous sodium chloride solution, dried over anhydrous magnesium sulfate, filtered and concentrated on a rotary evaporator to obtain 300 mg of an oil. Thick transparent yellow (99% isolated yield) congruent to the desired product, (E) -N-methyl 2- [2 - (((((1- (1, 2-diphenylcyclopropyl) ethylidene) amin) oxy) methyl) phenyl ] -2-methoxyiminoacetamide after analysis with 300 MHz XH NMR. NMR (300 MHz, XH, CDC13, TMS = 0 ppm) 1.26 (s, 3H), 1.3 (m, 1H), 2.2 (m, 1H), 2.7 (d, 3H), 2.8 (m, 1H), 3.95 (s, 3H), 5.0 (s, 2H), 6.5 (bs, 1H), 7.1-7.4 (m, 14H). The NMR data of protons (300MHz) are given in Table 19 for the typical examples of Tables 1 to 18 and are illustrative of the present invention.

Table 19 fifteen twenty 10 fifteen 25 Table 19 (continued) 10 fifteen 25 10 fifteen twenty Table 19 (continued) 10 fifteen 25 6. 9 (m, 1H), 7. 1 (d, 1H), 7. 2 (d, 1H), 7. 3-7. 5 (m, 3H) Example 12 Several compounds of the present invention were tested for fungicidal activity in vivo against the diseases described below. The compounds were dissolved in a 1: 1 mixture of acetone and methanol 2: 1: 1 or N, N-dimethylformamide and diluted with a mixture of water, acetone and methanol (by volume) 2: 1: 1 to reach the concentration adequate The solution was "sprayed on the plants and allowed to dry for two hours.The plants were inoculated with fungal spores.Each test used control plants that were sprayed with the appropriate solvent and inoculated.For these protection tests, the Plants were inoculated one day after being treated with the compounds of the present invention The remainder of the technique of each of the tests is mentioned below along with the results of various compounds described herein by the number of compound in comparison with the various fungi at a dose of 100 or 150 grams per hectare.The results are the percentage of control of the disease compared to the untreated verilfication, where one hundred was classified as complete disease control and zero as the control of The application of fungal test spores to these test plants was as follows: Brown Wheat Rust (WLR) Puccinia recóndi ta (f.str. tri tici) was cultivated in 7-day wheat (Fielder variety obtained by selection) during a period of 12 days in the greenhouse. The spores were collected from the leaves by etching in aluminum foil. The spores were cleaned by sieving through a mesh with opening of 250 microns and stored dry. The dried spores were used within a month. A suspension of spores was prepared from the dry uredia by adding 20 mg (9.5 million spores) per ml of Soltrol oil. The suspension was distributed in gelatin capsules (capacity of 0.7 ml) that are attached to the oil sprays. One capsule per plan of twenty 2-inch square pots of the 7-day plants, Fielder variety obtained by selection, is used. After waiting at least 15 minutes for the oil to evaporate from the wheat leaves, the plants were placed in a dark dew chamber (18-20 ° C and 100% relative humidity) for 24 hours. The plants were then placed in the greenhouse and evaluated after 12 days for the presence of disease. Scalding of Wheat Leaves (SNW) Septoria nodorum cultures were maintained on Czapek-Dox V-8 juice agar plants in an incubator at 20 ° C with alternating periods of 12 hours of light and 12 hours of darkness for 2 weeks . A suspension of water from the spores was obtained by stirring the portion of the plate with fungal material in deionized water and filtering through cheesecloth. The suspension of water containing spores was diluted to a spore concentration of 3.0 x 106 spores per ml. The inoculum was dispersed by a DeVilbiss atomizer over one week old Fielder wheat plants that had previously been sprayed with the fungicide compound. The inoculated plants were placed in a humidity cabinet at 20 ° C with 12 hours of light and 12 hours of alternating dark for 7 days. The inoculated seedlings were then transferred to a room with controlled environment at 20 ° C for 2 days of incubation. Disease control values were recorded as percentage control. Wheat powdery mildew (WPM) Erysiphe graminis (f.t. tri tici) was grown in wheat seedlings, Fielder variety obtained by selection, in a temperature controlled room at 18 ° C. the oidial spores were shaken from the crop plants in the olideous spores were shaken from the crop plants on the 7-day wheat seedlings that had previously been sprayed with the fungicide compound. The inoculated seedlings were kept in a room with controlled temperature at 18 ° C and rose. The percentage of disease control was classified 7 days after the inoculation. The control values of the disease were recorded as a percentage of control. Oideos of, Cucurbitaceae (CPM) Sphaerotheca fulginea was maintained in cucumber plants, Bush Champion variety obtained by selection, in the greenhouse. The inoculum was prepared by placing five to ten leaves with many oïdeos in a glass container with 500 ml of water containing one drop of Tween 80 (polyoxyethylene monooleate) per 100 ml. After shaking the liquid and the leaves, the inoculum was filtered through cheesecloth and sprayed on the plants with a nebulizer bottle. The spore count was 100,000 spores / ml. The plants were then placed in the greenhouse for infection and incubation. The plants were assigned a score 7 days after inaction. The control values of the disease were recorded as a percentage of control. Late Tomato Pizon (TLB) Cultures of Phytophthora infestans were maintained on a pea-amended agar for two to three weeks. The spores were washed from the agar with water and dispersed with a De Vilbiss atomizer on the leaves of three week Pixie tomato plants which had previously been treated with the compound of the present invention. The inoculated plants were placed in a humidity cabinet at 20 ° C for 24 hours for infection. The plants were then removed to a room with controlled environment at 20 ° C and 90% humidity. A score was assigned to the plants for disease control after five days. Mildeú de la Grava (GDM) Leaves of the Plasmopara viticola, Delaware variety obtained by selection, were kept in a chamber with controlled temperature at 20 ° C in humid air with moderate light intensity for 7 to 8 days. A suspension of water was obtained from the spores of the infected leaves and the concentration of spores was adjusted to approximately 3 x 55 per ml of water. The Delaware grape plants were inoculated by spraying the leaves with a De Vilbiss atomizer until small droplets were observed on the leaves. The inoculated plants were incubated in a haze chamber for 24 hours at 20 ° C. The plants were then removed to a room with controlled environment at 20 ° C. Disease control values were recorded as a control percentage seven days after inoculation. Rice Blight Cultures of Pylícularia oyrzae were maintained on potato dextrose agar for two to three weeks. The spores were washed from the agar with water containing one drop of Tween 80 per 100. After filtering the suspension of the spores through two layers of cheesecloth, the spore count was adjusted to 5 x 105. The suspension of the spores It was sprayed on 12-day rice plants, variety Ml obtained by selection, using a De Vilbiss atomizer. The inoculated plants were placed in a humid chamber at 20 ° C for 36 hours to allow infection. After the period of infection, the plants were placed in the greenhouse. After 6 days, a score was assigned to the plants in terms of disease control. The control values of the disease were recorded as a percentage of control.

Mildeu of the Cucurbitaceae Cucumber plants were kept in the greenhouse. Large, fully expanded leaves were collected from the plates. The stems were wrapped in cotton, the leaves were placed in a large petri dish (15-cm diameter) and the leaves were supported with glass rods. The top cover of the plate was removed and the top surface of the separated cucumber sheet was sprayed with the compounds of the present invention. The sheet was allowed to air dry for about 2 hours. The cultures of Pseudoperonospora cubenis were maintained in the cucumber plants. After extracting the spores by shaking the leaves in water, the lower surface of the treated cucumber leaves were sprayed with a spore concentration of 100,000 spores per ml. The plates were returned to a chamber with controlled environment at 20 ° C and 90% humidity for five days. After this time, the leaves were examined in view of the development of the disease. The control values of the disease were recorded as a percentage of control. Anthracnose of Curbitaceae The fungal pathogen Colletotrichum lagenarium was grown on pape dextrose agar (PDA) in the dark at 22 ° C for a period of 8 to 14 days. C. Lagenarium spores were removed from the PDA plates by flooding the surface of the plate with distilled water, amended with 0.5% volume / weight of yeast extract. The superior surface of the fungal colony was scraped with a piercing instrument until most of the spores were released into the aqueous environment. The suspension of the spores was filtered through cheesecloth, and the spore count was adjusted by adding more water, which contained the yeast extract, until a concentration of 3.0 x 106 spores per ml was reached. The chemically treated cucumber plants were 15 days old, they were of the Bus Champion variety obtained by selection. The upper surface of the leaves of the plants were sprayed with the suspension of the spores until there was runoff, using a manual rolling bottle. The plants were placed in a fog chamber illuminated by fluorescent light (12 hours of light, 12 hours of darkness) for 48 hours. After this period of infection, the plants were placed in a growth chamber for 3 days at 25 ° C and 90% humidity. The treated plants were then valued for disease control. The control values of the disease were recorded as a percentage of control. Sweet Pepper Gray Rot (BOT) The fungus pathogen Botrytis cinerea was grown on potato dextrose agar (PDA) under fluorescent lights (12 hours on, 12 hours off) for a period of 2 to 3 weeks. B. cinerea spores were removed from the PDA plates by flooding the surface of the plate with distilled water, amended with 0.5% volume / weight of yeast extract. The upper surface of the fungal colony was scraped with a rubber instrument until most of the spores were released into the aqueous environment. The suspension of the spores was filtered through cheese cloth, and the spore count was adjusted by adding more water, which contained the yeast extract, until a concentration of 3.0 x 10d per ml was reached. The sweet pepper plants treated chemically were 18 days old, and were of the California Wonder variety obtained by selection. The entire surface of the leaves of the plants was sprayed with the suspension of the spores until the scouring, using a De Vilbiss atomizer. The plants were placed in a low light haze chamber (12 hours of light, 12 hours of darkness) at 22 ° C for 4 or 5 days. The treated plants were then valued for disease control. The values of disease control were recorded as a percentage of control.

When tested against brown wheat rolla at a dose of 150 grams per hectare, the compounds 2.99, 2,129, 2,157, 3,99 and 3,157 showed a control of 90% or better. When tested against the scald of wheat leaves at a dose of 150 grams per hectare, compounds 2.99 and 3.99 showed a control of 85% or better. When tested against oidium of wheat at a dose of 150 grams per hectare, compounds 2.129, 2.99, 2.157 and 3.157 showed a control of 90% or better. When tested against the powdery mildew of the cucurbits at a dose of 150 grams per hectare, the compounds 2.129, 2.157 and 3.157 showed a control of 85% or better. When tested against tomato late blight at a dose of 150 grams per hectare, compounds 2.99 and 3.99 showed a control of 90% or better. When tested against the powdery mildew of the grape at a dose of 150 grams per hectare, the compounds 2.129 and 3.157 showed a control of 75% or better. When tested against rice blight at a dose of 150 grams per hectare 2.99, 2.107, 2.157 and 2.129 showed a control of 85% or better.

When tested against the powdery mildew of the cucurbits at a dose of 150 grams per hectare, the compounds 2.99, 3.103, 3.106 and 3.107 showed a control of 90% or better. When tested against the gray rot of sweet peppers at a dose of 150 grams per hectare, compound 2.99 showed a control of 80% or better. When tested against the anthracnose of cucurbits at a dose of 150 grams per hectare, compounds 2.99 and 3.99 showed a control of 75% or better. The compounds of the present invention are useful as agricultural fungicides and, as such, can be applied in various places such as the seed, soil or foliage of the plants that will be protected. The compounds of the present invention can be applied as fungicide sprays by commonly applied methods, for example, conventional large volume hydraulic sprays, low volume sprays, air blast sprays, aerial sprays and powders. The dissolution and the application rate will depend on the type of equipment used, the method of application, the plants to be treated and the diseases to be controlled. In general, the compounds of the present invention will be applied in an amount of from about 0.005 kilograms to about 50 kilograms per hectare and preferably from about 0.025 to about 25 kilograms per hectare of active ingredient. As a seed protector, the amount of toxicant coated in the seed is generally from a dosage rate of from about 0.05 to about 20, preferably from about 0.05 to about 4, more preferably from about 0.1 to about 1 gram per one hundred kilograms of seed. As a soil fungicide the chemical compound can be incorporated into the soil or applied to the surface generally at a rate of from about 0.02 to about 20, preferably from about 0.05 to about 10, and more preferably from 0.1 to about 5 kilograms per hectare. As a foliar fungicide, the toxicant is generally applied to growing plants at a rate of from about 0.01 to about 10, preferably from 0.02 to about 5, and more preferably from 0.25 to about 1 kilogram per hectare. While the compounds of the present invention exhibit fungicidal activity, these compounds can be combined with other known fungicides to provide a broad spectrum activity. Suitable fungicides include, but are not limited to, the compounds listed in U.S. Patent No. 5,252,594 (see in particular columns 14 and 15). Other known fungicides which can be combined with the compounds of the invention are dimethomorph, ciymoxanil, trifluzamide, furalaxyl, ofurace, benalaxyl, oxadixyl, propamocarb, ciprofuram, phenpiclonil, fludioxonil, pyrimethanil, cyprodinil, triticonazole, fluquinconazole, metconazole, spiroxamine, carpropamide, azoxystrobin , queroxim-de methyl, metominoestrobin and trifloxeistrobin. The compounds of the present invention can be advantageously employed in various ways. Since these compounds possess a broad spectrum fungicidal activity, they can be used in the storage of cereal grains. These compounds can also be used as fungicides in cereals including wheat, barley and rye, in rice, peanuts, beans and grapes, in grass, in fruits, nut and vegetable orchards, and applications for golf courses. Examples of the diseases against which the compounds of the invention are useful are helminthosporiosis of wheat and barley, powdery mildew of wheat and barley, rusts of the leaf and stem of wheat, blotch and rust of barley leaves, early tomato blight, tomato late blight, early peanut leaf spot, grape powdery mildew, rot of grape leaves, apple scab, apple powdery mildew, powdery mildew Cucurbitaceae, money rot of fruits, gray rot, powdery mildew of beans, antragnosis of cucurbits, septoria of wheat, blight of rice pod and rice blight.

Example 13 Numerous compounds of the present invention were tested for in vivo insecticidal activity against the insects described below. The following test method was applied to evaluate the components of the present invention in terms of insecticidal activity. The compound to be evaluated was dissolved in a suitable solvent, usually a mixture of acetone, methanol and water, and sprayed on three sheet discs cut using a flat fan nozzle. After spraying, the leaf discs were allowed to dry. Two discs were infested with leaf-eating insects (southern black caterpillar and Mexican bean weevil) and the third leaf disk was already infested with red spider two spots before spraying. The species of insects tested were: AW southern black caterpillar Spodoptera eridamia BB Mexican bean weevil Epilachna varivestis MTA two-spotted red spider Teranychus uricate Observations as percentage of control were made by visual inspection 24-48 hours after spraying. When tested against the southern black caterpillar at 300 grams per hectare 1.11, 1.102, and 1.105 provided control of 90% or better and when tested at 150 grams per hectare 1.14, 2.19, 2.28, 3.28A provided control from 90% or better. When tested against the Mexican bean weevil at 300 grams per hectare 1.11, 1.22A 1.22B, 1.27, 1.61A, 1.67, 1.94, 1.102, 1.105, 1.116, 1.116A, 2.11, 3.11, provided a 90% control or better and when tested at 150 grams per hectare 1.14, 2. HA, 2.12A, 2.19, 2.24, 2.25A, 2.25B, 2.27, 2.28, 2.34, 3. HA, 3.11B, 3.12A, 3.14A, 3.19 A, 3.24A, 3.25A, 3.26A, 3.27, 3.28A, 3.33A, 3.34A, 11.02A, 12.02A, 11.50A and 11.98A provided a control of 90% or better. When tested against the two-spotted red spider at 300 grams per hectare 1.11, 1.22A, 1.271.61A, 1.61B, 1.67, 1.94, 1.102, 1.105, 1.116, and 1.116A provided control of 90% or better and when tested at 150 grams per hectare 1.14, 2.12A, 2.14A, 2.19, 2.20A, 2.22A, 2.23A, 2.24 2.26A, 2.27, 2.28, 2.34. 3.12A, 3.14A, 3.19A, 3.20A, 3.23A, 3.26A, 3.27, 3.28A, 3.33A, 3.34 and 11.50A provided a control of 90% or better.

The compositions and compounds of the present invention can be applied directly to the site to be protected, for example, the area around or on the economic plants infected with insects or the plants on which infection is to be prevented. Examples of harmful insects belong to the orders Lepidoptera, Coleóptera, - Diptera, Thysanoptera, Hymenoptera, Heteroptera, Homoptera, Orthopera, and Acariña. The compounds and compositions can be applied as contact or systemic pesticides. The compounds of the invention are applied to the habitat of the insect at a rate of 0.0005 to 10 kilograms per hectare, preferably 0.05 to 5 and more preferably 0.1 to 1 kilograms per hectare. In the practice of the method of the invention, the active compound can be applied to the soil or foliage where it is absorbed by the plant, transmitted to other parts of the plant and, in the long run, ingested by the pest or insects by ingestion of the part or parts of the plant. This means of application is called systemic application. Alternatively, the active compound can be applied to the soil and contacted there with the insects and other pests that it is desired to control. This means of application is called soil application. Another possibility is that the active compound can be applied to the foliage of plants that will be released from insects and other pests that feed on the foliage. The compositions and formulations according to the present invention may also include known pesticidal compounds. This broadens the spectrum of activity of the preparation and can give rise to synergism. Among the suitable insecticides known in the art are those listed in the United States Patent 5, 075,471, see in particular columns 14 and 15. The compounds of the present invention can be applied in the form of compositions or formulations. An example of the preparation of compositions and formulations can be found in the publication of the American Chemical Society "Pesticidal Formulation Research" (1969), Series of Advances in Chemistry No. 86, written by Wade Van Valkenburg and in the publication of Marcel Dekker, Inc . "Pesticide Formulations", (1973) edited by Wade Van Valkenburg. In these compositions and formulations, the active substance is mixed with the conventional inert element acceptable from the agronomic point of view (that is, compatible with the plant or inhented from the point of view of the pesticide, or both), diluents or extenders of plagiarids, for example solid transported material or liquid transported material, of the type usable in conventional compositions or formulations of plagicides. By "agronomically acceptable carriers" is meant any substance that can be applied to dissolve, disperse or diffuse the active ingredient in the composition without hindering the effectiveness of the active ingredient and which alone has no significant harmful effect on the soil. , equipment, desirable plants or agronomic environment. If desired, adjuvants can also be combined, for example, sulfactants, stabilizers, antifoaming agents and anti-aging agents. Examples of compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes, dusting powders, wettable powders, emulsifiable concentrates, flowable elements, granules, baits, invert emulsions, aerosol compositions and Fumigating candles. Moisturizing powders, pastes, flowable elements, emulsifiable concentrates are concentrated preparations that are diluted with water before or during their use. In such formulations, the compounds are expanded with a liquid or solid carrier and, when desired, suitable surfactants are incorporated. Decoys are preparations that generally comprise a food or other substance attractive to insects, which includes at least one compound of the instant invention. Generally, it is desirable, particularly in the case of foliar spray formulations, to include adjuvants, for example, wetting agents, spreading agents, dispersing agents, tackifiers, adhesives and similar agents in accordance with a list of the adjuvants commonly used in the art. The technique, and an analysis thereof, can be found in many references, for example in the publication of John W. McCutcheon, "Detergents and Emulsifiers, Annual". The active compounds of the present invention can only be used as mixtures with one another or with solid or liquid dispersible carrier vehicles or other compatible active agents, especially plant protection agents, for example insecticides, arthropodicides, nematicides , fungicides, bactericides, rodenticides, herbicides, fertilizers, growth regulating agents and cinergists. In the composition of the invention, the active compound is present in an amount substantially between about 0.0001 (1: 999,999) -99 (99: 1)% by weight. For compositions suitable for storage or transportation, the amount of the active ingredient is preferably between about 0.5 (1: 199) -90 (9: 1)% by weight, and more preferably between about (1:99) -75 ( 3: 1)% weight of the mixture. Suitable compositions for direct filtration or field application generally contain the active compound in an amount substantially between 0.0001 (1: 999,999) -95 (19: 1)%, and more preferably between about 0.0005 (1: 199,999) -75 (3: 1)% by weight of the mixture. The composition can also be designated as a proportion of the compound with respect to the carrier. In the present invention, the proportion by weight of these materials (active compound / carrier) can vary from 99: 1 (99%) to 1: 4 (20%) and more preferably from 10: 1 (91%) to 1: 3 (25%). In general, the compounds of the present invention can be dissolved in certain solvents, for example, acetone, methanol, ethanol, dimethylformamide, pyridine or dimethylsulfoxide and the solutions can be diluted with water. The concentrations of the solution may vary from about 1% to about 90% with a preferred range of about 5% to about 50%. For the preparation of emulsifiable concentrates, the composition can be dissolved in suitable organic solvents, or a mixture of solvents, together with an emulsifying agent to improve the dispersion of the compound in water, the concentration of the active ingredient in the emulsifiable concentrates is generally about 10. % to about 90%, and in fluid emulsion concentrates it can be up to about 75%. Wettable powders suitable for sprinkling, can be prepared by mixing the compound with a finely divided solid, such as clay, inorganic silicate and carbonate, and silica and incorporating wetting agents, sticking agents or dispersing agents in mixtures. The concentration of the active ingredients of the formulations is generally in the range of from about 20% to about 99%, preferably from about 40% to about 75%. A typical wetting powder is made by mixing 50 parts of a compound of Formula I, 45 parts of a silicon dioxide, and 5 parts of sodium lingosulfonate. In another preparation a kaolin clay (Barden) is used in place of synthetic precipitated hydrated silicone dioxide in the above wetting powder, and in another preparation 25% is replaced with a synthetic sodium silicoaluminate. The powders are prepared with the compounds of Formula I, or the enantiomorphs, salts and complexes thereof having finely divided inert solids which may be organic or inorganic in nature. Useful materials for this purpose include botanical flours, silicas, silicates, carbonates and clays. A convenient method for preparing a powder is to dilute a wetting powder with a finely divided carrier. Powder concentrates containing from about 20% to about 80% active ingredient are commonly manufactured and are subsequently diluted from about 1% to about 10% to be used in the concentration. The active compounds can be applied as sprays and insecticides by commonly used methods, for example high gallonage hydraulic sprays, low gallonage sprays, ultra low volume sprays, air blast sprays, aerial sprays and powders. The present invention also contemplates methods for killing, combating or controlling pests comprising contacting the pests with a combative or toxic amount. (that is, an amount effective from a pesticidal point of view) of at least one active compound of the invention alone or together with a transported vehicle (composition or formulation) as noted above. The term "contacting" as used in the present specification and the claims means applying at least one of (a) said pests and (b) the corresponding habitat thereof (ie, the place to be protected, by example, a crop being grown or an area where a crop will be grown) the active compound of the present invention alone or as a constituent of a composition or formulation. In addition to the aforementioned ingredients, the preparations according to the invention may also include other substances commonly used in preparations of this type. For example, a lubricant, for example calcium stearate or magnesium stearate, can be added to the wetting powder or to a mixture to be granulated. In addition, for example, "adhesives" may be added, for example, polyvinyl alcohol-based cellulose derivatives or other colloidal materials, for example caffeine to improve the adhesion of the plasmicide to the surface to be protected.

Claims

CLAIMS A compound of the formula: (I) where X is N or CH; Y is 0, S, or NR8; A is selected from the group consisting of hydrogen, halo, cyano, (C1-C12) alkyl, and (C1-C12) alkoxy; Ri and R8 are independently selected from the group consisting of hydrogen and (C1-C4) alkyl; R2 is selected from a group consisting of hydrogen, alkyl (C? -C? 2), haloalkyl (C? -C12), cycloalkyl (C3-C-7), halo cycloalkyl (C3-C7), alkenyl (C2) -C8), halo alkenyl (C2-C8), alkynyl (Cz-C8), haloalkynyl (C2-C8), aryl, aralkyl, alkyl (C? -C4) heterocyclic and C (Rio) = N-0R9; R3 is selected from the group consisting of aryl, aralkyl, heterocyclic and (C1-C4) alkyl heterocyclic; R4 and R5 independently selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo (C1-C12) alkyl, cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2-Cd) ), halo alkenyl (C? -Cs), alkynyl (C2-C8), halo alkynyl (C2-C8), halo, cyanoalkoxycarbonyl (C? -C4), aryl, aralkyl, aryl cycloalkyl (C3-C7), aryl (C2-C8) alkenyl, heterocyclic and heterocyclic alkyl (C? -C4); Rβ, is selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? ~ C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2) -C8), halo alkenyl (C2-C8), alkynyl (C2-C8), halo alkynyl (C2-C8), halo, cyano, alkoxycarbonyl (C? -C4), aryl, aralkyl, aryl cycloalkyl (C3-C7) , aryl (C2-C8) alkenyl, heterocyclics and heterocyclic (C1-C4) alkyl; R7 is selected from the group consisting of aryl, aralkyl, heterocyclics and heterocyclic alkyl (C? -C4); R9 / is selected from the group consisting of hydrogen, (C1-C12) alkyl, halo alkyl (C? -C? 2), alkenyl (C2-C8), halo alkenyl (C2-Ca), alkynyl (C2-Cs) , halo alkynyl (C2-Ce), alkylcarbonyl, (C? ~ C4), alkoxycarbonyl (C1-C4), aryl, and aralkyl; Rio, is selected from the group consisting of hydrogen, alkyl (Cx-C? 2), halo alkyl (U-C12, cycloalkyl (C3-C7), halo cycloalkyl (C3 ~ C7), alkenyl (C2-C8), halo alkenyl (C2-C8), (C2-C8) alkynyl, (C2-C8) alkynyl, aryl, aralkyl, heterocyclic and heterocyclic (C1-C4) alkyl; and enantiomers, stereoisomers, and salts acceptable from the agronomic point of view of these.
2. The compound of claim 1 wherein X is CH, Y is 0, R2 is (Ci-C12) alkyl, and R6 and R7 are each independently of H or (C? -C) alkyl.
3. The compound of claim 2 wherein R7 is selected from the group consisting of phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-trifluoromethylphenyl, 3-chlorophenyl, 3-fluorophenyl, 3-trifluoromethylphenyl, 4-chlorophenyl, 4- fluorophenyl, 4-trifluoromethylphenyl and 2,4-dichlorophenyl.
4. The compound of claim 1 wherein X is N, Z is O or NH, R2 is (C? -C? 2) alkyl and R? - is H or (C1-C4) alkyl.
5. The compound of claim 4 wherein R7 is selected from the group consisting of phenyl, 2-chlorophenyl, 2-fluorophenyl, 2-trifluoromethylphenyl, 3-chlorophenyl, 3-fluorophenyl, 3-trifluoromethylphenyl, 4-chlorophenyl, 4- fluorophenyl, 4-trifluoromethylphenyl and 2,4-dichlorophenyl.
6. The compound of claim 1 wherein the compound is N-methyl-2- [2- (((1- (1- (3'-trifluoromethylphenyl) cyclopropyl) ethylidene) amin) oxy) -methyl) phenyl] -2-methoxyiminoacetamide.
7. The compound of claim 1 wherein the compound is N-methyl -2- [2- (((1- (2- (4'-chlorophenyl) cyclopropyl) ethylidene) amin) oxy) methyl) phenyl ] -2-methoxy-iminoacetamide.
8. A fungicide composition for controlling phytopathogenic fungi, which comprises an agronomically acceptable carrier and the compound of claim 1 wherein the ratio between the carrier and the compound is between 99.1 and 1: 4.
9. A method for controlling phytopathogenic fungi, which comprises applying the compound of claim 1 at the point of location where control is desired, at a rate of 0.005 to 50 kilograms per hectare.
10. A method for controlling insects, comprising applying to the insect habitat the compound of claim 1 at a rate of 0.005 to 10 kilograms per hectare. SUMMARY OF THE INVENTION Compounds with fungicidal and insecticidal properties having the formula: (I) where X is N or CH; Z is 0, S or NR8; A is hydrogen, halo, cyano, (C1-C12) alkyl, or alkoxy (C1-C12); Ri and R8 are independently hydrogen or (C1-C14) alkyl; R2 is selected from a group consisting of hydrogen, alkyl (CC? 2), halo (C1-C12) alkyl, (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, (C2-C8) alkenyl, (C2-C8) alkenyl halo, (C2-C8) alkynyl , (C2-C8) alkenyl halo, aryl, aralkyl, heterocyclic (C1-C4) alkyl and C (Rio) = N-0R9; R3 is selected from a group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? -C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl ( C2-C8), halo alkenyl (C2-Ca), (C2-C8) alkynyl, (C2-C8) alkynyl, aryl, aralkyl, aryl (C3-C7) cycloalkyl, heterocyclic and heterocyclic alkyl (C? -C); R4 and R5 independently selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (Q? - C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2-C8), halo (C2-C8) alkenyl, (C2-C8) alkynyl, haloalkynyl (C2-Ca), halo, cyano (C1-C4) alkoxycarbonyl, aryl, aralkyl, aryl cycloalkyl (C2-C? ), aryl (C2-C8) alkenyl, heterocyclic and heterocyclic (C1-C4) alkyl; R6 is selected from the group consisting of hydrogen, (C1-C12) alkyl, halo (C? -CX2) alkyl, (C3-C7) cycloalkyl, halo (C3-C7) cycloalkyl, (C2-C8) alkenyl, halo alkenyl (C2-C8), alkynyl (C2-Cs), halo alkynyl (C2-C8), halo, cyano, alkoxycarbonyl (C1-C4), aryl, aralkyl, aryl cycloalkyl (C3 ~ C), aryl alkenyl C2-C &;), heterocyclics and heterocyclic alkyl (C1-C4); R7 is selected from the group consisting of aryl, aralkyl, heterocyclics and heterocyclic alkyl (C1-C4); Rg is selected from the group consisting of hydrogen, (C1-C12) alkyl, halo (C1-C12) alkyl, (C2-C8) alkenyl, (C2-C8) halo alkenyl, (C2-C8) alkynyl, halo alkynyl (C2-C8), alkylcarbonyl, (C1-C4), alkoxycarbonyl (C1-C4), aryl, and aralkyl; Rio, is selected from the group consisting of hydrogen, alkyl (C? -C? 2), halo alkyl (C? -C? 2), cycloalkyl (C3-C7), halo cycloalkyl (C3-C7), alkenyl (C2) -C8), halo alkenyl (C2-C8), alkynyl (C2-C8), halo alkynyl (C2-C8), aryl, aralkyl, heterocyclic and heterocyclic alkyl (C1-C4).