MXPA99001278A - Unsaturated ether oximes, and its use as fungicides and insecticides - Google Patents

Abstract

Compuestos con propiedades fungicidas e insecticidas, que tienen la fórmula:en donde X es N o CH;Y es 0, S o NR6;A es independientemente hidrógeno, halo, ciano, alquilo (C1-C12) o alcoxi (Cl-C12);R1 y R6 son, independientemente, hidrógeno o alquilo (Cl-C4);R2 es hidrógeno, alquilo (C1-C12), halo (C1-C12)alquilo, cicloalquilo (C3-C7), alquenilo (C2-C8), halo(C2-C8)alquenilo, alquinilo (C2-C8), halo (C2-C8)alquinilo, arilo, aralquilo, heterocíclico o heterocíclic(C1-C4) alquilo;R3 es independientemente hidrógeno o alquilo (C1-C4) R4 y R5, son, independientemente, hidrógeno, alquilo(C1-C4)arilo, aralquilo, aril (C2-C8)alquenilo, aril (C2-C8)alquinilo, heterocíclico o heterociclic(C1-C4)alquilo, en donde si uno de R4 y R5 es hidrógeno o alquilo (Cl-C4) entonces el otro de R4 y R5 es otro que no sea hidrógeno o alquilo (Cl-C4) y sus enantiómeros, estereoisómeros y sales agron6micamente aceptables.

Description

Ether Unsaturated Oximes, and Their Use As Fungicides and Insecticides The present invention relates to certain ether oxime structures, compositions containing these compounds and methods for controlling fungi and insects by means of the use of a fungitoxic or insecticidal amount of these compounds. It is known that compounds having ether oxime structures have been disclosed in US Pat. No. 5,555,471, and that they are useful as fungicides. However, the effective antimicrobial spectrum of these compounds is still not enough. New ether oxime structures possessing a substituted alkenyl moiety have been discovered. These new compounds have fungicidal and insecticidal properties with a broad spectrum. The novel oximes of the present invention have the formula (I) (I) where X is N or CH; And it is O, S or NR6; A is hydrogen, halo, cyano, alkyl (C? -C12) or alkoxy (C? C? 2); Ri and Rs are, independently, hydrogen or (C1-C4) alkyl; R2 is hydrogen, (C-C12) alkyl, (C1-C12) alkyl, (C3-C7) cycloalkyl, (C2-C8) alkenyl, (C2-C8) alkenyl halo, (C2-C8) alkynyl, halo ( C2-C8) alkynyl, aryl, aralkyl, heterocyclic or heterocyclic (C1-C4) alkyl; R3 is hydrogen or (C1-C4) alkyl; R4 and R5 are, independently, hydrogen, (C1-C4) alkyl, aryl, aralkyl, aryl (C2-C8) alkenyl, aryl (C2-C8) alkynyl, heterocyclic or heterocyclic (C1-C4) alkyl, wherein only one of R and R5 can be selected from the group consisting of hydrogen and (C1-C4) alkyl. The (C1-C4) alkyl, (C1-C12) alkyl, alkenyl groups (C2-C8), (C2-C8) alkynyl and (C3-C7) cycloalkyl mentioned above can optionally be substituted with up to three substituents selected from the group consisting of nitro, halomethyl, alkoxycarbonyl (C? -C4) and cyano. The term "alkyl" includes both branched and straight chain alkyl groups having from 1 to 12 carbon atoms. Typical alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, t-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, isooctyl, 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 ethylenically unsaturated hydrocarbon group, straight or branched, having a chain length of 2 to 8 carbon atoms and one or two ethylenic bonds. The term "haloalkenyl" refers to an alkenyl group substituted with one to three halogen atoms. The term "alkynyl" refers to an unsaturated hydrocarbon group, straight or branched, having a chain length of 2 to 12 carbon atoms and one or two acetylenic bonds. The term aryl includes phenyl or naphthyl, which may be substituted with up to three substituents independently selected from the group consisting of halogen, cyano, trihalomethyl, phenyl, phenoxy, (C1-C3) alkyl, alkylthio (Ci-C4), alkylsulfoxide (C1 -C4), and halo (C? -C4) alkyl. Typical aryl substituents include, but are not limited to, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 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 unsubstituted six-membered unsaturated ring, containing one, two or three heteroatoms, preferably one, two or three heteroatoms independently selected from oxygen, nitrogen and sulfur, or a bicyclic unsaturated ring system containing up to 10 atoms, including a heteroatom selected from oxygen, nitrogen and sulfur. The term heterocyclic also refers to a five-membered unsaturated ring containing two or three heteroatoms, preferably two heteroatoms independently selected from oxygen, nitrogen or sulfur. Examples of heterocycles include, but are not limited to, 2-, 3- or 4-pyridinyl, pyrazinyl, 2-, 4- or 5-pyrimidinyl, pyridazinyl, triazolyl, imidazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl. , quinolyl and isoquinolyl. The heterocyclic ring can be optionally substituted with up to two substituents selected independently from the alkyl (C? -C2), halogen, cyano, nitro and trihalomethyl. The term "aralkyl" is used to describe a group wherein the alkyl chain is from 1 to 10 carbon atoms and can be branched or straight chain, preferably a straight chain, with the aryl portion, as defined above, forming a terminal portion of the part of aralkyl. Typical aralkyl moieties are optionally substituted benzyl, phenethyl, phenpropyl and phenylbutyl moieties. 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 parts are 2- (2-chlorophenyl) ethyl, 2- (3-chlorophenyl) ethyl, 2- (4-chlorophenyl) ethyl, 2- (2-fluorophenyl) 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- (2,4-dichlorophenyl) -ethyl, 2- (3,5-dimethoxyphenyl) ethyl. Typical phenpropyl portions 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 phenylbutyl 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-methyl-phenyl) butyl and 4- (2,4-dichlorophenyl) butyl. By saying halogen or halo, parts of iodine, fluorine, bromine and chlorine are included. Due to the double bonds of C = C or C = N, the new compounds of the general formula I can be obtained when preparing as E / Z isomeric mixtures. These isomers can be separated into individual components by conventional means. The alkenes of formula I can be obtained in the preparation as cis and trans isomeric mixtures, and can be separated into individual components by conventional means. Both the individual isomeric compounds and their mixtures are subject of the invention, and can be used as fungicides and insecticides. The present invention also includes the enantiomorphs, the agronomically acceptable salts, and the complexes of the formula (I). A preferred embodiment of this invention are the compounds, enantiomorphs, salts and complexes of the formula (I7), wherein A is hydrogen, R2 is hydrogen or alkyl (Cx-C4), R3 and R5 are hydrogen and R4 is aryl, aryl (C2-C8) alkenyl and heterocyclic. < r) A more preferred embodiment of this invention are the compounds, enantiomorphs, salts and complexes of the formula (I ''), where X is CH, Y is O, Rx and R2 are methyl, and R4 is aryl. d ") Typical compounds encompassed by the present invention of formula I include the compounds presented in table 1 of formula IV (X = CH) and formula V (X = N), where Y is O and A, X, R2, R3, R4 and s are defined in the table 1. Formula IV and V Table I Compound A E2 £ l Es. X Ei Point no. merger / Property 1. 01 H CH3 H H CH 2 -Cl-Ph oil 1. 02 H CH 3 H H CH 3-Cl-Ph. 1.03a H CH3 H H CH 4-Cl-Ph oil 1. 03b H CH3 H H CH 4-Cl-P oil 1. 04 H CH3 H H CH 2-CF3-Ph 1.05 H CH3 H H CH 3-CF3-Ph oil 1. 06 H CH3 H H CH 4-CF3-Ph 1.07 H CH3 H H CH 2-0CH3-Ph oil 1. 08 H CH3 H H CH 3-OCH3-Ph 1.09 H CH3 H H CH 4-OCH3-P 1.10 H CH3 H H CH 2 -CH3-Ph oil 1. 11 H CH3 H H CH 3 -CH 3 -P Ph 1.12 H CH 3 H H CH 4 -CH 3 -P P 1. 13 H CH3 H H CH l-Naphthyl oil 1. 14 H CH3 H H CH Ph-CH = CH- 1.15 H CH3 H H CH 4 Cl-PhCH = CH- oil 1. 16 H CH3 H H CH 2 -F-Ph oil 1. 17 H CH3 H H CH 3-F-Ph oil 1. 19 H CH3 H H CH 2-Br-Ph 1.20 H CH3 H H CH 4-Br-Ph 1.21 H CH 3 H H CH 2 -Furfuryl 1.22 H CH 3 H H CH 2,4-Cl-Ph oil 1. 23 H CH3 H H CH 3,4-Cl-Ph 1. 24 H CH 3 H H CH 3,5-Cl-Ph 1.25 H CH 3 H H CH 2-Pyridyl 1.26 H CH 3 H H CH 3-Pyridyl oil 1. 27 H CH3 H H CH 4-Pyridyl 1.28 H t -butyl H H CH 4 -Cl-Ph oil 1. 1. 33 H c -C3H5 HH CH 3-CF3-Ph 1.34 H c -C3H5 HH CH 4-CF3-Ph 1.35 H c -C3H5 HH CH 4-F-Ph 1.36 H 4 -Cl-Ph HH CH 4-Cl-Ph oil 1. 37 H 4 -Cl-Ph HH CH 3-CF 3-Ph 1.38 H 4 -Cl-Ph HH CH 4-CF 3-Ph 1.39 H 4 -Cl-Ph HH CH 4-F-PH 1.40 H CH3 HHN 2-Cl- Ph 1.41 H CH3 HHN 3-Cl-Ph 1.42 H CH3 HHN 4-Cl-Ph oil 1. 43 H CH3 HHN 2-CF3-Ph 1.44 H CH3 HHN 3-CF3-Ph 1.45 H CH3 HHN 4-CF3-Ph 1.46 H CH3 HHN 2-OCH3-Ph 1.47 H CH3 HHN 2-CH3-Ph 1.48 H CH3 HHN 3 -CH3-Ph 1.49 H CH3 HHN 4-CH3-Ph 1. 50 H CH3 H H N l-Naphthyl 1.51 H CH3 H H N Ph-CH = CH- 1.52 H CH3 H H N 2 -F-Ph 1.53 H CH3 H H N 3-F-Ph 1.54a H CH3 H H N 4-F-Ph oil 1. 54b H CH3 H H N 4-F-Ph oil 1. 55 H CH3 HHN 2-Br-Ph 1.56 H CH3 HHN 4-Br-Ph 1.57 H CH3 HHN 2-Furfuryl 1.58 H CH3 HHN 3.5-Cl-Ph 1.59 H CH3 HHN 2-Pyridyl 1.60 H CH3 HHN 3 -Pyridyl 1.61 H CH3 HHN 4-Pyridyl 1.62 H t -butyl HHN 4-Cl-Ph 1.63 H t -butyl HHN 3-CF3-Ph 1.64 H t -butyl HHN 4-CF3-Ph 1.65 H t -butyl HHM 4-F- Ph 1.66 H c -C3HS HHH 4-Cl-Ph 1.67 H c -C3H5 HHN 3-CF3-Ph 1.68 H c -C3H5 HHN 4-CF3-P 1.69 H c -C3H5 HHN 4-F-Ph 1.70 H 4 -ClPh HHN 4-Cl-Ph 1.71 H 4- -ClPh HHN 3-CF3-Ph 1.72 H 4 -Cl-Ph HHN 4-CF3-Ph Note that 1.03a and 1.03b are separate oxime isomers Typical compounds encompassed by the present invention of formula I include the compounds presented in Table II of formula VII (X is NH) and A, X, R2, R3, R4 and R5 are defined in Table II Formula VII Formula VII Table II Compound A E2 E2 Sfi X Ei Point no. fusion / Property 2.01 H CH3 HHN 2 -Cl-Ph 2.02 H CH3 HHN 3 -Cl-Ph 2.03 H CH3 HHN 4-Cl-Ph oil 2.04 H CH3 HHN 2-CF3-Ph 2.05 H CH3 HHN 3-CF3-Ph 2.06 H CH3 HHN 4-CF3-Ph 2.07 H CH3 HHN 2-OCH3-Ph 2.08 H CH3 HHN 2-CH3-Ph 2.09 H CH3 HHN 3-CH3-Ph 2. 10 H CH3 HHN 4-CH3-Ph 2.11 H CH3 HHN l-Naphthyl 2.12 H CH3 HHN Ph-CH = CH- 2.13 H CH3 HHN 2-F-Ph 2.14 H CH3 HHN 3-F-Ph 2.15 H CH3 HHN 4- F-Ph 2.16 H CH3 HHN 4-F-Ph 2.17 H CH3 HHN 2-Br-Ph 2.18 H CH3 HHN 4-Br-Ph 2.19 H CH3 HHN 2-Furfuril 2.20 H CH3 HHN 3 -pyridyl 2.21 H CH3 HHN 4- pyridyl 2.22 H t -butyl HHN 4-Cl-Ph 2.23 H t -butyl HHN 3-CF3-Ph 2.24 H t -butyl HHN 4-CF3-Ph 2.25 H t -butyl HHN 4-F-Ph 2.26 H c -C3H5 HHN 4-Cl-Ph 2.27 H c -C3H5 HHN 3-CF3-Ph 2.28 H c -C3H5 HHN 4-CF3-Ph 2.29 H c -C3H5 HHN 4-F-Ph 2.30 H 4 -Cl-Ph HHN 4-Cl -Ph 2.31 H 4 -Cl-Ph HHN 3-CF3-Ph 1. 03a, 1.03b and 1.54a, 1.54b are isomers of separate oximes. As used herein, "Ph" is understood as phenyl, and "c- denotes a cyclic compound.

Scheme A describes the preparation of the compounds of the formula (I), wherein X is CH or N, and Y is O (compounds of the formulas IV and V). Unsaturated oximes (III) are reacted with properly substituted benzyl (II) derivatives, wherein A is a halogen such as bromine, chlorine or iodine, preferably a benzyl bromide. An unsaturated oxime, represented by the general formula (III), is treated, at room temperature, with an appropriate base to form an anion, followed by the addition of the benzyl bromides (II). Typical bases used are metal hydrides such as sodium hydride, alkoxides such as sodium methoxide, and hydroxide bases such as sodium or potassium hydroxide, and alkaline bases such as sodium or potassium carbonate. Typical solvents used with the hydride bases are N, N-dimethylformamide (DMF) and tetrahydrofuran (THF); with hydroxide bases, solvents such as DMF, THF, methyl ethyl ketone (MEC) and ketone; and with alkaline bases, solvents such as DMF, acetone and MEC. As shown in scheme A, oxime appears at position E (assuming that R3C = CR4R5 is the longest substituent). It will be recognized that the Z isomer can also be produced as the mixtures. When the isomers are produced they are designated isomer A (higher Rf in thin layer chromatography) and isomer B (lower Rf in the thin layer chromatography). The determination of isomer A or B possesses an E or Z geometry that can be elaborated by means of conventional techniques, such as X-ray crystallography, or by means of spectroscopy such as nuclear magnetic resonance spectroscopy.

Scheme A X = CH (IV) X = N (V) The compounds of formula IV (X is CH) are prepared by alkylation with methyl Ea- (2-bromomethylphenyl) -β-methoxyacrylate in the presence of a base, preferably NaOH or KOH, in a solvent, preferably acetone or methyl ethyl ketone. The methyl 2- (bromomethyl) phenylglyoxylate O-methyloxime can be prepared as described in U.S. Pat. 4,999,042, columns 17-18, and 5,157,144, columns 17-18. The methyl 2- (bromomethyl) phenylglyoxylate O-methyloxime is prepared from 2 - . 2-methylphenyl-methyl acetate by treating it with an alkyl nitrite under basic conditions to provide, after methylation, the O-methyl oxime of methyl 2-methyl-phenyl-glyoxalate which can also be prepared from 2- methyl methyl phenylglyoxalate by means of treatment with 2-hydroxylamine hydrochloride and methylation or by means of treatment with methoxylaraine 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 to oximinoacetamides has been described in US Pat. Nos. 5,185,342, columns 22, 48 and 57, 5,221,691, columns 26 to 27, and 5,407,902, column 8. For example, the compounds of Table I of formula V, where X is N and Y is O, are treated with 40% of aqueous methylamine in methanol to provide the compounds of Table II of Formula VIII, where Y is NH. Alternatively, as shown in scheme B, intermediate unsaturated oximes (III) are reacted with (E) -2-methoxyimino-2- [2- (bromomethyl) phenyl] -acetamide of N-methyl in the presence of a base such as a hydroxide base, preferably in a solvent such as acetone or the methyl ethyl ketone, to provide the compounds of Table II of the formula (VII). N-methyl (E) -2-methoxy-imino-2- [2- (bromomethyl) phenyl] -acetamide is described in U.S. Pat. 5,387,714, column 13. As shown in scheme C, the oximes of the general formula (III) can be obtained by reacting the corresponding α, β-unsaturated aldehyde or ketone (VIII) with hydroxylamine hydrochloride at room temperature at reflux, preferably at room temperature, in a suitable solvent such as methanol or ethanol in the presence of an appropriate alkali such as sodium hydroxide or potassium carbonate. A general description of the synthesis of oxides with hydroxyl amine is described in March, Advanced Organic Chemistry, 4a. Ed., Pgs. 906-907, and its references. Oximes of the general formula (III), when obtained as a mixture of syn or anti oxime isomers, can be separated into individual isomers and alkylated, as described in schemes A and B. When a mixture of oximes of the general formula (III) is used in schemes A and B, the compounds of the formulas IV, V and VII can be separated into their individual isomers by means of conventional chromatography techniques.

Scheme C (vpi) (ni) The α, β-unsaturated aldehydes or ketones (VII) can be prepared by conventional condensation techniques. An extensive description of the synthesis of α, β-unsaturated aldehydes or ketones (enones) is described in March, Advanced Organic Chemistry, 4a. Ed. Pages. 937-955, and its references. For example, Organic Reactions, volume 16, describes the general condensation of aldol of ketones and aldehydes. For the compounds of the formula I of this invention, the ketones or aldehydes in general can be R4COR5, where R4 and R5 are previously defined or the ketones or aldehydes can be R2COCH2R3, where R2 and R3 are defined as in formula I. Typically, the ketone is dissolved in a hydroxylic solvent, such as methanol or ethanol, to which a solution of aldehyde in an aqueous basic solution is added dropwise. The typical bases used may be alkali metal hydroxides, such as barium, potassium or sodium hydroxide, and drip addition is conducted at 0 ° C. at 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 R4COR5 is added followed by the aqueous hydroxide solution. The following examples illustrate the present invention.

Example 1. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (2'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (Compound 1.01, Table 1 ). In a single-neck flask, with a capacity of 250 ml. , 14 gr. (99.6 moles, 1.0 eq) of o-chlorobenzaldehyde dissolved in 30 ml. of acetone. To this was added 5 gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125 eq) per drop and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. minutes 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase was washed with water three times and then dried, and concentrated to obtain 13.8 g. of (E) -4- (2-chlorophenyl) -3-buten-2-one as a light yellow oil in a yield of 76.9%. In a single neck flask, with a capacity of 250 ml., 5.4 gr. (29.9 moles, l.Oeq) of (E) -4- (2-chlorophenyl) -3-buten-2-one and 5.2 g. (75.4 moles, 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.) And then extracted with ethyl acetate (2 x 50 ml). The organic phase was dried and concentrated to obtain 3.4 g. of 2-oxime of 4- (2-chlorophenyl) -3-buten-2-one (E / Z mixture of oximes), in the form of an oil with a production of 58.1%. In a single-neck flask, with a capacity of 250ml. a suspension of 60% sodium hydride, 0.2gr. (5.0 moles, 1.03eq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.95 g was added to this stirred suspension. of 2-oxime of 4- (2-chlorophenyl) -3-buten-2 -one (4.86 moles, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1. 43gr. (5.01 moles, 1.Oeq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to silica gel column chromatography, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.45 g. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (2'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (single oxime isomer), a way of a slightly yellow oily substance in a production of 23.1%. ^ -HNMR (90MHz, CDC13): 2.07 (3H, s), 3.68 (3h, s), 3.80 (3H, s), 6.6-6.8 (2H, d), 7.0 -7.6 (8H, m), and 7.57 (1H, s).

Example 2a. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (compound 1.03a, table 1).

In a single-neck flask, with a capacity of 250 ml., 14 gr. (99.6 moles, l.Oeq) of p-chlorobenzaldehyde dissolved in 30ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles), 0.125eq), drip and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 15.5 g. of (E) -4- (4-chlorophenyl) -3-buten-2-one, in the form of a slightly yellow oil in an 86.2% yield. In a single-neck flask, with a capacity of 250ml. 5.4gr was loaded (29.9 moles, l.Oeq.) Of (E) -4- (2-chlorophenyl) -3-buten-2-one and 5.2 g. (75.4 moles, 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.2 g. of 2-oxime of 4- (4-chlorophenyl) -3-buten-2-one (E / Z mixture of oxime isomers), as an oil in a production of 54.7%.

In a single neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, 1.03eq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.95 g was added to this stirred suspension. of 2-oxime of 4- (4-chlorophenyl) -3-buten-2-one (4.86 moles, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 moles, 1.Oeq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and stirred continuously for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.55 g. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (single oxime isomer), a way of a slightly yellow oily substance in a production of 27.5%. 1 NMR (90MHz, CDC13): 2.07 (3H, s), 3.68 (3h, s), 3.80 (3H, s), 6.6-6.8 (2H, d), 7.0 -7.6 (8H, m), and 7.57 (1H , s).

Separation of the E / Z mixture of the oxime isomers of the 2-oxime of 4- (4-chlorophenyl) -3-buten-2-one. A 3: 2 mixture of the oxime isomers of the 2-oxime of 4- (4-chlorophenyl) -3-buten-2-one was chromatographed on two consignments using flash chromatography with silica gel: 1.4 g. of the oxime mixture using 1: 4 EtOAC / hexane, and 3gr. of the oxime mixture with 1: 3 EtOAc / hexane. The two separations were combined to provide a 1.14gr. of isomer of the highest Rf material (Rf = 0.36 in 1: 3 EtOAc: hexanes), designated as oxime isomer A, as a white / yellow solid, and 1.04g. of isomer of a lower Rf material (Rf = 0.21 in 1: 3 of EtOAc: exanos), designated as product of isomer of oxime B, as an off-white solid. The alkylation of the oxime isomer A gave a material identical to that prepared in example 2a as compound 1.03a.

Example 2b. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl-phenyl] propenoate (compound 1.03b, table 1). In a 28.7 g bottle, 0.94 grams (leq., 4.8 moles) of B-isomer of 4- (4-chlorophenyl) -3-buten-2-one 2-oxime (lower Rf oxime isomer) were charged. ) only, 1.37gr. (l.Oeq., 4. 8 moles) of methyl (E) -a- [2-bromomethyl) phenyl] -β-methoxyacrylate in 6 ml. of DMF, and 0.40gr. (1.5eq., 7.2 moles) of KOH powder pellets alone. The reaction was stirred at room temperature for four hours controlled by means of TLC, then the reaction was quenched with ethyl acetate and water, the phases were separated, dried, and the removal of the solvent gave 2.2 g. of the crude product as a yellow oil. The crude product was purified by flash chromatography with silica gel with 1: 3 EtOAc / hexane eluent to give 500 mg. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (4 '' chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (single oxime isomer of 1.03b ), in the manner of a light yellow oil in a production of 26.0%. NMR (Hl, 300MHz): 2.08 (s, 3H), 3.63 (s, 3H), 3.78 (s, 3H), 5.07 (s, 2H), 6.8-6.85 (d, lH), 7.1-7.6 (m, 10H).

E-i emplo 3. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (3'-trifluoromethylphenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (Compound 1.05, Table 1). In a single neck flask, with a 250ml capacity, 7.5gr was loaded. (43.1 moles, l.Oeq) of m-trifluoromethylbenzaldehyde dissolved in 15ml. of acetone. TO this one added 17.2gr. of 10% aqueous solution of sodium hydroxide (43 mol, l.Oeq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C. , while the mixture was stirred continuously for 30 minutes. 50ral was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 9.5 g. of 4- (3-trifluoromethylphenyl) -3-buten-2-one, in the form of a slightly yellow oil in a yield of 88.7%. In a single neck flask, with a capacity of 250 ml., 6.4 gr. (29.9 moles, l.Oeq.) Of 4- (3-trifluoromethylphenyl) -3-buten-2 -one and 5.2 g. (75.4 moles, 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours.

The reaction mixture was concentrated, diluted with water (50ml.), And then extracted with ethyl acetate (2 x 50ml.).

The organic phase was dried and concentrated to obtain 4.4 g. of 2-oxime of 4- (3-trifluoromethylphenyl) -3-buten-2-one (E / Z mixture of isomers), in the form of an oil in a 64.2% yield. In a single neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 1.15gr was added dropwise to this stirred suspension. of 2-oxime of 4- (3-trifluoromethylphenyl) -3-buten-2-one (5.02 moles, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 moles, 1.Oeq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.55 g. of methyl 3-methoxy-2- [2- ((((1-methyl-3- (3'-trifluoromethylphenyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (single oxime isomer), as a slightly yellow oily substance in a production of 29.9%. ^ -HNMR (90MHz, CDC13): 2.08 (3H, s), 3.68 (3H, s), 3.79 (3H, s), 5.12 (2H, s), 5.12 (2H, s), 6.7-6.9 (2H, m), 7.0-7.8 (8H, m) and 7.59 (1H, s).

Maximum point of IR absorption: 1697cm. -i, 1620cm. 1258cm "1, lllOcm." 1.

Use 4. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (2'-methoxyphenyl) -2-propenylidene) amino) -oxy) -methyl) phenyl] propenoate (Compound 1.07, Table 1). In a single-neck flask, with a capacity of 250 ml., 13.6 g. (100 moles, l.Oeq) of o-methoxybenzaldehyde dissolved in 30 ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C. , while the mixture was stirred continuously for 30 minutes. 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 14.5 g. of 4- (2-methoxyphenyl) -3-buten-2-one, in the form of a slightly yellow oil in a production of 82.3%. In a single neck flask, with a 250ml capacity, 5.28gr was loaded. (.30 mol, l.Oeq) of 4- (2-methoxyphenyl) -3-buten-2-one and 5.2 g. (75.4 moles, 2.5eq) of hydroxylamine hydrochloride, and 6 gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred at reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.1 g. of 2-oxime of 4- (2-methoxyphenyl) -3-buten-2 -one (E / Z mixture of isomers), in the form of an oil in a production of 54.1%. In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.95 g was added to this stirred suspension. of 2-oxime of 4- (2-methoxyphenyl) -3-buten-2 -one (4.97 moles, l.Oeq) in 10 ml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 mol, l.Oleq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.45 g. of 3- methyl methoxy-2- [2- ((((1-methyl-3- (3'-trifluoromethylphenyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (enriched in a major oxime isomer), way of a slightly yellow oily substance in a production of 22.7%, 1 NMR (90MHz, CDC13): 2.11 (3H, s), 3.68 (3h, s), 3.82 (3H, s), 3.87 (3H, s), 5.10 (2H, s) 6.8-7.0 (2H, m), 7.1 -7.8 (8H, m), and 7.58 (1H, s).

Ex ß plo 5. Methyl 3-methoxy-2 - [2 - ((((l (methyl-3- (2'-methylphenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (compound 1.10, table 1). In a single neck flask, with a 250ml capacity, it was loaded with 12.0gr. (100 moles, l.Oeq) of o-tolualdehyde dissolved in 30ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. minutes 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 13.8 g. of 4- (o-tolyl) -3-buten-2-one, in the form of a slightly yellow oil in an 86.3% yield.

In a single-neck flask, with a capacity of 250 ml, 4.8 g (30.0 mol, l.Oeq) of 4- (2-methoxyphenyl) -3-buten-2-one and 5.2 g (75.4 mol) were charged. , 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.0 g. of 2-oxime of 4- (o-toyl) -3-buten-2-one (E / Z mixture of isomers), as an oil in a production of 57.1%. In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.88gr was added dropwise to this stirred suspension. of 2-oxime of 4- (o-tolyl) -3-buten-2-one (5.03 moles, l.Oeq) in 10 ml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 mol, l.Oleq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.45 g. of methyl 3-methoxy-2- [2- (((((1-methyl-3- (o-tolyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (a major oxime isomer), as a a slightly yellow oily substance in a production of 23.7%, 1 NMR (90MHz, CDC13): 2.05 (3H, s), 2.33 (3H, s), 3.62 (3H, s), 3.74 (3H, s), 5.03 (2H , s) 6.8-7.0 (2H, m), 7.0 -7.5 (8H, m), and 7.37 (1H, s).

Example 6. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (4'-methylphenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (Compound 1.12, Table 1) . In a single neck flask, with a 250ml capacity, it was loaded with 12.0gr. (100 moles, l.Oeq) of p-tolualdehyde dissolved in 30ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. minutes 50 ml was added to the mixture. of water, followed by lOOml. of acetate ethyl, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 13.5gr. of 4- (p-tolyl) -3-buten-2-one, in the form of a slightly yellow oil in a yield of 84.3%. In a single-neck flask, with a capacity of 250 ml, were charged 4.8 g (30.0 mol, l.Oeq) of 4- (p-tolyl) -3-buten-2-one and 5.2 g (75.4 mol). , 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.2 g. of 2-oxime of 4- (p-tolyl) -3-buten-2-one (E / Z mixture of isomers), as an oil in a 60.9% yield. In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.88gr was added dropwise to this stirred suspension. from 2-oxime of 4- (p-tolyl) -3-buten-2-one (5.02 moles, l.Oeq) in IOml. of N, -dimethylformamide. After 30 minutes, 1.43gr. (5.01 mol, l.Oleq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and stirred continuously for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography by silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.44 g. of methyl 3-methoxy-2- [2 - ((((l-methyl-3- (p-tolyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (a major oxime isomer), as a a slightly yellow oily substance in a production of 23.7%, 1 NMR (90MHz, CDC13): 2.04 (3H, s), 2.31 (3H, s), 3.64 (3H, s), 3.76 (3H, s), 5.04 (2H , s) 6.73 (2H, s), 7.0 -7.5 (8H, m), and 7.48 (1H, s).

Example 7. Methyl 3-methoxy-2- [2- ((((1-methyl-3- (1-naphthyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (Compound 1.13, Table 1) . In a single neck flask, with a 250ml capacity, it was loaded with 15.6gr. (100 moles, l.Oeq) of l-naphthaldehyde dissolved in 30 ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0. 125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 16.5 g. of 4- (l-naphthyl) -3-buten-2-one, in the form of a slightly yellow oil in a production of 84.3%. In a single-neck flask, with a capacity of 250 ml, 5.88 g (30.3 mol, l.Oeq) of 4- (l-naphthyl) -3-buten-2-one and 5.2 g (75.4 mol) were charged. , 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.9 g. of 2-oxime of 4- (l-naphthyl) -3-buten-2-one (E / Z mixture of isomers), as an oil in a 62% yield. In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 1.05 gr. Were added to this stirred suspension. from 2-oxime of 4- (l-naphthyl) -3-buten-2-one (5.02 moles, l.Oeq) in 10 ml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 moles, lOOOq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.75 g. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (1-naphthyl) -2-propenylidene) amino) oxy) methyl) methylphenyl] copolynate (a major oxime isomer), as a a slightly yellow oily substance in a production of 36.1%, 1 NMR (90MHz, CDC13): 2.02 (3H, s), 3.69 (3H, s), 3.80 (3H, s), 5.14 (2H, s), 6.8-7.0 (2H, d) 7.1 -8.2 (11H, m), and 7.58 (1H, s).

Example 8. 3-methoxy-2- [2- ((((1-methyl-3- (2-phenylethenyl) -2-propenylidene) amino) oxy) methyl) phenyl] propenoate (Cund 1.14, Table 1).

In a single-neck flask, with a capacity of 250ml., They loaded 13.2gr. (100 moles, l.Oeq) of cinnamaldehyde dissolved in 30ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C, while the mixture was stirred continuously for 30 minutes. minutes 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 15.7 g. of 4- (2-phenylethenyl) -3-buten-2-one, in the form of a slightly yellow oil in a 91% yield. In a single-neck flask, with a capacity of 250 ml, 5.28 g (30 mol, l.Oeq) of 4- (l-naphthyl) -3-buten-2-one and 5.2 g (75.4 mol) were charged. , 2.5eq) of hydroxylamine hydrochloride, and 6gr. of 50% sodium hydroxide (75 moles, 2.5eq) and 100 ml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.4 g. of 2-oxime of 4- (2-phenylethenyl) -3-buten-2-one (E / Z mixture of isomers), in the manner of an oil in a yield of 60.6%.

In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.94 g was added to this stirred suspension. of 2-oxime of 4- (2-phenylethenyl) -3-buten-2-one (5.02 moles, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 moles, 1.Oeq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.65 g. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (2-phenylethenyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (a major oxime isomer), as a a slightly yellow oily substance in a production of 33.2%. 1 NMR (90MHz, CDC13): 2.01 (3H, s), 3.62 (3H, s), 3.75 (3H, s), 5.02 (2H, s), 6.1-6.8 (4H, m) 7.0 - 7.5 (9H, m ), and 7.47 (1H, s).

Example 9. Methyl 3-methoxy-2 - [2- ((((l-methyl-3- (4-fluorophenyl) -2-propenylidene) mino) oxy) methyl) phenyl] -roperoxide (cund 1.18, Table 1 ). In a single-neck flask, with a 250ml capacity, it was loaded with 12.4gr. (100 moles, l.Oeq) of 4-fluorobenzaldehyde dissolved in 30ml. of acetone. To this was added 5gr. of 10% aqueous solution of sodium hydroxide (12.5 moles, 0.125eq), by dripping and, during the course of the addition, the temperature was maintained at no more than 25 ° C. , while the mixture was stirred continuously for 30 minutes. 50 ml was added to the mixture. of water, followed by lOOml. of ethyl acetate, the phases were separated and the organic phase washed with water three times and then dried, and concentrated to obtain 13.5 g. of 4- (4-fluorophenyl) -3-buten-2-one, in the form of a slightly yellow oil in a yield of 82.3%. In a single-neck flask, with a capacity of 250 ml., 4.92 g (30 mol, l.Oeq) of 4- (4-fluorophenyl) -3-buten-2-one and 5.2 g. (75.4 moles, 2.5eq) of hydroxylamine hydrochloride, and 6gr. 50% sodium hydroxide (75%) moles, 2.5eq) and lOOml. of methanol. The reaction mixture was stirred under reflux for two hours. The reaction mixture was concentrated, diluted with water (50 ml.), And then extracted with ethyl acetate (2 x 50 ml.). The organic phase was dried and concentrated to obtain 3.4 g. of 2-oxime of 4- (4-fluorophenyl) -3-buten-2 -one (E / Z mixture of isomers), in the manner of an oil in a yield of 63.3%. In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.90 g was added to this stirred suspension. of 2-oxime of 4- (4-fluorophenyl) -3-buten-2-one (5.02 moles, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1.43gr. (5.01 moles, 1.Oeq) of methyl (E) -a- [2- (bromomethyl) phenyl] -β-methoxyacrylate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of ethyl acetate. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and oil as the elutive solution to obtain 0.55gr. of methyl 3-methoxy-2- [2- ((((l-methyl-3- (4-fluorophenyl) -2-propenylidene) amino) oxy) methylphenyl] propenoate (a major oxime isomer), as a a slightly yellow oily substance in a production of 28.6%. ^? MR (90MHz, CDC13): 2.07 (3H, s), 3.68 (3H, s), 3.80 (3H, s), 5.07 (2H, s), 6.78 (2H, s) 7.0 - 7.5 (8H, m), and 7.53 (1H, s).

Example 10. 2- [2- ((((L-Methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] -2-methoxyiminoacetate (Compound 1.42, Table 1). In a single-neck flask, with a capacity of 250 ml., A suspension of 60% sodium hydride, 0.2 g. (5.0 moles, l.Oeq., Washed with n-hexane) in lOml. of N, N-dimethylformamide (DMF). While stirring at room temperature, 0.95 g was added to this stirred suspension. of 2-oxime of 4- (4-chlorophenyl) -3-buten-2-one (4.87 mol, l.Oeq) in lOml. of N, N-dimethylformamide. After 30 minutes, 1.44gr. (5.01 moles, l.Oleq) of methyl 2- (2-methylphenyl) -2-methoxyiminoacetate in lOml. of DMF were added to the reaction mixture, and were continuously stirred for two hours at room temperature. The reaction mixture was emptied in 50 ml. of water, extracted with 2 x 50ml. of acetate ethyl. The combined organic extracts were washed with 3 x 50ml. of water, dried and concentrated, to obtain the raw product. The above was subjected to column chromatography on silica gel, using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution to obtain 0.57 g. of methyl 2- [2- ((((1-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] -2-methoxyiminoacetate (a major oxime isomer), way of a slightly yellow oily substance in a production of 29.2%. ^? NMR (90MHz, CDC13): 2.12 (3H, s), 3.83 (3H, s), 4.03 (3H, s), 5.08 (2H, s), 6.82 (2H, d) and 7.1-7.5 (8H, m).

Example 11. 2- [2- ((((L-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] -2-methoxyiminoacetamide (compound 2.03, table 1). In a round bottom flask, with a capacity of 100 ml., 0.25 g was added. (0.625 moles, l.Oeq) of 2- [2 - (((methyl (l-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] -2-methoxyiminoacetate ( compound 1.42), and 0.097gr. of 40% aqueous methylamine (1250 moles, 2. Oeq) were stirred overnight in 30 ml. of methanol. After concentrating the mixture, it was extracted with 2 x 50ml. of ethyl acetate. The extract collected was washed three times with water, and then dried and concentrated to obtain a crude product. It was subjected to column chromatography using a 1: 2 mixture of ethyl acetate and petroleum ether as the eluent solution, to obtain 0.21 g. of the title compound, as a slightly yellow oily substance in an 84% yield. 1HNMR (90MHz, CDC13): 2.11 (3H, s), 2.90 (3H, d), 3.96 (3H, s), 5.10 (2H, s), 6.57 (lH, br), 6.81 (2H, s), and 7.1 -7.7 (8H, m).

Example 12. The NMR proton data (200MHz) is given in Table III for representative compounds typical of Tables I and II.

Table III Compound no. Proton NMR d (chemical changes related to TMS) 1. 16 2.02 (s, 3H), 3.68 (s, 3H), 3.77 (s, 3H), 5.12 (s, 2H), 6..8-7.2 (? Bq, 2H), and 7.0-7.8 (m, 9H) ). 1. 17 2.07 (s, 3H), 3.68 (s, 3H), 3.79 (s, 3H), 5.11 (s, 2H), 6..79-6.80 (? Bq, 2H), and 6.9-7.7 (m, 9H) ). 1. 22 2.10 (s, 3H),? 3.69 (s, 3H), 3.81 (s, 3H), 5.11 (s, 2H), 6..80-7.11 (ABq, 2H)) and 7.2-7.7 (m, 8H) ). 1. 28 2.02 (s, 3H), 3.68 (s, 3H), 3.77 (s, 3H), 5.12 (s, 2H), 6..8-7.2 (ABq, 2H), and 7.0-7.8 (m, 9H) . 1. 32 0.79-0.87 (m, 4H), 1.7-1.8 (m, lH), 3.61 (s, 3H), 3.79 (s, 3II), 5.04 (s, 2H), and 7.1-7.8 (m, llH). 1. 36a 3.61 (s, 3H), 3.74 (s, 3H), 5.20 (s, 2H), 6.60-6.65 (d, lH), and 7.2-7.5 (m, 14H). 1.36b 3.65 (s, 3H), 3.74 (s, 3H), 5.09 (s, 2H), 6.3-6.4 6.8-6.9 (ABq, 2H), and 7.1-7.8 (m, 14H). 1.54a 2.04 (s, 3H), 3.84 (s, 3H), 4.04 (s, 3H), 5.07 (s, 2H), 6..72-6.85 (? Bq, 2H), and 7.0-7.5 (m, 8H). 1. 54b 2.06 (s, 3H), 3.72 (s, 3H), 4.02 (?, 3H), 5.04 (s, 2H), and 6..80-7.6 (m, 10H).

Note: the 1HNMR spectrum was recorded using CDCI3. The following codes were used: s = single, d = double, t = triple, m = multiple, br = larger point.

Example 13. Numerous compounds of this 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 2: 1: 1 mixture of water, acetone and methanol (by volume) to achieve the proper concentration. The solution was sprayed on the plants, and allowed to dry for two hours. Next, 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 the treatment of the plants with the compounds of this invention. The rest of the technique of each of the tests is given below along with the results for various compounds described herein by the "compound no." against the various fungi in a dose of 100 or 150 grams per hectare. The results are the control of disease in percentage compared to the untreated table, where with one hundred the complete control of the disease was qualified and with zero the control of the disease was not. Disease control in percentage is reported in activity groups, where A is 90-100% disease control, B is 70-89% control, C is 50-69% control, and D is less than 50% of disease control. The application of test fungal spores to the test plants was as follows: Triso leaf blight (AHT). Puccinia recóndi ta (f.sp.trítici) was cultivated on seven days old wheat (Fielder culture) during a period of 12 days in the greenhouse. The spores were collected from the leaves by placing them on aluminum sheets. The spores were cleaned by sieving them in a sieve with 250 micron openings, and they were stored dry. The dried spores were used in a month. A suspension of spores was prepared from the dry uredia by adding 20gr. (9.5 million spores) per ml. of Soltrol® oil. The suspension was placed in gelatin capsules (0.7 ml capacity) that were added to the oil sprays. One capsule is used per square spot of two square inches of plants with seven days old, Fielder culture. After waiting at least 15 minutes for the The oil was evaporated from the wheat leaves, the plants were placed in a black steam chamber (18-20 ° C and 100% relative humidity) for 24 hours. Then, the plants were placed in the greenhouse, and the disease was evaluated after twelve days.

Pustule of wheat hort (PHT). The cultures of Septoria nodorum were maintained on agar plates with Czapek-Dox V-8 juice in an incubator at 20 ° C., with alternating periods of twelve hours of light and twelve hours of darkness for two weeks. A water suspension of the spores was obtained by stirring the part of the plate that had fungus material in deionized water, and filtering through cheesecloth. The water suspension containing spores was diluted to a spore concentration of 3.0 x 106 spores per ml. The inoculum was dispersed by means of 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 humid showcase at 20 ° C, with alternating periods of twelve hours of light and twelve hours of darkness for seven days. The inoculated seedbeds were then t to a room with controlled temperature at 20 ° C. for incubate them for two days. Disease control values were recorded as percent control.

Wheat blight (TPT). The Erysiphe graminis (f., Tri tici) was cultivated on wheat seedlings, Fielder culture, in a room with controlled temperature at 18 ° C. The blight spores were shaken from the cultivation plants in seven-day-old wheat seedbeds, which had previously been sprayed with the fungicide compound. The inoculated seedlings were stored in a room with a controlled temperature of 18 ° C, and they were harvested. Disease control in percent was assessed seven days after inoculation.

Cucumber powder blight (TPP). The Sphaerotheca fulginea was kept on cucumber plants, Bush Champion crop, in the greenhouse. The inoculum was prepared by putting five to ten leaves with a lot of blight in a 500ml glass jar. of water containing one drop of Tween® per lOOml. After stirring the liquid and the leaves, the inoculum was filtered through cheesecloth and sprayed on the plants with a spray bottle atomizer. The spore count was 100,000 spores / ml. Then, the Plants were put in the greenhouse for infection and incubation. The plants were graded seven days after inoculation. Disease control values were recorded as percent control.

Late tomato rust (RTT). Cultures of Phytophthora infestans were maintained on agar-agar enhanced with green pea for two to three weeks. The spores were removed from the agar-agar and washed with water and dispersed with a DeVilbiss atomizer on the leaves of three-week-old Pixie tomato plants, which had been previously treated with the compound of the present invention. The inoculated plants were placed in a humid showcase at 20 ° C. for 24 hours for the infection. Then the plants were taken to a room with a controlled environment at 20 ° C. and 90% humidity. Plants were scored with respect to disease control after five days.

Hairy grape mildew (MVTJ). The Plasmopara vi tícola remained on leaves of grape plants, culture Delaware, in a chamber of temperature controlled to 20 ° C. in humid air with moderate light intensity for seven to eight days. A suspension was obtained of water from the spores of the infested leaves, and the concentration of spores was adjusted to approximately 3 x 105 per ml. of water. The Delaware grape plants were inoculated by spraying the back of the leaves with a De Vilbiss atomizer, until small drops were observed on the leaves. The inoculated leaves were incubated in a steam chamber for 24 hours at 20 ° C. Then, the plants were taken to an environmental room controlled at 20 ° C. The control values of the disease were recorded as control in percent seven days after the inoculation.

Rice blight (AA). Cultures of Pyricularia oyrzae were maintained on potato dextrose agar for two to three weeks. The spores were removed from the agar-agar and washed with water containing one drop of Tween 80 per 100. After filtering the spore suspension through two sheets of cheesecloth, the spore count was adjusted to 5 x 105. Spore suspension was sprayed on rice plants with twelve days old, culture Ml, using a De Vilbiss atomizer. The inoculated plants were placed in a humidity chamber at 20 ° C. for 36 hours for the infection to happen. After the period of infection, the plants were taken to the greenhouse. After six days, the plants were rated for disease control.

Botrytis in the cucumber (BOT). The cucumber plants were kept in the greenhouse. Large, fully expanded leaves were collected from the plates. The stems were wrapped with cotton, the leaves were placed in a large petri dish (15cm in diameter), and the leaves were held with glass sticks. 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 approximately two hours. Botrytis cinerea cultures were maintained on potato dextrose agar for two to three weeks. 6mm agar-agar plugs were cut. in diameter with a cork drill from the periphery of the margin of the mushroom colony. These agar-agar plugs were placed with the fungal surface in contact with the treated upper surface of the cucumber leaf. Each leaf received two mycelial plugs. After placing the cover of the petri dish on the leaves, the plates were returned to a controlled environmental chamber at 20 ° C. and 90% humidity for three to four days. After this time, the diameter of the lesions produced by the mycelial plug was measured. The average lesion size was compared with the size of the lesion produced in the control leaves. The data were expressed as control in percent.

Cucumber Hairy Blight (TVP). The cucumber plants were kept in the greenhouse. Fully expanded long leaves were collected from the plates. The stems were wrapped in cotton, the leaves were placed in a large petri dish (15 cm in diameter), and the leaves were held with glass sticks. 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 approximately two hours. The cultures of Pseudoperonospora cubensis were kept on the cucumber leaves. 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 controlled environmental chamber at 20 ° C. and 90% humidity for five days. After this time, the leaves were examined to see the development of the disease. The data were expressed as control in percent.

Rhizoctonia leaf rust (RHR). The bean plants were kept in the greenhouse. The fully expanded leaves containing two leaflets were collected from the plates. The stems were wrapped with cotton, the leaves placed in a large petri dish (15cm in diameter), and the leaves were held with glass sticks. The upper cover of the plate was removed and the upper surface of the bean leaf was sprayed with the compounds of the present invention. The sheet was allowed to air dry for about two hours. Cultures of Rhizoctonia solani were maintained on potato dextrose agar for one week. 6mm agar-agar plugs. in diameter were cut with a cork drill from the periphery of the margin of the fungal colony. These agar-agar plugs were placed with the fungal surface in contact with the treated upper surface of the bean leaf. Each leaf received two mycelial plugs. After placing the cover of the petri dish on the leaves, the plates were returned to a controlled environmental chamber at 20 ° C. and 90% humidity for five days. After this time, the diameter of the lesions produced by the mycelial plug was measured. The average lesion size was compared with the size of the lesion produced on the control sheets. The data were expressed as control in percent. When tested against blast of wheat leaf at 150 grams per hectare, compounds 1.03a, 1.03b, 1.05, 1.07, 1.10, 1.12, 1.14, 1.16, 1.17, 1.18, 1.26, 1. 42 and 2.03 exhibited control in the classification group A. When tested against the wheat leaf pustule at 150 grams per hectare, compounds 1.03a, 1.03b, 1.10, 1.16, 1.17, 1.18, and 2.03 exhibited control in the classification group A. When tested against dust wheat blight at 150 grams per hectare, compounds 1.03a, 1.05, 1.07, 1.13, 1.16, 1.18 and 1.32 exhibited control in classification group A. When tested against cucumber powder blight in a dose of 150 grams per hectare, compounds 1.03a, 1.03b, 1.05, 1.10, 1.12, 1.16, 1.17, 1.18 and 2. 03 exhibited control in classification group A (> .90% control). When tested against tomato late blight at 150 grams per hectare, compounds 1.03a, 1.03b, 1.12, 1.16, 1.17, 1.14, 1.18, 1.42 and 2.03 exhibited control in classification group A.

When tested against hairy grape mildew at 150 grams per hectare, compounds 1.03a, 1.03b, 1. 05, 1.07, 1.10, 1.12, 1.14, 1.16, 1.17, 1.18, 1.26, 1.28, 1. 32, 1.42 and 2.03 exhibited control in classification group A. When tested against rice blast at 150 grams per hectare, compounds 1.03a, 1.03b, 1.10, 1.10, 1.16, 1.17 and 1.18 exhibited control in the classification group A. When tested against gray mold of cucumber at 100 grams per hectare, compounds 1.03a, 1.03by 1.42 exhibited control in the classification group A. When tested in 100 grams per hectare. Compounds 1.05, 1.10, 1.14, 1.18 and 2.03 exhibited control in the classification group B. When tested against cucumber hairy blight at 100 grams per hectare, compounds 1.01, 1.03a, 1.03b, 1.05, 1.07, 1.10, 1.12, 1.13, 1.14, 1.18, 1.42 and 2.03 exhibited control in the classification group A. When tested against rhizoctonia leaf rust at 100 grams per hectare, compounds 1.05 and 1.14 exhibited control in the group of Classification A. Compounds 1.01 1.03a, 1.10, 1.12, 1.13, 1.42 and 2.03 exhibited control in the classification group B.

The compounds of this 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 to be protected. The compounds of this invention can be applied as fungicidal sprays by means of commonly employed methods, such as conventional high volume hydraulic sprayers, low volume sprayers, spray / air injection, powders and aerial sprays. The dilution and index of application will depend on the type of equipment used, the method of application, plants to be treated and diseases that will be controlled. In general, the compounds of this invention will be applied in amounts 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 the active ingredient. As a seed protector, the amount of toxic covered in the seed is usually at a dose rate of from about 0.05 to about 20, preferably from about 0.05 to about 4, and more preferably from about 0.1 to about 1 gram per hundred. kilograms of seed. As a fungicide for the earth, the chemical can be incorporated into the soil or applied to the surface usually at an index of from about 0.02 to about 20, preferably from about 0.05 to about 10, and more preferably from about 0.1 to about 5 kilograms per hectare. As a foliar fungicide, the toxicant is usually applied to growing plants at an index of about 0.01 to about 10, preferably about 0.02 to 5, and more preferably about 0.25 to about one kilogram per hectare. Since the compounds of this invention exhibit fungicidal activity, these compounds can be combined with other known fungicides to provide more extensive spectrum activity. Suitable fungicides include, but are not limited to, those 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 this invention are dimetomorph, cymoxanil, trifluzamide, furalaxyl, ofurace, benalaxyl, oxadixyl, propamocarb, ciprofuram, phenpiclonil, fludioxonil, pyrimethanil, cyprodinil, triticonazole, fluquinconazole, metconazole, spiroxamine, carpropamid. , azoxystrobin, cresoxim-methyl, metominostrobin and trifloxystrobin.

The compounds of this invention can be advantageously employed in various ways. Since these compounds possess extensive spectrum fungicidal activity, they can be employed in the storage of cereal grain. These compounds can also be used as fungicides in cereals including wheat, barley and rye, in rice, peanuts, beans and grapes, on turf, in cereal, nuts and vegetable gardens, and for applications in courses of golf courses. Examples of diseases against which the compounds of the invention are useful include corn helminthosporium and barley, wheat and barley powder blight, blight of the stem and leaf of wheat, leaf blight and barley strips, early tomato scab, late tomato scab, early peanut leaf stains, powdery mildew of grape, black grape rot, apple scab, powdered apple blight, cucumber powder blight, rot fruit coffee, botrytis, bean powder blight, cucumber anthracinia, wheat nodorum septoria, rice leaf rust and rice blast.

Example 14, Numerous compounds of this invention were tested for insecticidal activity in vivo against the insects described below. The following test method was used to evaluate the compounds of the present invention in relation to the insecticidal activity. The compound to be evaluated was dissolved in an appropriate solvent, usually a mixture of acetone, methanol and water, and sprayed on three discs with sated leaves using a horizontal fan injector. After the spraying, the discs were allowed to dry with leaves. Two discs were infested with leaf-chewing insects (southern earthworm and Mexican bean beetle) and the third disk with leaves was already infested with spider mites of two veins before spraying it. The species of insects tested were: AW southern worm Spodoptera eridamia BB Mexican bean beetle Epilachna varivestis MTA double-spider spider mite Teranychus uricate Observations as percent control were made by visual inspection 24 to 48 hours after spraying. When tested against the southern earthworm, at 300 grams per hectare, compounds 1.03a, 1.05 and 1.13 gave 50% or better control, and when subjected to test at 150 grams per hectare compounds 1.16, 1.17, 1.18, 1.32 and 2.03 gave 50% or better control. When tested against the Mexican bean beetle, at 300 grams / hectare, the compounds 1.03a, 1.05, 1.07, 1.13 gave 50% or better control, and when they were tested at 150 grams per hectare, the compounds 1.16 , 1.18, 1.22 and 1.32 gave 50% or better control. When tested against the double-spider mite, at 300 grams / hectare, compound 1.05 gave 50% or better control, and when tested, at 150 grams per hectare, compound 1.16 gave a 50 % or better control.

Example 15 Lethal activity and anti-food activity were tested with earthworms (Leucaniar Separata). A certain number of three-month-old larvae were released in a culture vessel, and were cultured with the corn liquor treated with medicament, soaking. A ceramic spray tower was employed in the manner of the method of administration of the medicament. The sprayed amount was 1ml. , the spray pressure was 13.51b. / inch2 (93kPa), and the concentration of the applied compound was 500ppm and 120ppm. The results of the test are presented in the following table. The percentage of food consumed, as shown in the table, should be related to the number of remaining organisms and their health.

Table IV Co pußsto no. Dosage 24hrs. 48 rs. 5 days (ppm) death% food death% food death% food (%) consumed (%) consumed (%) consumed 1. 03a 500 0 3 40 5 80 10 1. 03a 120 0 15 0 25 0 40 1. 05 500 0 0 60 3 100 3 1.05 120 0 10 0 15 20 20 no 0 100 0 100 0 100 The compositions and compounds of this invention can be applied directly to the site to be protected, for example, the surrounding area or in the economic plants infected with the insects or in the plants where the infestation is to be prevented. Examples of harmful insects belong to the orders Lepidoptera, Coleoptera, Diptera, Thysanoptera, Hymenoptera, Heteroptera, Homoptera, Orthoptera and Acariña. The compounds and compositions can be used as both systemic or contact pesticides. The compounds of the invention are applied to the habitat of insects at an index of 0.0005 to 10 kilograms per hectare, preferably 0.05 to 5 and more preferably 0.1 to 1 kilogram 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, transferred to other parts of the plant and finally eaten by the plague or insects when eating the Parts of the plant. The means of application refers to the systemic application. Alternatively, the active compound can be applied to the ground and contacted there with the insects and other pests that will be controlled. This means of application refers to the application on earth. In another alternative, the active compound can be applied to the leaves of the plants that want to be released from insects and other pests that feed on the foliage. The compositions and formulations according to the present invention can also include known pesticidal compounds. This expands the spectrum of activity of the preparation, and may increase synergism. Suitable insecticides known in the art include those listed in U.S. Pat. No. 5,075,471, see in particular columns 14 and 15. The compounds of the present invention can be used in the form of compositions or formulations. Examples of the preparation of the compositions and formulations may found in the American Chemical Society publication "Pesticidal Formulation Research" (Publication of the American Chemical Society, "Research on the Pesticide Formulation") (1969), Advances in Chemistry Series No.86, written by Wade Van Valkenburg; and Marcel Dekker, Inc. publication "Pesticide Formulations" (Marcel Dekker, Inc.'s publication, "Pesticide Formulations"), (1973) edited by Wade Van Valkenburg. In these compositions and formulations, the active substance is mixed with inert and agronomically acceptable (ie, plant compatible and / or inert pesticide) pesticide extenders or diluents, such as solid carrier material or liquid carrier material, of the type that can be Use in conventional pesticide formulations or compositions. By "agronomically acceptable carrier" is meant any substance that can be used to dissolve, disperse or diffuse the active ingredient in the composition without impairing the effectiveness of the active ingredient, and which by itself does not have significant harmful effects on the earth, the equipment, desirable plants or the agronomic environment. If desired, auxiliaries such as surfactants, stabilizers, anti-foaming agents and anti-displacement agents can also be combined.

Examples of the compositions and formulations according to the invention are dispersions and aqueous solutions, oily solutions and oily dispersions, pastes, powders, wetting powders, emulsifying concentrates, fluids, granules, baits, inverted emulsions, aerosol compositions and candles. fumigation. Wetting powders, pastes, fluids and emulsifying concentrates are concentrated preparations that are diluted with water before or during use. In such formulations, the compounds are extended with a solid or liquid carrier and, when desired, suitable surfactants are incorporated. Baits are preparations that generally comprise a food or other substance attractive to insects, which include at least one compound of the current invention. It is usually desired, particularly in the case of sheet spray formulations, to include auxiliaries, such as wetting agents, blowing agents, dispersing agents, gums, adhesives and the like in accordance with agricultural practice. A list of such auxiliaries commonly used in the art, and a discussion of auxiliaries, can be found in several references such as in the publication of John W. McCutcheon, Inc. "Detergents and Emulsifiers, Annual" (Annual of detergents and emulsifiers) .

The active compounds of the present invention can be used alone or in the form of mixtures with another and / or said solid and / or liquid dispersion carrier carriers, and / or with other known compatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth regulating agents, synergists. In the compositions of the invention, the active compound is present in an amount substantially between about 0.0001 (1: 99.999) -99 (99: 1) percent 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) percent by weight, and more preferably between about (1:99) - 75 (3: 1) percent by weight of the mixture. Compositions suitable for direct application or application in the field usually contain the active compound in an amount substantially between i about 0.0001 (1: 999.999) -95 (19: 1) percent, preferably between about 0.0005 (1 : 199,999) -90 (9: 1) percent by weight, and more preferably between about 0.001 (1: 99.999) -75 (3: 1) percent by weight of the mixture. The composition can also be expressed as index of the compound to the carrier. In the present invention the weight index 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 this invention can be dissolved in certain solvents such as acetone, methanol, ethanol, dimethylformamide, pyridine or dimethyl sulfoxide, and said solutions can be diluted with water. The concentrations of the solution may vary from about 1% to about 90% with a preferred index of about 5% to about 50%. For the preparation of the emulsifying concentrates, the compound 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 the water. The concentration of the active ingredient in the emulsifying concentrates is usually from about 10% to about 90%, and in the flowable emulsion concentrates, it can be as high as about 75%. Wettable powders suitable for spraying 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, adhesive agents and / or dispersing agents in said mixtures. The concentration of the active ingredients in said formulations is usually at the rate 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 the formula I, 45 parts of a hydrated, precipitated and synthetic silicone dioxide, such as that sold under the trademark HiSil®, and 5 parts of sodium lignosulfonate. . In another preparation, a kaolinite clay is used (Barden) instead of Hi-Sil® in the mentioned wetting powder, and in another preparation 25% of Hi-Sil® is replaced with a synthetic sodium silicoaluminate sold under the trademark Zeolex®3.

The powders are prepared by mixing the compounds of the formula I, or the enantiomorphs, salts and their complexes with inert, finely divided 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. The powder concentrates that contain from about 20% to about 80% of the active ingredient are commonly made, and subsequently diluted. about 1% to about 10% concentration of use. The active compounds can be applied as insecticidal sprays by means of commonly used methods, such as conventional high volume hydraulic sprayers, low volume sprayers, very small volume sprayers, air injection sprayers, overhead 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 (ie, an effective pesticidal amount) of at least one active compound of the invention alone or together with a carrier vehicle (composition or formulation) as indicated above. As used in the description and claims, the term "contact" means to apply to at least said pests or their corresponding habitat (i.e., the place to be protected, for example a growing crop or an area where it is going to grow a culture) the active compound of this 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 contain other substances commonly used in preparations of this type. For example, a lubricant, such as calcium stearate or magnesium stearate, can be added to a wetting powder or a mixture to be granulated. In addition, for example, "adhesives" such as polyvinyl alcohol-cellulose derivatives or other colloidal materials, such as casein, can be added to improve the adhesion of the pesticide to the surface to be protected.

Claims (10)

Claims

1. A compound of the formula: where X is N or CH; And it's O, S or NRS; A is hydrogen, halo, cyano, (C 1 -C 12) alkyl or (C 1 -C 12) alkoxy; Rx and R6 are, independently, hydrogen or alkyl (C? -C);

R2 is hydrogen, (C1-C12) alkyl, halo (C1-C12) alkyl, (C3-C7) cycloalkyl, (C2-C8) alkenyl, (C2-C8) alkenyl halo, (C2-C8) alkynyl, halo ( C2-C8) alkynyl, aryl, aralkyl, heterocyclic or (C1-C4) heterocyclic alkyl; R3 is hydrogen or (C1-C4) alkyl; R and R5 are, independently, hydrogen, (Cx-C4) alkyl, aryl, aralkyl, aryl (C2-C8) alkenyl, aryl (C2-C8) alkynyl, heterocyclic or heterocyclic (C1-C4) alkyl, wherein no more of one of R4 and R5 is selected from the group of hydrogen and alkyl

(Cx-C4); and enantiomers, stereoisomers and agronomically acceptable salts thereof. 2. The compound according to claim 1, wherein X is CH, Y is O, R2 is (C1-C12) alkyl and R is (C? -C4) alkyl. 3. The compound according to claim 2, wherein R4 and R5 are each independently selected from the group consisting of 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 according to claim 1, wherein X is N, Y is O or NH, R2 is alkyl (Cx-C? 2) and R3 is alkyl (C? -C4).

5. The compound according to claim 4, wherein R4 and R5 are each independently selected from the group consisting of 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 according to claim 1, wherein the compound is 3-methoxy-2- [2- ((((1-methyl-3- (2'-chlorophenyl) -2-propenylidene) mino) oxy) methyl) phenyl] propenoate.

7. The compound according to claim 1, wherein the compound is 3-methoxy-2- [2- ((((1-methyl-3- (4'-chlorophenyl) -2-propenylidene) amino) oxy) methyl) phenyl] methyl propenoate. A fungicidal composition for controlling phytopathogenic fungi, comprising an agronomically acceptable carrier and the compound of claim 1, wherein the carrier index to the compound is between 99: 1 and 1: 4. 9. A method for controlling phytopathogenic fungi, comprising applying the compound of claim 1 to the place where the control is desired, at an index of 0.005 to 50 kilograms per hectare. 10. A method for controlling insects, which comprises applying to the habitat of the insect the compound of claim 1, at an index of 0.0005 to 10 kilograms per hectare. Summary of the invention Compounds with fungicidal and insecticidal properties, having the formula: where X is N or CH; And it is 0, S or NR6; A is independently hydrogen, halo, cyano, alkyl (C x -C 2) or (C 1 -C 12) alkoxy; Ri and R-6 are, independently, hydrogen or (C 1 -C 4) alkyl; R2 is hydrogen, alkyl (C -C ^), halo (Cx-C ^) alkyl, cycloalkyl (C3-C7), alkenyl (C2-C8), halo (C2-C8) alkenyl, alkynyl (C2-C8), halo (C2-C8) alkynyl, aryl, aralkyl, heterocyclic or (C1-C4) heterocyclic alkyl; R3 is independently hydrogen or (C? -C4) alkyl; R4 and R5 are, independently, hydrogen, (C1-C4) alkyl, aryl, aralkyl, aryl (C2-C8) alkenyl, aryl (C2-C8) alkynyl, heterocyclic or heterocyclic (C1-C4) alkyl, wherein if one from R4 and R5 is hydrogen or (C1-C4) alkyl then the other of R4 and R5 is another that is not hydrogen or (C1-C4) alkyl, and its enantiomers, stereoisomers and agronomically acceptable salts.