MXPA99010283A - Substituted pyridylpyrazoles as herbicides, insecticides and acaricides - Google Patents

Abstract

The invention relates to novel substituted pyridylpyrazoles of general formula (I), wherein m=0 or 1;n=1, 2 or 3;R1=hydrogen, optionally cyano, halogen or C1-C4-alkoxy substituted alkyl with 1-6 C atoms, or optionally cyano or halogen substituted alkenyl or alkinyl with 2-6 C atoms;R2=hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen, or cyano, halogen or C1-C4-alkoxy substituted alkyl or cyano, halogen or C1-C4-alkoxy substituted alkoxy, alkoxycarbonyl, alkythio, alkylsulfinyl or alkylsulfonyl with 1-6 C atoms;R3=hydrogen, cyano, halogen or optionally cyano, halogen or C1-C4-alkoxy substituted alkyl with 1-6 C atoms and R4=nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the following groups:-Q-R5, -NH-R5, -NH-O-R5, -NH-SO2-R5, -N(SO2-R5)2, -CQ1-R5, -CQ1-Q2-R5, -CQ1-NH-R5, -Q2-CQ1-R5, -NH-CQ1-R5, -N(SO2-R5) (CQ1-R5), -Q2-CQ1-Q2-R5, -NH-CQ1-Q2-R5 or -Q2-CQ1-NH-R5, wherein Q=O, S, SO or SO2, Q1 and Q2=oxygen or sulfur, and R5 has the meaning cited in the description. The invention also relates to a method for the production and use of novel pyridylpyrazoles as phytosanitary agents, specially as herbicides, insecticides and acaricides.

Description

PIRIDILPIRAZOLSS SUBSTITUTED AS HERBICIDES, INSECTICIDES AND AQUARICIDES.

FIELD OF THE INVENTION.

The invention relates to novel pyridylpyrazoles, to the process for their preparation and to their use as agents for the treatment of plants, especially as herbicides, insecticides and acaricides.

BACKGROUND OF THE INVENTION "~ A large number of pyridylpyrazoles is already known from the literature (patent) (see J. Med. Chem. 38 (1995), 3524-3535; DE 2623302, DE 19530606, WO 93/07138; JP 08193067 - cited in Chem. Abstracts 125: 247808). The applicability as agents for the treatment of plants, for example as fungicides, herbicides, insecticides or acaricides, is also known from a part of them. However, these compounds have not acquired any notoriety.

New pyridylpyrazoles have now been found Ref .: 031917 substituted of general formula (I) where m represents the numbers 0 or 1, n represents the numbers 1, 2 or 3, R1 represents hydrogen, alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen or C? -C4 alkoxy, respectively, or alkenyl or alkynyl of 2 to 6 carbon atoms each, optionally substituted with cyano or halogen, respectively, R represents hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen, alkyl of 1 to 6 carbon atoms given the a case substituted with cyano, halogen or C 1 -C 4 alkoxy, or alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl of 1 to 6 carbon atoms each substituted, respectively, with cyano, halogen or C 1 -C 4 alkoxy R 3 represents hydrogen, cyano, halogen or alkyl of 1 to 6 carbon atoms optionally substituted with cyano, halogen or C 1 -C 4 alkoxy and R 4 represents nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the groups -Q-R 5, -NH-R5, -NH-O-R5-, -NHS02-R5, -N (S02-R5) 2. -CO ^ R5, -CQ1-Q2-R5, -C? ^ - NH-R5, -Q2-CQ2-R5, -NH-C? ^ - R5, -N (S02-R5) (C? ^ - R5), -Q2-CQ1-Q2-R5, -NH-CQ1-Q2-H5, or -Q2-CQX-NH-R5, representing QO, S ,. SO or S02, and Q1 and Q2 in each case oxygen or sulfur, and R5 represents alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen, alkoxy-C? -C4 / alkylthio C? -C4, alkyl ( C? ~ C4) carbonyl, (C? -C4) alkoxycarbonyl or alkylamino (C? -C) carbonyl, R5 further represents alkenyl or alkynyl of 2 to 6 carbon atoms each optionally substituted respectively with cyano, carboxy, halogen, alkyl (C? -C4) carbonyl, (C? -C4) alkoxycarbonyl or alkylamino (C? C) carbonyl, R5 also represents cycloalkyl or cycloalkylalkyl with 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, each optionally substituted each with cyano, carboxy, halogen, alkyl (C? -C) carbonyl or (C? -C4) alkoxycarbonyl, further represents aryl or arylalkyl having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part respectively given case each substituted with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarba oyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C alkoxy, C 1 -C 4 haloalkoxy, C 4 -C 4 alkylthioalkylthio C? -C4, alkylsulfinyl C? -C, alkylsulfonyl C? -C, alkylamino C? -C or dime tilamino, or further represents heterocyclyl or heterocyclylalkyl with 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and / or 1 or 2 oxygen atoms and / or a sulfur atom in the heterocyclyl group and optionally 1 to 4 atoms of carbon in the alkyl part optionally substituted each with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 4 -C 4 alkoxy, C 4 -C 4 haloalkoxy , alkylthio C? ~ C, halogenalkylthio Cx-C4, alkylsulfinyl C? -C4, alkylsulfonyl C? -C4, alkylamino C? -C or dimethylamino.

The new substituted pyridylpyrazoles of general formula (I) are obtained by reacting hydrazine or its derivatives of general formula (II), H2N-NH-R1 (II) wherein R1 has the meaning indicated above, with substituted pyridyl-1,3-dicarbonyl compounds of general formula (III), wherein m, n, R2, and R4 have the meaning indicated above, or with pyridyl-carbonyl compounds of general formula (IV) < IV) in which m, n, R3 and R4 have the meaning indicated above, Q3 represents oxygen or sulfur and R represents hydrogen or alkyl, and / or optionally tautomers of the compounds of formula (IV), optionally in the presence of a reaction coadjuvant and optionally in the presence of a diluent, and If appropriate, the compounds of formula (I) thus obtained are subjected to other transformations within the framework of the definitions of the above substituents.

The compounds of the general formula (I) can be converted by customary methods to other compounds of the general formula (I) according to the definitions of the above substituents, for example by usual alkylation, acylation or sulfonylation reactions (for example R1: H - >) CH3, CHF2, C2H5, CH2CH = CH2, R4: OH -> 0CH3, 0C2H5, 0CHF2, 0CH2CH = CH2, 0C0CH3, SH -> SCH3, SC2H5, NH2 -> NHC3H7, NHCOCH3, NHS02CH3), or electrophilic or nucleophilic substitution reactions (for example R3: H -> Cl, Br; R4: F -> OH, SH, NH2) - see also Preparation examples.

The new substituted pyridylpyrazoles of general formula (I) have interesting biological properties that make possible their use as agents for the treatment of plants. They have an intense herbicidal, insecticidal and acaricidal activity and are characterized especially by an outstanding and selective herbicidal activity.

In the definitions, the saturated or unsaturated hydrocarbon radicals, such as alkyl, alkenyl or alkynyl, are in each case straight-chain or branched.

Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially fluorine or chlorine.

Preferable objects of the invention are preferably compounds of formula (I) in which m represents the numbers 0 or 1, n represents the numbers 1, 2 or 3, 1 represents hydrogen, methyl, ethyl, n- or i-propyl, n- optionally substituted with cyano, fluorine, chloro, methoxy or ethoxy, or propenenyl, butenyl, propynyl or butynyl substituted respectively with cyano, fluoro, chloro or bromo, R2 represents hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, fluorine, chlorine, bromine, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted respectively with cyano , fluorine, chlorine, methoxy or ethoxy, or methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n -, i- s- or t-butylthio, 'methylsulfinyl, ethylsulfinyl, n- or i-propylsulfinyl, n-, i-, s- or t-butylsulfinyl, methylsulfonyl, ethylsulphonyl, n- or i-propylsulphonyl, n-, i-, s- or t-butyl sulfoni If appropriate, substituted respectively with cyano, fluoro, chloro, methoxy or ethoxy, R3 represents hydrogen, fluorine, chlorine, bromine or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted with cyano, fluorine, chlorine, methoxy or ethoxy, and R4 represents nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, fluoro, chloro, bromo or one of the groups -Q-R5, -NH-R5, -NH-O-R5, -NHS02-R5, -N (S02-R5) 2, -CQ1-R5, -CQ1-Q2-R5, -CQX-NH-R5, -Q2-CQ1-R5, -NH-C? ^ - R5, -NS02-R5) (CQ1-R5), -Q ^ C? ^ - Q? -R5, -NH-CQ1-Q2-R5 or -Q2-CQ1-NH-R5, representing QO, S SO or S02, and Q1 and O2 in each case of oxygen or sulfur, and R5 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted respectively with cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio , acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl, R5 also represents propenyl, butenyl, propinyl or butininyl, optionally substituted respectively with cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl, R5 further represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl each optionally substituted with cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, R5 further represents phenyl, benzyl or phenylethyl each optionally substituted with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulphinyl, methylsulfonyl, ethylsulphonyl, methylamino, ethylamino or dimethylamino, or furthermore represents heterocyclyl or heterocyclylalkyl of the oxiranyl, oxetanyl, furyl, tetrahydrofuryl series , dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl case each substituted with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl , chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulphonyl, methylamino, ethylamino , not i-propylamino or dimethylamino.

The invention relates in particular to compounds of formula (I) in which m represents the numbers 0 or 1, n represents the numbers 1, 2 or 3, R 1 represents methyl or ethyl optionally substituted respectively with cyano, fluorine, chlorine methoxy or ethoxy, R2 represents hydroxy, mercapto, fluorine, chlorine, bromine, or represents methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl each substituted by cyano, fluorine, chlorine, methoxy or ethoxy R3 represents fluorine, chlorine, bromine or methyl or ethyl optionally substituted with cyano, fluorine, chlorine, methoxy or ethoxy, and R4 represents nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the groups -Q-R5, -NH-R5, -NH-O-R5, -NHS02-R5, -N (S02-R5) 2, -CQ1-R5, -CQX-Q-R5, -CQX-NH-R5, -Q2-CQ1-R5, -NH-C? ^ - R5, - N (S02-R5) (CQ1-R5), -Q2-CQ1-Q-R5, -NH-CQ1-Q2-R5 or -Q2-CQ1-NH-R5, representing Q O, S, SO or S02, and Q1 and Q2 in each case oxygen or sulfur, and R5 represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted respectively with cyano, fluoro, chloro, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl , ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl, R5 represents also propenyl, butenyl, propynyl or butininilo optionally substituted radicals repectivamente with cyano, carboxy, fluoro, chloro, bromo, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl, R5 represents addition cyclopropyl, cyclobutyl, cyclopentyl, ciciohexilo, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl optionally substituted each with cyano, carboxy, fluoro, chloro, bromo, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl, R5 represents also phenyl, benzyl or phenylethyl optionally substituted each with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- ot butyl, difluoromethyl, trifluoromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulphonyl, methylamino, ethylamino or dimethylamino, or R5 further represents heterocyclyl or heterocyclylalkyl series oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl,. pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazolylmethyl, pyridinylmethyl, pyrimidinylmethyl optionally substituted each with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i- • propyl, n- , i-, s- or t-butyl, dichloromethyl, trichloromethyl, difluoromethyl, trifluoromethyl, chlorodifluoromethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio , trifluoromethylthio, chlorodifluoromethylthio, fluorodichloromethylthio, methylsulinyl, ethylsulphinyl, ethylsulfonyl, ethylsulphonyl, methylamino, ethylamino, n- or i-propylamino or dimethylamino.

An especially preferred group of compounds of general formula (1) are the compounds of formula (la), wherein n, R1, R2, R3 and R4 have the meanings indicated above as being especially preferred.

Another especially preferred group of compounds of general formula (I) are the compounds of formula (Ib), wherein n, R1, R2, R3 and R4 have the meanings indicated above as being especially preferred.

Another especially preferred group of compounds of general formula (I) are the compounds of the general formula (le), wherein n, R1, R2, R3 and R4 have the meanings indicated above as being especially preferred.

The definitions of the abovementioned radicals indicated in general or in degrees of preference are valid both for the final products of formula (I) and also as regards the intermediate or starting products necessary for their preparation. These definitions of remains can be combined discretionally with each other, thus also between the indicated preferred grades.

If, for example, methylhydrazine and 2-chloro-1- (4-cyano-3-methoxy-pyridin-2-yl) -4,4-difluoro-butane-1,3-dione are used as starting products, then the development of the reaction in the process according to the invention is schematized by the following scheme of formulas: The hydrazine derivatives to be used in the process according to the invention as starting substances for the preparation of the compounds of formula (I) are in general defined by formula (II). In the formula (II) R1 preferably has or in particular that meaning which was already indicated above as preferred or especially preferred for R 1 in the context of the description of the compounds of formula (I) according to the invention.

The starting substances of the general formula (II) are known synthesis reagents.

The pyridyl-1,3-dicarbonyl compounds to be used in the process according to the invention as starting substances are generally defined by the formula (III). In the formula (III) n, R2, R3 and R4 preferably have, or in particular, the meaning already indicated above as preferred or especially preferred for n, R2, R3 and R4 in the context of the description of the compounds of the formula (I) according to the invention.

The pyridylcarbonyl compounds to be used in the process according to the invention as starting substances are in general defined by the formula (IV). In formula (IV) n, R 3 and R 4 preferably have, or in particular, the meaning already indicated above as preferred or especially preferred for n, R 3 and R 4 in the context of the description of the compounds of formula (I) according to the invention; Q3 preferably represents oxygen or sulfur and R preferably represents hydrogen or C? -C alkyl, especially hydrogen, methyl or ethyl.

The starting substances of formulas (III) and (IV) are known or can be prepared by known methods (see J. Chem. Soc. C 1969, 2738-2747: loe. Cit. C 1979, 796-800; J. Chem Soc., Perkin Trans. I 1988, 2785-2789, J. Hetroycl. Chem. 30 (1993), 855-859, J. Med. Chem. 33 (1990), 1859-1865, J. Org. Chem. (1982), 3027-3038, loc 49 (1984), 3733-3742, Pharmazie 23 (1968), 557-560, Synthesis 1993, 290-292, DE 2458808, DE 4031798, DE 4425650, EP 206294, EP 306251; US 4026900; US 4980357; Preparation examples).

Suitable diluents for carrying out the process according to the invention for the preparation of the novel compounds of the formula (I) are primarily organic solvents. These include aliphatic, alicyclic or aromatic hydrocarbons, optionally halogenated, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers, diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran ethylene glycol dimethyl or diethyl ether, ketones, such as acetone, butanone or methyl isobutyl ketone; carboxylic acids, such as for example acetic acid or propionic acid, nitriles such as acetonitrile, propionitrile or butyronitrile; amides, such as N, -dimethylformamide, N, N-dimethylacetamide, -methylformanilide, N-methylpyrrolidone or hexamethylphosphoratriamide; esters such as methyl acetate or ethyl acetate, sulfoxides, such as dimethylsulfoxide, alcohols, such as methanol, ethanol, n- or -i-propanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.

As a reaction aid for the process according to the invention, the usual inorganic or organic bases or acid acceptors are generally considered. These preferably include acetates, amides, carbonates, hydrogen carbonates, hydrides, hydroxides or alkanolates of alkali metal or alkaline earth metal, such as, for example, sodium, potassium or calcium acetate, lithium amide, sodium, potassium or calcium, sodium carbonate., potassium or calcium, sodium, potassium or calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, lithium, sodium, potassium or calcium hydroxide, methanolate, ethanolate, n- or i-propanolate, n-, i-, s- or sodium or potassium t-butanolate, furthermore also basic organic nitrogenous substances, such as for example trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl-aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl-, 3-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethyl-, 3, 4 -dimethyl- and 3, 5-dimethyl-pyridine, 5-ethyl-2-methyl-pyridine, 4-dimethylamino-pyridine, N-methyl-piperidine, 1,4-diazabicyclo [2, 2, 2] -octane ( DABCO), 1,5-diazabicyclo [4, 3, 0] -non-5-ene (DBN) or 1,8-diazabicyclo [5,, 4,0] -undec-7-ene (DBU).

The reaction temperatures can be varied by carrying out the process according to the invention over a wide range. In general, work is carried out at temperatures between 0 ° C and 150 ° C, preferably between 20 ° C and 120 ° C.

The process according to the invention is generally carried out at normal pressure. However, it is also possible to carry out the process according to the invention at elevated or reduced pressure - in general between 0.1 and 10 bar.

For carrying out the process according to the invention, the starting substances are generally used in approximately equimolar quantities. However, it is also possible to use one of the components in excess. The reaction is generally carried out in a suitable diluent and the reaction mixture is generally stirred for several hours a. the precise temperature. The processing is carried out according to usual methods (see Preparation examples).

The active ingredients according to the invention can be used as defoliants, desiccants, herbaceous destroying agents and especially as weed killers. Weeds should be understood in the broadest sense all plants that grow in places where you do not want. Whether the substances according to the invention act as total or selective herbicides depends essentially on the amounts used.

The active compounds according to the invention can be used, for example, in the following plants: Dicotyledonous weeds of the genera: Synapses, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Calinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum , Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Línum, Ipomea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, Cucumis, Cucurbita.

Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Oats, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemun, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocotilidonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Oats, Sécale, Sorghum, Panicum, Sacharum, Ananas, Asparagus, Allium.

The use of the active principles according to the invention is not however limited in any way to these genera, but extends in the same way also to other plants.

The compounds are suitable as a function of concentration for the total eradication of weeds, for example in industrial and railway installations and in roads and places with and without tree vegetation. The compounds can also be used to combat weeds in perennial crops, for example, forest, ornamental fruit tree plantations, vineyards, citrus fruits, walnuts, bananas, coffee plantations, tea, rubber, oil palm, cocoa, fruit trees of berries and hops, ornamental and sportive lawns and pasture surfaces and to selectively combat weeds in annual crops.

The compounds of formula (I) according to the invention are especially suitable for selectively controlling monocotyledonous and dicotyledonous weeds in monocotyledonous and dicotyledonous cultures in both pre-emergence and post-emergence procedures.

The active ingredients are suitable for combating animal parasites, preferably arthropods and nematodes, especially insects and arachnids present in agriculture, in forests, for the protection of provisions and materials as well as in the hygiene sector. They are effective against normal and resistant types of sensitivity as well as against all or certain stages of development. To the aforementioned parasites belong: From the order of the Isopoda for example Oniscus asellus, Armadillidium vulgare, Porcellio s.caber.

From the order of the Diploda for example Blanillus guttulatus.

From the order of the Chilopoda for example Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla for example Scutigerella immaculata.

From the order of the Thynasura for example Lepisma sacharina.

From the order of the Collembola for example Onychiurus armatus.

From the order of the Orthoptera for example Blatta orientalis, Periplaneta americana, Leucophaea maderae, Germanic Blattella, Acheta domesticus, Gryllotalpa spp., Locusta migratory migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera for example Forfícula auricularia.

From the order of Isoptera for example Reticulitermes spp.

From the order of the Anoplura for example Pediculus humanus corporis, Hae atopinus spp., Linognathus spp.

From the order of the Mallophaga for example Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera for example Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera for example Eurygaster spp., Dysdercus intermedius, Phisma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of the Homoptera for example Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae, Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Pemphigus spp., Phorodon humuli , Phylloxera vastatrix, Rhopalosiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugeus, Aonidella aurantii, Aspidiotus hederae, Pseudococccus spp., Pysilla spp.

From the order of the Lepidoptera for example Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana; Heliothis spp., Spodoptera exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocasia pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Tineola bisselliella, Tinea pellionella, Hofmannophila pseudospretella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanimous, Tortrix viridana.

From the order of coleoptera, for example Anobium punctatum, Rhizopertha domonica, Acanthoscelides obtectus, Bruchidius obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthono us spp., Sitophilus spp., Otiorrynchus sulcatus, Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melo.lontha melolontha, Amphi allon solstitiallis, Costelytra zealandica.

From the order of the Hymenoptera for example Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera, for example Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomia hyoscyami, Ceratitis capitata, Dacus oleae, Typula paludosa.

From the order of the Siphonaptera for example Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida for example Scorpio maurus, Latrodectus mactans.

From the order of the Acariña for example Acarus siró, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phylocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp. , Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp.

The nematode phytoparasites include, for example, Pratylenchus spp., Radopholus spp., Ditylenchus spp., Tylenchulus spp., Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphidema spp., Trichodorus spp. , Tylenchus spp., Helicotylenchus spp., Rotylenchus spp., Tylenchulus spp.

The active ingredients can be incorporated into customary formulations, such as solutions, emulsions, spray powders, suspensions, powders, dusts, pastes, soluble powders, granules, suspension-emulsion concentrates, natural and synthetic materials impregnated with active principle as well as fine powders encapsulated in polymer materials.

These formulations are prepared in a known manner, for example by mixing the active ingredient with extenders, ie liquid solvents and / or solid carriers, optionally using surfactants, ie emulsifiers or dispersants and / or foaming agents.

In the case of using water as an extender, organic solvents can also be used, for example, as dissolving aids. Suitable liquid solvents are substantially: aromatic hydrocarbons such as xylene, toluene, or alkylnaphthalenes, chlorinated aromatic hydrocarbons and gold aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, mineral oils and vegetables, alcohols, such as butanol or glycol as well as their ethers or esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethylsulfoxide, as well as water.

As solid vehicles are considered: for example, ammonium salts and natural mineral flours, such as kaolins, aluminas, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth and synthetic mineral flours such as high dispersion silicic acid, aluminum oxide and silicates, as solid carriers for granulates are considered: for example crushed and fractionated natural minerals such as calcite, marble, pumice, sepiolite, dolomite as well as synthetic granules of inorganic and organic flours, as well as granulates of organic materials such as sawdust, coconut husks corn cobs and tobacco stems; as emulsifier and foaming agent are considered: for example nonionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkyl sulfates, arylsulfonates as well as albumin hydrolyzates; as dispersants are considered: for example lignin-sulphite residual liquors and methylcellulose.

In the formulations can be used binders such as carboxymethylcellulose, natural and synthetic polymers pulveriform, granular or in the form of latex, such as gum arabic, poly (vinyl alcohol), polyvinyl acetate), as well as natural phospholipids, such as cephalins and lecithins and synthetic phospholipids . Other additives can be mineral and vegetable oils.

Dyes can be used as inorganic pigments, for example iron oxide, titanium oxide, prussian blue and organic dyes, such as alizarin, azo and metal phthalocyanine dyes and oligonutrients such as iron, manganese, boron, copper, cobalt, molybdenum salts and zinc.

The formulations generally contain between 0.1 and 95 weight percent active ingredient, preferably between 0.5 and 90 weight%.

The active principles according to the invention can also be used as such or in their formulations in admixture with known herbicides for controlling weeds, with possible finished formulations or mixtures for tank dilution.

For mixtures, known herbicides are considered, for example: Acetochlor, Acifluorofen (sodium), Aclonifen, Alachlor, Aloxidim (sodium), Ametrine, Amidochlor, Amidosulfuron, Asulam, Atrazine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap, Benzoylprop (ethyl-), Bilafos, Bifenox, Bromobutide, Bromofenoxim, Bromoxinil, Butachlor , Butílate, Cafenstrole, Carbetamide, Clometoxifén, Clorambén, Cloradizone, Clorimuron (-ethyl), Cloritriphen, Clorsulfuron, Clortoluron, Cinmetilin, Cinosulfuron, Cletodim, Clodinafop (-propargyl), Clomazone, Clopyralid, Clopyrasulfuron, Cloransulam (-methyl), Cumiluron, Cianazine, Cycloate, Ciclosulfamuron, Cycloxydim, Cihalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedifam, Dialate, Dicamba, Doclofop (-methyl), Dibenzoquat, Diflufenican, Dimefuron, Dimepiperate, DDiimmeettaacclloorr ,, Dimetametrin, Dimetenamid, Dinitramine, - Difenamid, Diquat, Ditiopir, Diuron, Di rón, EPTC, Esprocarb, Etalfluralin, Etamethysulfuron (-methyl), Etofumesate, Etoxifen, Etobenzanid, Fenoxaprop-ethyl, Flamprop (-isopropyl), Flamprop (-isopropyl-L), Flamprop (-methyl), Flazasulfuron, Fluazifop (-butyl), Flumetsulam, Flumiclorac (-pentyl), Flumioxazine, Flumipropin, Fluometuron, Fluorochloridone, Fluoroglycophene (-ethyl), Flupoxam, Flupropacil, Flurenol, Fluridone, Fluroxipir, Flurprimidol, Flurtamone, Fomesafen, Glufosinate (ammonium), Glyphosate (isopropylammonium), Halosafen, Haloxifop (-ethoxyethyl), Hexazinone, Imazametabenz (-methyl), Imezametapir, Imazamox, Imazapir, Imazaquin, Imazetapir, Imazosulfuron, Ioxinil, Isopropalin, Isoproturon, Isoxaben, Isoxaflutole, Isoxapirifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Metamitrom, Metazachlor, Metabenzothiazuron, Metobenzuron, Metobromuron, Metolachlor, Metosulam, Metoxuron, Metsulfuron (-methyl), Metribuzin, Molinate, Monolinunoron, Naproanilide, Naproamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Orizalin, Oxadiazon, Oxifluorophen, Paraquat, Pentadimetalin, Fenmedifan, Piperophos, Pretilachlor, Primisulfuron ( -methyl), Prometrin, Propaclor, Propanil, Propaquizafop, Propizamide, Prosulfocarb, Prosulfuron, Pirazolate, Pyrazosulfuron (-ethyl), Pyrazoxifen, Pyributicarb, Pyridate, Piritiobac (sodium), Quinclorac, Quinmerac, Quizalofop (-ethyl), Quizalofo (p -tefuril), Ri sulfuron, Sethoxydim, Simazine, Simetrin, Sulcotrione, Sulfentrazone, Sulfometuron (-methyl), Sulfosate, Tebutam, Tebutiuron, Terbutilazine, Terbutrin, Tenilclor, Tiafluamide, Tiazopir, Tidiazimin, Tifensulfuron (-methyl), Thiobencarb, Tiocarbazil , Tralkoxidim, Ttrialate, Triasulfuron, Tribenuron (-methyl), Triclopir, Tridifane, Trifluralin and Trisulfuron.

A mixture with other known active principles is also possible, such as fungicides, insecticides, acaricides, nematicides, protective substances against attack by birds, plant nutrients and agents for improving the structure of the soil.

The active ingredients can be used as such, in the form of their formulations or in forms of application prepared therefrom by subsequent dilution, such as solutions, suspensions, emulsions, powders, pastes and granules ready for use. The application is carried out in the usual way, for example by pouring, spraying, spraying, spreading.

The active ingredients according to the invention can be applied both before and after the emergence of the plants. They can also be incorporated into the soil before sowing.

The amount of active ingredient used may vary within wide limits. It depends essentially on the type of effect desired. In general, the amounts applied are between 1 g and 10 kg of active principle per hectare of soil surface, preferably between 5 g and 5 kg per ha.

The preparation and use of the active principles according to the invention is described in the following Examples.

Preparation examples; Example 1 .2 g (89 mmol) of 3- (6-chloro-pyridin-3-yl) -3-oxo-propionic acid ethyl ester were placed in 40 ml of acetic acid and mixed at an indoor temperature of about 40 ° C. drop by drop with 5.8 g (126. mmol) of methylhydrazine. Then the mixture was heated for approximately 90 minutes at 90 ° C-100 ° C, forming a brownish solid. The cooled mixture was poured into 300 ml of water, the precipitated solid was filtered off, washed with water and dried under vacuum at 50 ° C. 13.6 g (73% of theory) of 5- (6-chloropyridin-3-yl) -2-methyl-2H-pyrazol-3-ol of melting point 220 ° C were obtained.

Example 2 To a solution of 33.5 g (133 mmol) of 3- (6-chloropyridin-3-yl) -4,4,4-trifluorobutane-1,3-dione in 160 ml of acetic acid were added successively 8.0 g (160 g. mmol) of hydrazine hydrate and 16.3 g (160 mmol) of acetic anhydride. The reaction mixture was heated for one hour between 90 ° C and 100 ° C and the cooled mixture was poured into 800 ml of ice water. The precipitated solid was separated by filtration, washed with water and dried under vacuum at 50 ° C. 29.8 g (90% of theory) of 2-chloro-5- (5-trifluoromethyl-1H-pyrazol-3-yl) -pyridine of melting point 183 ° C were obtained.

Example 3 To a mixture of 12.6 g (60 mmol) of 5- (6-chloro-pyridin-3-yl) -2-methyl-2H-pyrazol-3-ol and 100 ml of N, N-dimethylformamide were added. 16.5 g of potassium carbonate and heated for approximately 60 minutes at 50 ° C. Then approximately 30 g (0.35 mol) of chlorodifluoromethane were introduced at a temperature between 60 ° C and 70 ° C within one hour. The reaction mixture was cooled to room temperature, poured into 1.3 liters of water and acidified with 2N hydrochloric acid. The precipitated solid was filtered off with suction, dissolved in dichloromethane, washed successively with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous solution of common salt, dried with magnesium sulfate and filtered. The filtrate was concentrated in water-pump vacuum and the residue was purified by column chromatography with toluene / ethyl acetate (vol .: 1: 1).

In the main fraction, 6.5 g (42% of theory) of 2-chloro-5- (5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -pyridine of melting point 102 ° C were obtained.

Example 4 . To a solution of 3.6 g (13.9 mmol) of 2-chloro-5- (difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -pyridine in 15 ml of dichloromethane was added at room temperature (about 20 ° C) with stirring 2.2 g (1.62 mmol) of sulfuryl chloride. The mixture was stirred for three hours at about 20 ° C, diluted with 20 ml of dichloromethane, washed with saturated aqueous solution of sodium hydrogencarbonate and with saturated aqueous solution of common salt, dried with magnesium sulfate and filtered. From the filtrate the solvent was removed carefully by vacuum distillation of water pump. 4.05 g (99% of theory) of 2-chloro-5- (4-chloro-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) -pyridine of melting point 42 ° C were obtained.

If a corresponding solution of bromine in dichloromethane is used instead of sulfuryl chloride, 2-chloro-5- (4-bromo-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl) - pyridine ("Example 11") of melting point 60 ° C.

Example 5 To a mixture of 10.1 g (40 mmol) of 2-chloro-5- (5-trifluoromethyl-1H-pyrazol-3-yl) -pyridine and 8.4 g (60 pmol) of potassium carbonate in 150 ml of acetonitrile are added to the mixture. 18.3 g (129 mmol) of iodomethane were added at about 20 ° C over the course of about two minutes. The reaction mixture was stirred for 3 hours at 40 C and after cooling it was concentrated in water-jet vacuum. The residue was suspended in 100 ml of dichloromethane and 200 ml of water, the organic phase was separated, washed with water, dried with magnesium sulfate and filtered. The filtrate was concentrated in water-pump vacuum and the residue was purified by column chromatography with n-hexane / ethyl acetate (vol .: 2: 1). 6.6 g (50.5% of theory) of 2-chloro-5- (1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -pyridine of melting point 95 ° C were obtained.

Example 6 To a solution of 2.0 g (7.6 mmol) of 2-chloro-5- (l-methyl-5-trifluoromethyl-lH-pyrazol-3-yl) -pyridine in 40 ml of acetic acid was introduced at 75 ° C. 85 ° C stirring in the course of 2 hours 10 g (141 mmol) of chlorine gas. The reaction mixture was cooled, poured into 100 ml of ice water and extracted with ethyl acetate. The separated organic phase was washed sequentially with saturated sodium hydrogencarbonate solution and saturated aqueous common salt solution, dried with magnesium sulfate and filtered. The filtrate was concentrated under water-pump vacuum. 2.05 g (91% of theory) of 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl) -pyridine of melting point 55 ° C were obtained.

Example 7 To a solution of 23.0 g and 88.6 mmol) of l- (6-chloro-pyridin-3-yl) -3,3-bis-methylthio-2-propen-1-one in 145 ml of acetonitrile was added to approximately 20 ° C 10.3 g (224 mmol) of methylhydrazine The reaction mixture was refluxed for 120 minutes and then poured into ice water. The precipitated solid was filtered off with suction, washed with water and dried under vacuum.

There were obtained 17.9 g (84% of theory) of 3- (6-chloro-pyridin-3-yl) -l-methyl-5-methylthio-1H-pyrazole of melting point 93 ° C.

Example 8 To a solution of 3.8 g (16 mmol) of 3- (6-chloro-pyridin-3-yl) -l-methyl-5-methylthio-1H-pyrazole in 30 ml of diethyl ether was added sequentially at 0 ° C a drop of acetic acid and 1.8 g (9 mmol) of 1,3-dichloro-5,5-dimethyl-hydantoin. The reaction mixture was stirred for 18 hours at room temperature (about 20 ° C) and mixed successively with 20 ml of water and 20 ml of ethyl acetate. The organic phase was separated, washed sequentially with saturated aqueous sodium hydrogencarbonate solution and saturated aqueous common salt solution, dried with magnesium sulfate and filtered. The filtrate was concentrated under water-pump vacuum. 3.8 g (87% of theory) of 4-chloro-3- (6-chloro-pyridin-3-yl) -l-methyl-5-methylthio-1H-pyrazole were obtained as an amorphous residue.

Example 9 To a solution of 1.9 g (7.7 mmol) of 4-chloro-3- (6-chloro-pyridin-3-yl) -l-methyl-5-methylthio-1H-pyrazole in 30 ml of dichloromethane was added to 0 ° C with stirring 7.5 g (30 mmol) of 3-chloroperbenzoic acid. The reaction mixture was stirred for 18 hours at room temperature (about 20 ° C), the precipitated solid was filtered off and the filtrate was washed successively with saturated sodium thiosulfate solution, saturated sodium hydrogencarbonate solution and saturated salt solution common, dried with magnesium sulfate and filtered. The filtrate was concentrated under water-pump vacuum. 2.0 g (81% of theory) of 4-chloro-3- (6-chloro-l-oxy-pyridin-3-yl) -1-methyl-5-methylsulfonyl-1H-pyrazole were obtained as an amorphous residue.

Analogously to the preparation examples 1 to 9 and to the general description of the preparation process according to the invention, compounds of the formula can also be prepared, for example.

(I) listed in the following Table 1.

Tpm a i: E epgslos dß compounds of formula (I) Starting substances of formula (III) Example (III-l) To a mixture of 89.3 g (0.525 mol) of potassium monoethylmalonate in 500 ml of acetonitrile, 50.5 g (0.5 mol) of triethylamine and 58.8 (0.617 mol) of anhydrous magnesium chloride were successively added between 10 ° C and 15 ° C. . The mixture was stirred for 150 minutes at about 20 ° C, cooled to a temperature of -10 ° C to -5 ° C and at this temperature 88.0 g 0.50 mol) of 2-chloro-pyridine-2-chloride were successively added. -carboxylic and 5.05 g (0.05 mol) of triethylamine. The reaction mixture was stirred for 18 hours at about 20 ° C and then 'concentrated. The residue was stirred with 500 ml of toluene and 240 ml of 33% hydrochloric acid were added slowly. The mixture was stirred for 3 hours at room temperature, filtered to remove the precipitated solid and the organic phase was separated from the filtrate. This was washed with dilute hydrochloric acid and with water, dried with magnesium sulfate and filtered. The filtrate was concentrated under water-pump vacuum and the residue was separated by column chromatography with dichloromethane / methanol (vol .: 9: 1).

The main fraction was 82.9 g (73% of theory) of 3- (6-chloro-pyridin-3-yl) -3-oxo-propionic acid ethyl ester of melting point 48 ° C.

Example (III-2) Step 1 A solution of 40 g (0.176 mol) of 3- (6-chloro-pyridin-3-yl) -3-oxo-propionic acid ethyl ester in 60 ml of acetic acid was mixed successively with 40 ml of water and 7.5 ml of concentrated sulfuric acid and then heated for 90 minutes at about 80 ° C. The reaction mixture was allowed to cool to room temperature and poured into 600 ml of ice water. The suspension formed was neutralized with dilute sodium hydroxide solution and extracted with dichloromethane. The organic phase was washed with concentrated aqueous solution of common salt, dried with magnesium sulfate and filtered. From the filtrate the solvent was carefully removed by vacuum distillation of water pump. 21.4 g (78% of theory) of 5-acetyl-2-chloro-pyridine of melting point 98 ° C were obtained.

Step 2 To a solution of 17.4 g (0.112 mol) of 5-acetyl-2-chloro-pyridine in 200 ml of diethyl ether was added successively first at about 20 ° C 20.7 g (0.146 mol) of ethyl trifluoroacetate and then a -5 ° C 30.2 g (0.168 mol) of 30% methanolic solution of sodium methylate. The reaction mixture was stirred for 2 hours at 0 ° C, then poured into 200 ml of ice water and adjusted with IN hydrochloric acid to a pH value between 2 and 3. The organic phase was then separated, washed with saturated aqueous solution of common salt, dried with magnesium sulfate and filtered. From the filtrate the solvent was carefully removed by vacuum distillation of water pump. 27.1 g (96% of theory) of l- (6-chloro-pyridin-3-yl) -4,4,4-trifluorobutane-1,3-dione of melting point 54 ° C were obtained.

Example (III-3) To a suspension of 33.6 g (0.3 mol) of potassium t-butylate in 210 ml of tetrahydrofuran, a solution of 23.3 g (0.15 mol) of 5-acetyl was added dropwise at -40 ° C over the course of 15 minutes. -2-chloro-pyridine in 50 ml of tetrahydrofuran. The mixture was stirred for 30 minutes at -40 ° C and then mixed with 11.4 g (0.15 mol) of carbon sulfide. After 30 more minutes, 42.6 g (0.3 mol) of methyl iodide was added and the reaction mixture was allowed to reach room temperature over the course of two hours. The reaction mixture was poured into 1.5 liters of ice water, adjusted between pH 2 and 3 with IN hydrochloric acid and extracted with 1.5 liters of ethyl acetate. The organic phase was washed with common salt solution, dried over magnesium sulfate and the solvent was removed in vacuo. The obtained crude product was stirred with about 100 ml of diethyl ether, the solid which precipitated was separated by filtration and dried. 24.3 g (62% of theory) of l- (6-chloro-pyridin-3-yl) -3,3-bis-methylthio-2-propen-1-one were obtained as light yellow crystalline solid of melting point. ° C.

Application examples EXAMPLE A PRE-EMERGENCY TEST Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To obtain a suitable active ingredient preparation, 1 part by weight of active compound was mixed with the indicated amount of solvent, the indicated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

Seeds were planted from the test plants in a normal soil. After approximately 24 hours the soil was watered with the preparation of active principle. In this respect, the quantity of water per unit area was suitably constant. The concentration of active principle in the preparation plays no role, only the amount of active principle applied per unit area is decisive.

After three weeks the degree of damage of the plants was evaluated in% damage compared to the development of the untreated controls.

They mean: 0% = no effect (like untreated controls) 100% = total annihilation In this test, the compounds according to Preparation Examples 4, 6 and 7 have, for example, application rates of 60 to 2,000 g / ha with a good tolerance for crop plants, for example cotton (0%). ), an intense activity against weeds, such as Digitaria (100%), Sorghum (95%), Amaranthus (100%), Chenopodium (100%), Solanum (100%), Fact Oat (80-100%), Setaria (100%), Abutilón (100%), Galiu (90-100%), as well as Sinapsis (80-100%).

Example B Post-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To obtain a suitable active ingredient preparation, 1 part by weight of active compound was mixed with the indicated amount of solvent, the indicated amount of emulsifier was added and the concentrate was diluted with water to the desired concentration.

With the preparation of active principle, the test plants were sprayed, which had a height of 5 to 15 cm, so that the amounts of active principle respectively desired per unit area corresponded. The concentration of the spray liquid was chosen so that the amounts of active principle respectively desired were in 1,000 liters of water / ha.

After three weeks the degree of damage of the plants was evaluated in% damage compared to the development of the untreated controls.

They mean: 0% = no effect (like untreated controls) 100% = total annihilation In this test, the compounds according to Preparation Examples 4, 6 and 7 have, for example, application rates of 15 to 2,000 g / ha and good tolerance for crop plants, for example wheat (10%). , intense activity against weeds, such as Alopecurus (100%), Oats fatua (100%), Setaria (100%), Abutilon (100%), Amaranthus (100%), Galium (100%), Ipomea (100%) %), Polygonum (100%) as well as Solanum (100%).

Tested C Test with Tetranychus (immersion treatment / resistant OP) Solvent: 5 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether I 1 part by weight of principle was mixed in order to obtain a suitable preparation of active principle.

I active with the indicated amount of solvent and the indicated amount of emulsifier the concentrate was diluted with water to the desired concentration. 1 Bean plants (Phaseolus vulgaris) strongly attacked by the common mite (Tetranychus I urticae) of all the stages were immersed in a I preparation of active principle of the desired concentration.

After the desired time, the effect was determined in i%. In this respect 100% means that all the mites were 'exterminated; 0% means that no mite has been exterminated.

In this test the compound according to the Example I of Preparation 1 shows, for example, at a concentration of active principle of 0.01% a degree of extermination of 95 'after 7 days.

Example D Test with Spodoptera frugiperda / artificial feed Solvent: 100 parts by weight of acetone 1,900 parts by weight of methanol To obtain a suitable active ingredient preparation, 1 part by weight of active compound was mixed with the indicated amount of solvent and the concentrate was diluted with water to the desired concentration.

A given amount of active ingredient preparation was pipetted into a standardized amount of artificial feed. After the methanol evaporated. they were put with a triple repeat larvae paths (L2-L3) of Spodoptera frugiperda in the feed.

After the desired time the activity was determined in%. In this respect 100% means that all the animals were exterminated; 0% means that no animal was exterminated.

In this test, the compound according to Preparation Example 2 shows, for example, at a concentration of active principle of 0.05%, a degree of killing of 100% after 7 days.

It is noted that in relation to this date, the best method known to the applicant, to implement said invention is that which is clear from the manufacture of the objects to which it refers.

Having described the invention as above, the content of the following is claimed as property.

Claims (7)

1. Substituted pyridylpyrazoles of general formula (I), characterized in that m represents the numbers 0 6 1, n represents the numbers 1, 2 or 3, R1 represents hydrogen, alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen or C? -C4 alkoxy, or alkenyl respectively or alkynyl of 2 to 6 carbon atoms each, optionally substituted with cyano or halogen respectively, R2 represents hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen, alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen or C?-C 4 alkoxy, or alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl having from 1 to 6 carbon atoms each optionally substituted with cyano, halogen or C alco-C alkoxy, R 3 represents hydrogen , cyano, halogen or alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen or C 1 -C 6 alkoxy, and R 4 represents nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the. groups -Q-R5, -NH-R5, -NH-O-R5-, -NHSOz-R5, -N (S02-R5) 2 -COx-R5, -CQ1-Q2-R5, -CQ1-NH-R5 , -Q2-CQ2-R5, -NH-CQX-R5, -N (S02-R5) (CQX-R5), -Q2-CQX-Q2-R5, -NH-CQX-Q2-H5, or -Q2- CQX-NH-R5, representing QO, S, SO or S02, and Q1 and Q2 in each case oxygen or sulfur, and R5 represents alkyl of 1 to 6 carbon atoms, optionally substituted with cyano, halogen, C?-C alco alkoxy, C?-C 4 alkylthio, C (-C 4 alkylcarbonyl, C (-C 4 alkoxycarbonyl or alkylamino (C? -C4) carbonyl,. R5 further represents alkenyl or alkynyl of 2 to 6 carbon atoms each optionally substituted respectively with cyano, carboxy, halogen, alkyl (C? -C4) carbonyl, alkoxy (C? C) carbonyl or alkylamino (C? -C4) carbonyl, R also represents cycloalkyl or cycloalkylalkyl with 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl part, each optionally substituted each with cyano, carboxy, halogen, alkyl (C? -C4) carbonyl or (C? -C4) alkoxycarbonyl, R5 further represents aryl or arylalkyl having 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part respectively optionally substituted each with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, C 4 -C 4 haloalkoxy, C 1 -C alkyl halogen alkylthio C? -C4, C? -C4 alkylsulfinyl, C? -C4 alkylsulfonyl, C? -C alkylamino? or dimethylamino, or R5 further represents heterocyclyl or heterocyclylalkyl with 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and / or 1 or 2 oxygen atoms and / or a sulfur atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl part optionally each substituted with hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C 1 -C 4 alkyl, C 1 -C 4 haloalkyl, C 1 -C 4 alkoxy, haloalkoxy CC , C 1 -C 4 alkylthio, C 4 -C 4 haloalkyl, C 1 -C 4 alkylsulfinyl, C 1 -C 4 alkylsulfonyl, C 1 -C alkylamino or dimethylamino.

2. Process for the preparation of substituted pyridylpyrazoles of general formula (I), wherein, n, Rx, R2, R3 and R4 have the meaning indicated in claim 1, characterized in that hydrazine or its derivatives of general formula (II) are reacted, H2N-NH-RX n: wherein Rx has the meaning indicated above, with substituted pyridyl-1,3-dicarbonyl compounds of general formula (III), wherein m, n, R2, R3 and R4 have the meaning indicated above, or with pyridyl-carbonyl compounds of general formula (IV) wherein m, n, R3 and R4 have the meaning indicated above, Q3 represents oxygen or sulfur and R represents hydrogen or alkyl, and / or optionally tautomers of the compounds of formula (IV)

3. Herbicidal, insecticidal and acaricidal agents characterized by containing at least one substituted pyridylpyrazole of formula (I) according to claim 1.

4. Process for combating unwanted plants, characterized in that substituted pyridylpyrazoles of formula (I) are made to act according to claim 1 on unwanted plants and / or their environment.

5. Use of substituted pyridylpyrazoles of formula (I) according to claim 1 for combating unwanted plants, insects or mites.

6. Process for the manufacture of herbicidal, insecticidal or acaricidal agents, characterized in that pyridylpyrazoles of formula (I) are mixed according to claim 1 with extenders and / or surfactants.

7. Process for combating animal parasites, characterized in that pyridylpyrazoles of formula (I) are made to act according to claim 1 on animal parasites and / or their environment. SUMMARY OF THE INVENTION The invention relates to new substituted pyridylpyrazoles of general formula (I), wherein m = 0 or 1; n = 1, 2 or 3; Rx = hydrogen, alkyl of 1-6 C atoms, optionally substituted with cyano, halogen or C? -C alkoxy, or alkenyl or alkynyl of 2-6 C atoms, optionally substituted with cyano or halogen; R 2 = hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen or alkyl substituted with cyano, halogen or C 1 -C 4 alkoxy or alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl of 1-6 carbon atoms, as the case may be substituted with cyano, halogen or C 1 -C 4 alkoxy; R3 = hydrogen, cyano, halogen or alkyl of 1-6 C atoms substituted with cyano, halogen or C? -C4 alkoxy and R4 = nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or one of the following groups: -Q-R5, -NH-R5, -NH-O-R5, -NHS02-R5, -N (S02-R5) 2, -CQX-R5, -CQX-Q2-R5, - CQX-NH-R5, -Q2-CQX-R5, -NH-CQX-R5, -N (SQ-R5) (CQX-R5), -Q2-CQX-Q2-R5, -NH-CQ-Q2-RS , or -Q2-CQX-NH-R5, wherein Q = O, S, SO or S02, and Q1 and Q2 = oxygen or sulfur, and R5 has the meaning cited in the description. The invention also relates to a process for the production and use of new pyridylpyrazoles as phytosanitary agents, especially as herbicides, insecticides and acaricides.