CA2290379A1 - 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

Le A 32 417-Foreign Countries Kri/klu/NT
y S ~9~,~, 1°HIS A~EN~B~D
~E~fi TRANSLATION
Substituted pyridylpyrazoles The invention relates to novel substituted pyridylpyrazoles, to processes for their preparation and to their use as crop treatment agents, in particular as herbicides, in s secticides and acaricides.
A large number of substituted pyridylpyrazoles is already known from the (Patent) literature (cf. J. Med. Chem. 38 (1995), 3524-3535; DE 2623302; DE 1 9530606, WO 93/07138; JP 08193067 - cited in Chem. Abstracts 125:247808). Some of them are also known to be suitable for use as crop treatment agents, such as, for example, as fungicides, herbicides, insecticides or acaricides. However, these compounds have not attained any particular importance.
This invention, accordingly, provides the novel substituted pyridylpyrazoles of the general formula (I) R' I
R'' (R4)n in which m represents the number 0 or 1, n represents the number 1, 2 or 3, RI represents hydrogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, or represents in Le A 32 417-Foreign Countries each case optionally cyano- or halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, R2 represents hydrogen, nitro, hydroxyl, mercapto, carboxyl, cyano, thio-carbamoyl, halogen, represents cyano-, halogen- or C 1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms, R3 represents hydrogen, cyano, halogen or represents optionally cyano-, halogen-or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms and R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-capto, amino, hydroxyamino, halogen or represents one of the groupings -Q-RS, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -CQ1-R5, -CQ1-Q2-R5, -CQ1-NH-R5, -Q2-CQ1-R5, -NH-CQ1-R5, -N(S02-RS)(CQ1-RS), -Q2-CQ1-Q2_R5~ _NH-CQ1-Q2-RS or -Q2-CQ1-NH-R5, where Q represents O, S, SO or 502, Q1 and Q2 each represent oxygen or sulphur and RS represents optionally cyano-, halogen-, C 1-C4-alkoxy-, C 1-C4-alkylthio-, C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkyl having 1 to 6 carbon atoms, RS furthermore represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon at-oms, RS furthermore represents in each case optionally cyano-, carboxyl-, halogen-, C 1-C4-alkyl-carbonyl- or C 1-C4-alkoxy-carbonyl-substituted cycloalkyl or Le A 32 417-Foreign Countries cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C 1-C4-halo-genoalkyl-, C 1-C4-alkoxy-, C 1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon at-oms in the alkyl moiety, or RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C 1-C4-alkyl-, C 1-C4-haloge-noalkyl-, C 1-C4-alkoxy-, C 1-C4-halogenoalkoxy-, C 1-C4-alkylthio-, C 1-C4-halogenoalkylthio-, C 1-C4-alkylsulphinyl-, C 1-C4-alkylsulphonyl-, C 1-C4-alkylamino- or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or one sulphur atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.
The novel substituted pyridylpyrazoles of the general formula (I) are obtained when hydrazine or its derivatives of the general formula (II) H2N-NH-R1 (II) in which R1 is as defined above, are reacted with substituted pyridyl-1,3-dicarbonyl compounds of the general for-mula (III) Le A 32 417-Foreign Countries O~ R3 (III) R4)n N
I
(~)m in which m, n, R2 , R3 and R4 are each as defined above, or with substituted pyridyl-carbonyl compounds of the general formula (IV) R R

R3 (IV) \~R4)n ~)m in which m, n, R3 and R4 are each as defined above, Q3 represents oxygen or sulphur and R represents hydrogen or alkyl, - and/or, if appropriate, tautomers of the compounds of the formula (IV) -, Le A 32 417-Foreign Countries y if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent, and the resulting compounds of the formula (I) are, if desired, subjected to further conversions according to customary methods in the context of the above definition of substituents.
The compounds of the general formula (I) can be converted according to customary methods into other compounds of the general formula (I) according to the above definition of substituents, for example by customary alkylation, acylation or sulphonylation reactions (for example R1: H -~ CH3, CHF2, C2H5, CH2CH=CH2;
R4: OH ~ OCH3, OC2H5, OCHF2, OCH2CH=CH2, OCOCH3; SH -~ SCH3, SC2H5; NH2 ~ NHC3H~, NHCOCH3, NHS02CH3), or by electrophilic or nucleo-philic substitution reactions (for example R3: H ~ C1, Br; R4: F ~ OH, SH, NH2) -cf. also the Preparation Examples.
The novel substituted pyridylpyrazoles of the general formula (I) have interesting biological properties, which make it possible to use them as crop treatment agents.
They have strong herbicidal, insecticidal and acaricidal activity and have in particular excellent and selective herbicidal action.
In the definitions, the saturated or unsaturated hydrocarbon radicals, such as alkyl, alkenyl or alkinyl, are in each straight-chain or branched.
Halogen generally represents fluorine, chlorine, bromine or iodine, preferably fluo-rine, chlorine or bromine, in particular fluorine or chlorine.
The invention preferably provides compounds of the formula (I) in which m represents the number 0 or 1, Le A 32 417-Foreign Countries n represents the numbers 1, 2 or 3, R1 represents hydrogen, represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-or bromine-substituted propenyl, butenyl, propinyl or butinyl, R2 represents hydrogen, nitro, hydroxyl, mercapto, carboxyl, cyano, thiocar-bamoyl, fluorine, chlorine, bromine, represents in each case cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or represents in each case optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted 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, methylsulphinyl, ethylsulphinyl, n- or i-propylsulphinyl, n-, i-, s- or t-butylsulphinyl, methylsulphonyl, ethyl-sulphonyl, n- or i-propylsulphonyl, n-, i-, s- or t-butylsulphonyl, R3 represents hydrogen, fluorine, chlorine, bromine, or represents optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, n-or i-propyl, n-, i-, s- or t-butyl, and R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-capto, amino, hydroxyamino, fluorine, chlorine, bromine, or represents one of the groupings -Q-R5, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -CQ 1 _R5~ _CQ 1 _Q2_RS ~ _CQ 1 _NH_R5~ _Q2_CQ 1 _RS _NH_CQ 1 _R5, -N(S02-RS)(CQ 1-RS), -Q2-CQ 1-Q2-R5, -NH-CQ 1-Q2-RS or -Q2-CQ 1-NH--R5, where Q represents O, S, SO or 502, Q1 and Q2 each represent oxygen or sulphur and RS represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, eth-oxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxy-Le A 32 417-Foreign Countries -7_ carbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl, propinyl or butinyl, RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl- or ethoxy-carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-propylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-, eth-oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino- or dimethylamino-substituted phenyl, benzyl or phenylethyl, or RS furthernlore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluoro-methyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluoro-methylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methyl-amino-, ethylamino-, n- or i-propylamino- or dimethylamino-substituted het-erocyclyl or heterocyclylalkyl from the group consisting of oxiranyl, Le A 32 417-Foreign Countries _g_ oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyr-rolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothi-azolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-methyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thi-s azolylmethyl, pyridinylmethyl, pyrimidinylmethyl.
The invention relates in particular to the compounds of the formula (I) in which m represents the number 0 or 1, n represents the number 1, 2 or 3, R1 represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-or ethoxy-substituted methyl or ethyl, R2 represents hydroxyl, mercapto, fluorine, chlorine, bromine, or represents in each case cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulphinyl, ethyl-sulphinyl, methylsulphonyl or ethylsulphonyl, R3 represents fluorine, chlorine, bromine or optionally cyano-, fluorine-, chlorine-, methoxy- or ethoxy-substituted methyl or ethyl, and R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mer-capto, amino, hydroxyamino, halogen or represents one of the groupings -Q-R5, -NH-R5, -NH-O-R5, -NH-S02-R5, -N(S02-RS)2, -CQI-R5, -CQ1-Q2-R5, -CQ1-NH-R5, -Q2-CQ1-R5, -NH-CQ1-R5, -N(S02-RS)_ (CQ1-RS), -Q2-CQ1-Q2-R5, -NH-CQ1-Q2-RS or -Q2-CQ1-NH-R5, where Q
represents O, S, SO or 502, Q1 and Q2 each represent oxygen or sulphur and Le A 32 417-Foreign Countries RS represents in each case optionally cyano-, fluorine-, chlorine-, methoxy-, eth-oxy-, methylthio-, ethylthio-, acetyl-, propionyl-, methoxycarbonyl-, ethoxy-carbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl-, ethoxycarbonyl-, methylaminocarbonyl- or ethylaminocarbonyl-substituted propenyl, butenyl, propinyl or butinyl, RS furthermore represents in each case optionally cyano-, carboxyl-, fluorine-, chlorine-, bromine-, acetyl-, propionyl-, methoxycarbonyl- or ethoxy-carbonyl-substituted cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclo-propylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, difluoromethyl-, trifluoromethyl-, methoxy-, eth-oxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, difluoromethylthio-, trifluoromethylthio-, methylsulphinyl-, ethyl-sulphinyl-, methylsulphonyl-, ethylsulphonyl-, methylamino-, ethylamino- or dimethylamino-substituted phenyl, benzyl or phenylethyl, or RS furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, methyl-, ethyl-, n- or i-propyl-, n-, i-, s- or t-butyl-, dichloromethyl-, trichloromethyl-, difluo-romethyl-, trifluoromethyl-, chlorodifluoromethyl-, fluorodichloromethyl-, methoxy-, ethoxy-, n- or i-propoxy-, difluoromethoxy-, trifluoromethoxy-, methylthio-, ethylthio-, n- or i-propylthio-, difluoromethylthio-, trifluo-romethylthio-, chlorodifluoromethylthio-, fluorodichloromethylthio-, methyl-sulphinyl-, ethylsulphinyl-, methylsulphonyl-, ethylsulphonyl-, methyl-Le A 32 417-Foreign Countries amino-, ethylamino-, n- or i-propylamino- or dimethylamino-substituted het-erocyclyl or heterocyclylalkyl from the group consisting of oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyr-rolyl, pyrazolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothi-azolyl, oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolyl-methyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thi-azolylmethyl, pyridinylmethyl, pyrimidinylmethyl.
A particularly preferred group of compounds of the general formula (I) are com-pounds of the formula (Ia), R' Ra) n in which (la) n, R1, R2, R3 and R4 each have the meanings given above as being particularly pre-ferred.
A further particularly preferred group of compounds of the general formula (I) are compounds of the formula (Ib), R' I
RZ N~
N

Ni R4y Le A 32 417-Foreign Countries _ -11-in which n, R1, R2, R3 and R4 each have the meanings given above as being particularly pre-y ferred.
A further particularly preferred group of compounds of the general formula (I) are compounds of the formula (Ic), R' R' (Ic) R
in which n, R1, R2, R3 and R4 each have the meanings given above as being particularly pre-ferred.
The general or preferred radical definitions given above apply both to the end prod-ucts of the formula (I) and, correspondingly, to the starting materials or intermediates required in each case for the preparation. These radical definitions can be combined with each other as desired, i.e. including combinations between the given preferred ranges.
Using, for example, methylhydrazine and 2-chloro-1-(4-cyano-3-methoxy-pyridin-yl)-4,4-difluoro-butane-1,3-dione as starting materials, the course of the reaction in the process according to the invention can be illustrated by the following formula scheme:

Le A 32 417-Foreign Countries H3C CHFz N

Nhi + -~ ~ CI
NHz N
~OCH3 CN
The formula (II) provides a general definition of the hydrazine derivatives to be used as starting materials in the process according to the invention for preparing com-pounds of the formula (I). In the formula (II), R1 preferably or in particular has that meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for R1.
The starting materials of the general formula (II) are known chemical for synthesis.
The formula (III) provides a general definition of the substituted pyridyl-1,3-di-carbonyl compounds further to be used as starting materials in the process according to the invention. In the formula (III), n, R2, R3 and R4 each preferably or in particu-lar have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for n, R2, R3 and R4.
The formula (IV) provides a general definition of the substituted pyridyl-carbonyl compounds further to be used as starting materials in the process according to the invention. In the formula (IV), n, R3 and R4 each preferably or in particular have those meanings which have already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention as being preferred or as being particularly preferred for n, R3 and R4; Q3 preferably repre-Le A 32 417-Foreign Countries . -13-sents oxygen or sulphur and R preferably represents hydrogen or C1-C4-alkyl, in particular hydrogen, methyl or ethyl.
The starting materials of the-formulae (III) and (IV) are known and/or can be pre-y pared by known processes (cf. J. Chem. Soc. C 1969, 2738-2747; loc. cit. C
1970, 796-800; J. Chem. Soc., Perkin Trans. I 1988, 2785-2789; J. Heterocycl. Chem.

(1993), 855-859; J. Med. Chem. 33 (1990), 1859-1865; J. Org. Chem. 47 (1982), 3027-3038; loc. cit. 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 preparing the novel compounds of the formula (I) are especially organic solvents. These in-clude, in particular, aliphatic, alicyclic or aromatic, optionally halogenated hydrocar-bons, such as, for example, benzine, benzene, toluene, xylene, chlorobenzene, dichlo-robenzene, petroleum ether, hexane, cyclohexane, dichloromethane, chloroform, car-bon tetrachloride; ethers, such as diethyl ether, diisopropyl ether, dioxane, tetra-hydrofuran or ethylene glycol dimethyl ether or ethylene glycol diethyl ether;
ke-tones, 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,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide, N-methyl-pyrrolidone or hexamethylphosphoric triamide;
esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, 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.
Suitable reaction auxiliaries for the process according to the invention are in general the customary inorganic or organic bases or acid acceptors. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkoxides, such as, for example, sodium acetate, potassium Le A 32 417-Foreign Countries acetate or calcium acetate, lithium amide, sodium amide, potassium amide or calcium amide, sodium carbonate, potassium carbonate or calcium carbonate, sodium bi-carbonate, potassium bicarbonate or calcium bicarbonate, lithium hydride, sodium hydride, potassium hydride or calcium hydride, lithium hydroxide, sodium hydrox-ide, potassium hydroxide or calcium hydroxide, sodium methoxide, ethoxide n-or i-propoxide, n-, i-, s- or t-butoxide or potassium methoxide, ethoxide, n- or i-propox-ide, n-, i-, s- or t-butoxide; furthermore also basic organic nitrogen compounds, such as, for example, trimethylamine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N,N-dimethyl-cyclohexylamine, dicyclohexylamine, ethyl-di-cyclohexylamine, 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).
When carrying out the process according to the invention, the reaction temperatures can be varied within a relatively wide range. In general, the process 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 under atmospheric pressure. However, it is also possible to carry out the process according to the inven-tion under elevated or reduced pressure - in general between 0.1 bar and 10 bar.
To carry out the process according to the invention, the starting materials are gener-ally employed in approximately equimolar amounts. However, it is also possible to use one of the components in a relatively large excess. The reaction is generally car-ried out in a suitable diluent in the presence of a reaction auxiliary, and the reaction mixture is generally stirred for several hours at the temperature required.
Work-up is carried out according to customary methods (cf. the Preparation Examples).

Le A 32 417-Foreign Countries The active compounds according to the invention can be used as defoliants, desic cants, haulm-killers and, especially, as weed-killers. By weeds, in the broadest sense, are to be understood all plants which grow in locations where they are undesired.
Whether the substances according to the invention act as total or selective herbicides depends essentially on the amount used.
The active compounds according to the invention can be used, for example, in con-nection with the following plants:
Dicotyledonous weeds of the genera: Sinapis, Lepidium, Galium, Stellaria, Matri caria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abuti lon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus and Taraxacum.
Dicotyledonous crops of the genera: Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Bras-sica, Lactuca, Cucumis and Cucurbita.
Monocotyledonous weeds of the genera: Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sor ghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scir pus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus and Apera.
Monocotyledonous crops of the genera: Oryza, Zea, Triticum, Hordeum, Avena, Se-cale, Sorghum, Panicum, Saccharum, Ananas, Asparagus and Allium.
However, the use of the active compounds according to the invention is in no way restricted to these genera, but also extends in the same manner to other plants.

Le A 32 417-Foreign Countries The compounds are suitable, depending on the concentration, for the total control of weeds, for example on industrial terrain and rail tracks, and on paths and squares with or without tree plantings. Equally, the compounds can be employed for control-s ling weeds in perennial cultures, for example forests, decorative tree plantings, or-chards, vineyards, citrus groves, nut orchards, banana plantations, coffee plantations, tea plantations, rubber plantations, oil palm plantations, cocoa plantations, soft fruit plantings and hopfields, on lawns, turf and pasture-land, and for the selective control of weeds in annual crops.
The compounds of the formula (I) according to the invention are particularly suitable for the selective control of monocotyledonous and dicotyledonous weeds in mono-cotyledonous and dicotyledenous crops by both the pre- and the post-emergence method.
The active compounds are suitable for controlling animal pests, preferably arthropods and nematodes, in particular insects and arachnids, which are encountered in agri-culture, in forestry, in the protection of stored products and of materials, and in the hygiene sector. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Isopoda, for example, Oniscus asellus, Armadillidium vulgare and Porcellio scaber.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Chilopoda, for example, Geophilus carpophagus and Scutigera spec.
From the order of the Symphyla, for example, Scutigerella immaculate.
From the order of the Thysanura, for example, Lepisma saccharine.

Le A 32 417-Foreign Countries From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Orthoptera, for example, Blatta orientalis, Periplaneta ameri-cana, Leucophaea maderae, Blatella germanica, Acheta domesticus, Gryllotalpa spp., Locusts migratoria migratorioides, Melanoplus differentialis and Schistocerca gre-garia.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Pediculus humanus corporis, Haematopinus spp. and Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes spp. and Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis and Thrips tabaci.
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus interme-thus, Piesma quadrata, Cimex lectularius, Rhodnius prolixus and 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, Macro-siphum avenae, Myzus spp., Pemphigus spp., Phorodon humuli, Phylloxera vastatrix, Rhopalosiphum path, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidi-ella aurantii, Aspidiotus hederae, Pseudococcus spp. and Psylla spp.

Le A 32 417-Foreign Countries 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, Carpocapsa 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 magnanima and Tortrix viridana.
From the order of the Coleoptera, for example, Anobium punctatum, Rhizopertha dominica, Acanthoscelides obtectus, Bruchidius obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surina-mensis, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus 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., Melolontha melolontha, Amphimallon solstitialis and Costely-tra zealandica.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis and 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., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia spp., Bibio Le A 32 417-Foreign Countries hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae and Tipula paludosa.
From the order of the Siphonaptera, for example, Xenopsylla cheopis and Cerato-phyllus spp.
From the order of the Arachnida, for example, Scorpio maurus and Latrodectus mactans.
From the order of the Acarina, for example, Acarus situ, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp. and Tetranychus spp.
The phytoparasitic nematodes include, for example, Pratylenchus spp., Radopholus spp., Ditylenchus spp., Tylenchulus spp., Heterodera spp., Globodera spp., Meloido-gyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp., Trichodorus spp., Tylenchus spp., Helicotylenchus spp., Rotylenchus spp. and Tylenchulus spp..
The active compounds can be converted into the customary formulations, such as solu-tions, emulsions, wettable powders, suspensions, powders, dusting agents, pastes, solu-ble powders, granules, suspo-emulsion concentrates, natural and synthetic materials impregnated with active compound, and very fine capsules in polymeric substances.
These formulations are produced in a known manner, for example by mixing the active compounds with extenders, that is liquid solvents and/or solid carriers, optionally with the use of surface-active agents, that is emulsifying agents and/or dispersing agents and/or foam-forming agents.

Le A 32 417-Foreign Countries If the extender used is water, it is also possible to employ for example organic solvents as auxiliary solvents. Suitable liquid solvents are in the main: aromatics, such as xy-lene, toluene or alkylnaphthalenes, chlorinated aromatics and chlorinated aliphatic hy-drocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, for example petroleum fractions, min-eral and vegetable oils, alcohols, such as butanol or glycol and also their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclo-hexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulph-oxide, and also water.
Suitable solid carriers are: for example ammonium salts and ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatomaceous earth, and ground synthetic minerals, such as finely divided silica, alumina and sili-cates, suitable solid carriers for granules are: for example crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, and also synthetic granules of inorganic and organic meals, and granules of organic material such as saw-dust, coconut shells, maize cobs and tobacco stalks; suitable emulsifiers and/or foam-forming agents are: for example non-ionic and anionic emulsifiers, such as polyoxyeth-ylene fatty acid esters, polyoxyethylene fatty alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulphonates, alkyl sulphates, arylsulphonates and also protein hydrolysates; suitable dispersants are: for example lignin-sulphite waste liquors and methylcellulose.
Tackifiers such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvi-nyl acetate, and also natural phospholipids, such as cephalins and lecithins, and syn-thetic phospholipids, can be used in the formulations. Further additives can be mineral and vegetable oils.
It is possible to use colorants such as inorganic pigments, for example iron oxide, tita-nium oxide and Prussian Blue, and organic dyes, such as alizarin dyes, azo dyes and Le A 32 417-Foreign Countries metal phthalocyanine dyes, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general comprise between 0.1 and 95 per cent by weight of active compound, preferably between 0.5 and 90%.
For controlling weeds, the active compounds according to the invention, as such or in the form of their formulations, can also be used as mixtures with known herbicides, ready-to-use formulations or tank mixes being possible.
Possible components for the mixtures are known herbicides, for example acetochlor, acifluorfen(-sodium), aclonifen, alachlor, alloxydim(-sodium), ametryne, amidochlor, amidosulphuron, asulam, atrazine, azimsulphuron, benazolin, ben-furesate, bensulphuron(-methyl), bentazon, benzofenap, benzoylprop(-ethyl), biala-phos, bifenox, bromobutide, bromofenoxim, bromoxynil, butachlor, butylate, cafen-strole, carbetamide, chlomethoxyfen, chloroamben, chloroidazon, chloro-imuron(-ethyl), chloronitrofen, chlorosulphuron, chlorotoluron, cinmethylin, cino-sulphuron, clethodim, clodinafop(-propargyl), clomazone, clopyralid, clopyrasul-phuron, cloransulam(-methyl), cumyluron, cyanazine, cycloate, cyclosulphamuron, cycloxydim, cyhalofop(-butyl), 2,4-D, 2,4-DB, 2,4-DP, desmedipham, diallate, di-camba, diclofop(-methyl), difenzoquat, diflufenican, dimefuron, dimepiperate, di-methachlor, dimethametryn, dimethenamid, dinitramine, diphenamid, diquat, dithio-pyr, diuron, dymron, EPTC, esprocarb, ethalfluralin, ethametsulphuron(-methyl), ethofumesate, ethoxyfen, etobenzanid, fenoxaprop-ethyl, flamprop(-isopropyl), flam-prop(-isopropyl-L), flamprop(-methyl), flazasulphuron, fluazifop(-butyl), flumet-sulam, flumiclorac(-pentyl), flumioxazin, flumipropyn, fluometuron, fluoro-chloridone, fluoroglycofen(-ethyl), flupoxam, flupropacil, flurenol, fluridone, flur-oxypyr, flurprimidol, flurtamone, fomesafen, glufosinate(-ammonium), glyphosate(-isopropylammonium), halosafen, haloxyfop(-ethoxyethyl), hexazinone, imazametha-benz(-methyl), imazamethapyr, imazamox, imazapyr, imazaquin, imazethapyr, Le A 32 417-Foreign Countries imazosulphuron, ioxynil, isopropalin, isoproturon, isoxaben, isoxaflutole, isoxapyri-fop, lactofen, lenacil, linuron, MCPA, MCPP, mefenacet, metamitron, metazachlor, methabenzthiazuron, metobenzuron, metobromuron, metolachlor, metosulam, metox-uron, metsulphuron(-methyl), metribuzin, molinate, monolinuron, naproanilide, napropamide, neburon, nicosulphuron, norflurazon orbencarb, oryzalin, oxadiazon, oxyfluorfen, paraquat, pendimethalin, phenmedipham, piperophos, pretilachlor, primisulphuron(-methyl), prometryn, propachlor, propanil, propaquizafop, propyz-amide, prosulphocarb, prosulphuron, pyrazolate, pyrazosulphuron(-ethyl), pyrazoxy-fen, pyributicarb, pyridate, pyrithiobac(-sodium), quinchlorac, quinmerac, quizalo-fop(-ethyl), quizalofop(-p-tefuryl), rimsulphuron, sethoxydim, simazine, simetryn, sulcotrione, sulphentrazone, sulphometuron(-methyl), sulphosate, tebutam, tebuthi-uron, terbuthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiazimin, thifensulphuron(-methyl), thiobencarb, tiocarbazil, tralkoxydim, triallate, triasul-phuron, tribenuron(-methyl), triclopyr, tridiphane, trifluralin and triflusulphuron.
Mixtures with other known active compounds, such as fungicides, insecticides, acaricides, nematicides, bird repellents, plant nutrients and agents which improve soil structure, are also possible.
The active compounds can be used as such, in the form of their formulations or in the use forms prepared therefrom by further dilution, such as ready-to-use solutions, sus-pensions, emulsions, powders, pastes and granules. They are used in a customary man-ner, for example by watering, spraying, atomizing or scattering.
The active compounds according to the invention can be applied either before or after emergence of the plants. They can also be incorporated into the soil before sowing.
The amount of active compound used can vary within a substantial range. It depends essentially on the nature of the desired effect. In general, the amounts used are between 1 g and 10 kg of active compound per hectare of soil surface, preferably between 5 g and 5 kg per ha.

Le A 32 417-Foreign Countries The preparation and use of the active compounds according to the invention can be seen from the examples below.

Le A 32 417-Foreign Countries Preparation Examples:
Example 1 HO
CI
20.2 g (89 mmol) of ethyl 3-(6-chloro-pyridin-3-yl)-3-oxo-propionate are initially charged in 40 ml of acetic acid and, at an internal temperature of approximately 40°C, admixed dropwise with 5.8 g (126 mmol) of methylhydrazine. The mixture is subsequently heated at from 90°C to 100°C for approximately 90 minutes, and a brown solid precipitates out. The cold mixture is poured into 300 ml of water and the precipitated solid is filtered off, washed with water and dried at 50°C
under a reduced pressure.
This gives 13.6 g (73% of theory) of 5-(6-chloro-pyridin-3-yl)-2-methyl-2H-pyrazol-3-0l of melting point 220°C.
Example 2 H
i FsC N.N
N
CI
8.0 g (160 mmol) of hydrazine hydrate and 16.3 g (160 mmol) of acetic anhydride are added successively to a solution of 33.5 g (133 mmol) of 1-(6-chloro-pyridin-3-yl)-4,4,4-trifluorobutane-1,3-dione in 160 ml of acetic acid. The reaction mixture is Le A 32 417-Foreign Countries heated at from 90°C to 100°C for one hour and the cold mixture is poured into 800 ml of ice-water. The precipitated solid is filtered off, washed with water and dried at SO°C under a reduced pressure.
S This gives 29.8 g (90% of theory) of 2-chloro-S-(S-trifluoromethyl-1H-pyrazol-3-yl)-pyridine of melting point 183°C.
Example 3 i F2CH0 N' N
N
CI
A mixture of 12,6 g (60 mmol) of S-(6-chloro-pyridin-3-yl)-2-methyl-2H-pyrazol-ol and 100 ml of N,N-dimethyl-formamide is admixed with 16.5 g of potassium carbonate and heated at SO°C for approximately 60 minutes. At a temperature be-tween 60°C and 70°C, approximately 30 g (0.35 mol) of chlorodifluoromethane are 1 S then introduced over a period of one hour. The reaction mixture is cooled to room temperature, poured into 1.3 litres of water and acidified using 2N
hydrochloric acid.
The precipitated solid is filtered off with suction, dissolve in dichloromethane, washed successively with saturated aqueous sodium bicarbonate solution and satu-rated aqueous sodium chloride solution, dried with magnesium sulphate and filtered.
The filtrate is concentrated under water pump vacuum and the residue is separated by column chromatography using toluene/ethyl acetate (Vol.: l:l).
In the main fraction, 6.S g (42% of theory) of 2-chloro-S-(S-difluoro-methoxy-methyl-1H-pyrazol-3-yl)-pyridine of melting point 102°C are obtained.

Le A 32 417-Foreign Countries Example 4 i F2CH0 N' N
CI
N
CI
At room temperature (approximately 20°C), 2.2 g (1.63 mmol) of sulphuryl chloride are added with stirring to a solution of 3.6 g (13.9 mmol) of 2-chloro-5-(5-difluo-romethoxy-1-methyl-1H-pyrazol-3-yl)-pyridine in 15 ml of dichloromethane. The mixture is stirred at approximately 20°C for three hours, diluted with 20 ml of di-chloromethane, washed with saturated aqueous sodium bicarbonate solution and with saturated aqueous sodium chloride solution, dried with magnesium sulphate and fil-tered. The solvent is carefully distilled off from the filtrate under water pump vac-uum.
This gives 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.
Using, instead of sulphuryl chloride, a corresponding solution of bromine in dichlo-romethane, 2-chloro-5-(4-bromo-5-difluoromethoxy-1-methyl-1H-pyrazol-3-yl)-pyridine ("Example 11") of melting point 60°C is obtained in a similar yield.
Example 5 i FsC N . N
N
CI

Le A 32 417-Foreign Countries At approximately 20°C, 18.3 g (129 mmol) if iodomethane are added over a period of approximately two minutes to a solution of 10.1 g (40 mmol) of 2-chloro-5-(5-tri-fluoromethyl-1H-pyrazol-3-yl)-pyridine and 8.4 g (60 mmol) of potassium carbonate in 150 ml of acetonitrile. The reaction mixture is stirred at 40°C for 3 hours and, after cooling, concentrated under water pump vacuum. The residue is taken up in 100 ml of dichloromethane and 200 ml of water, and the organic phase is separated off, washed with water, dried with magnesium sulphate and filtered. The filtrate is con-centrated under water pump vacuum and the residue is separated by column chro-matography using n-hexane/ethyl acetate (Vol.: 2:1).
This gives 6.6 g (50,5% of theory) of 2-chloro-5-(1-methyl-5-trifluoromethyl-pyrazol-3-yl)-pyridine of melting point 95°C.
Example 6 i FsC N . N
CI
N
CI
At from 75°C to 85°C, 10 g (141 mmol) of chlorine gas are introduced with stirring over a period of 2 hours in a solution of 2.0 g (7.6 mmol) of 2-chloro-5-(1-methyl-5-trifluoromethyl-1H-pyrazol-3-yl)-pyridine in 40 ml of acetic acid. The reaction mix-ture is cooled, poured into 100 ml of ice-water and extracted with ethyl acetate. The organic phase is separated off and washed successively with saturated aqueous so-dium bicarbonate solution and saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered. The filtrate is concentrated under water pump vacuum.

Le A 32 417-Foreign Countries This gives 2.05 g (91% of theory) of 2-chloro-5-(4-chloro-1-methyl-5-trifluoro-methyl-1H-pyrazol-3-yl)-pyridine of melting point SS°C.
Example 7 H3C-S~ CH3 N
/N
/N
CI
At approximately 20°C, 10.3 g (224 mmol) of methylhydrazine are added to a solu-tion of 23.0 g (88.6 mmol) of 1-(6-chloro-pyridin-3-yl)-3,3-bis-methylthio-2-propen-1-one in 145 ml of acetonitrile. The reaction mixture is heated under reflux for 120 minutes and then poured into ice-water. The precipitated solid is filtered off with suction, washed with water and dried under reduced pressure.
This gives 17.9 g (84% of theory) of 3-(6-chloro-pyridin-3-yl)-1-methyl-5-methyl-thin-1H-pyrazole of melting point 93°C.
Example 8 H3C-S~ CH3 N
CI ~ N
/N
I

Le A 32 417-Foreign Countries At 0°C, a drop of acetic acid and 1.8 g (9 mmol) of 1,3-dichloro-5,5-dimethyl-hy-dantoin are added successively to a solution of 3.8 g (16 mmol) of 3-(6-chloro-pyr-idin-3-yl)-1-methyl-5-methylthio-1H-pyrazole in 30 ml of diethyl ether. The reaction mixture is stirred at room temperature (approximately 20°C) for 18 hours and ad-mixed successively with 20 ml of water and 20 ml of ethyl acetate. The organic phase is separated off, washed successively with saturated aqueous sodium bicarbon-ate solution and saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered. The filtrate is concentrated under water pump vacuum.
This gives 3.8 g (87% of theory) of 4-chloro-3-(6-chloro-pyridin-3-yl)-1-methyl-5-methylthio-1 H-pyrazole as an amorphous residue.
Example 9 At 0°C, 7.5 g (30 mmol) of 3-chloro-perbenzoic acid are added with stirring to a so-lution of 1.9 g (7.7 mmol) of 4-chloro-3-(6-chloro-pyridin-3-yl)-1-methyl-5-methyl-thio-1H-pyrazol in 30 ml of dichloromethane. The reaction mixture is stirred at room temperature (approximately 20°C) for 18 hours, the precipitated solid is filtered off and the filtrate is washed successively with saturated sodium thiosulphate solution, with saturated sodium bicarbonate solution and saturated sodium chloride solution, dried with magnesium sulphate and filtered. The filtrate is concentrated under water pump vacuum.

Le A 32 417-Foreign Countries This gives 2.0 g (81% of theory) of 4-chloro-3-(6-chloro-1-oxy-pyridin-3-yl)-1-methyl-5-methylsulphonyl-1H-pyrazole as an amorphous residue.
By the methods of Preparation Examples 1 to 9, and in accordance with the general description of the preparation processes according to the invention, it is also possible to prepare, for example, the compounds of the formula (I) listed in Table 1 below.
R' R3 \ 4 ~R ~n N

Le A 32 417-Foreign Countries Table 1: Examples of compounds of the formula (I) Ex. No. R R R ~ Melting " point (°C) I
~~~m CH3 S02CH3 Cl ~ 169 N CI
11 CH3 OCHF2 Br ~ 60 N CI
12 CH3 SCH3 Br ~ 95 N CI
13 CH3 S02CH3 Br N CI
14 CH3 SOCH3 Cl N CI
CH3 SOCH3 Br ~ 184 i N CI
16 CH3 CN Cl N CI

Le A 32 417-Foreign Countries Table 1: (Continued) Ex. No. R1 R~ R~ . ~ Melting " point (°C) I
~~~m 17 CH3 CN Br N CI

N CI

N CI

N CI

N Br N Br N Br N Br Le A 32 417-Foreign Countries Table 1: (Continued) Ex. No. R1 Rz R ~ Melting N~(R4>" point (°C) I
~~~m N CI

N Br 27 CH3 S02CH3 CH3 ~ 126 N CI
28 CH3 OCHF2 C1 ~ 90 N CN

N CN
30 CH3 CF3 Br N CN
31 CH3 OCHF2 Br ~ 120 N CN

N CN

N CN
34 CH3 S02CH3 Cl N CN

Le A 32 417-Foreign Countries Table 1: (Continued) Ex. No. R1 R~ R-~ ~ Melting " point (°C) I
~~~m 35 CH3 SCH3 Br N CN
36 CH3 CN Br i N CN
37 CH3 S02CH3 Br N CN

N CN

N CI

N CN

N CN

N CI

N CI
b Le A 32 417-Foreign Countries Table 1: (Continued) Ex. No. R1 Rl R ~ Melting 1" point (C) ~~~m 44 CH3 OCHF2 Cl ~ 141 N CI

45 CH3 CF3 Br i N
I

C

46 CH3 OCHF2 Br ~ 127 N CI
b N

CI

48 CH3 CN Br i N CI

b N
I

C

50 CH3 S02CH3 Br ~ 178 N CI
b N

Br Le A 32 417-Foreign Countries Table 1: (Continued) Ex. No. RI R R ~ Melting " point (C) I
~~~m 52 H CF3 Cl ~~~ 146 N CI

53 CH3 SCH3 H ~~~ 93 N CI

54 CH3 OH H ~~~ 236 N CN

55 CH3 OCHF2 H ~~~ 102 N CN

N C

I

Le A 32 417-Foreign Countries Starting materials of the formula (III):
Example (III-1) i2Hs O O
O
/N
I
At from 10°C to 15°C, 50.5 g (0.5 mol) of triethylamine and 58.8 g (0.617 mol) of anhydrous magnesium chloride are added successively to a mixture of 89.3 g (0.525 mol) of potassium monoethyl malonate in 500 ml of acetonitrile. The mixture is stirred at approximately 20°C for 150 minutes, cooled to from -10°C to -5°C and, at this temperature, admixed successively with 88.0 g (0.50 mol) of 2-chloro-pyridin-5-carbonyl chloride and 5.05 g (0.05 mol) of triethylamine. The reaction mixture is stirred at approximately 20°C for 18 hours and then concentrated. The residue is stirred with 500 ml of toluene and admixed slowly with 240 ml of 33% strength hy-drochloric acid. The mixture is stirred at room temperature for 3 hours, the precipi-fated solid is filtered off and the organic phase is separated off from the filtrate. The organic phase is washed with dilute hydrochloric acid and with water, dried with magnesium sulphate and filtered. The filtrate is concentrated under water pump vac-uum and the residue is separated by column chromatography using dichlo-romethane/methanol (Vol.: 9:1).
As main fraction, 82.9 g (73% of theory) of ethyl 3-(6-chloro-pyridin-3-yl)-3-oxo-propionate of melting point 48°C are obtained.

Le A 32 417-Foreign Countries , -38-Example (III-2) FsC O
O
~N
CI
Step 1 N
CI
A solution of 40 g (0.176 mol) of ethyl 3-(6-chloro-pyridin-3-yl)-3-oxo-propionate in 60 ml of acetic acid is admixed successively with 40 ml of water and 7.5 ml of conc.
sulphuric acid and then heated at approximately 80°C for 90 minutes.
The reaction mixture is allowed to cool to room temperature and poured into 600 ml of ice-water.
The resulting suspension is neutralized using dilute aqueous sodium hydroxide solu-tion and extracted with dichloromethane. The organic phase is washed with saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered.
The solvent is carefully distilled off from the filtrate under water pump vacuum.
This gives 21.4 g (78% of theory) of 5-acetyl-2-chloro-pyridine of melting point 98°C.

Le A 32 417-Foreign Countries Step 2 FsC O
O
N
CI
Initially, at approximately 20°C, 20.7 g (0.146 mol) of ethyl trifluoroacetate and then, at -5°C, 30.2 g (0.168 mol) of 30% strength methanolic sodium methoxide so-lution are added successively to a solution of 17.4 g (0.112 mol) of 5-acetyl-2-chloro-pyridine in 200 ml of diethyl ether. The reaction mixture is stirred at 0°C for two hours and then poured into 200 ml of ice-water, and the pH is adjusted to between 2 and 3 using 1N hydrochloric acid. The organic phase is then separated off, washed with saturated aqueous sodium chloride solution, dried with magnesium sulphate and filtered. The solvent is carefully distilled off from the filtrate under water pump vac-uum..
This gives 27.1 g (96% of theory) of 1-(6-chloro-pyridin-3-yl)-4,4,4-trifluorobutane-1,3-dione of melting point 54°C.
Example (III-3) ~S S
HsC ~ wCH3 O
N
CI

Le A 32 417-Foreign Countries At -40°C, a solution of 23.3 g (0.15 mol) of 5-acetyl-2-chloro-pyridin in 50 ml of tetrahydrofuran is added dropwise over a period of 1 S minutes to a suspension of 33.6 g (0,3 mol) of potassium t-butoxide in 210 ml of tetrahydrofuran. The mixture is stirred at -40°C for 30 minutes and then admixed with 11.4 g (0.15 mol) of carbon disulphide. After a further 30 minutes, 42.6 g (0.3 mol) of methyl iodide are added, and the reaction mixture is allowed to warm to room temperature over a period of two hours. The reaction mixture is poured into 1.5 1 of ice-water, adjusted to a pH
between 2 and 3 using 1N hydrochloric acid and extracted with 1.5 litres of ethyl acetate. The organic phase is washed with sodium chloride solution, dried over mag-nesium sulphate and freed from the solvent under reduced pressure. The resulting crude product is stirred with approximately 100 ml of diethyl ether and the precipi-tated solid is filtered off and dried.
This gives 24.3 g (62% of theory) of 1-(6-chloro-pyridin-3-yl)-3,3-bis-methylthio-2-propen-1-one as a crystalline light-yellow solid of melting point 145°C.

Le A 32 417-Foreign Countries Use examples:
Example A
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate is diluted with water to the desired concentration.
Seeds of the test plants are sown in normal soil. After approximately 24 hours, the soil is watered with the preparation of active compound. The amount of water per unit area is advantageously kept constant. The concentration of active compound in the preparation is immaterial, only the active compound application rate per unit area matters.
After three weeks, the degree of damage to the plants is rated in % damage in com-parison with the development of the untreated control.
The figures denote:
0% - no effect (like untreated control) 100% - total destruction In this test, for example, the compounds of Preparation Examples 4, 6 and 7 exhibit, at application rates of from 60 to 2000 g/ha, very strong activity against weeds such as Digitaria (100%), Sorghum (95%), Amaranthus (100%); Chenopodium (100%), Solanum (100%), Avena fatua (80-100%), Setaria (100%), Abutilon (100%), Galium Le A 32 417-Foreign Countries (90-100%), and Sinapis (80-100%), while being tolerated well by crop plants, such as, for example, cotton (0%).

Le A 32 417-Foreign Countries Example B
Pre-emergence test Solvent: 5 parts by weight of acetone Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, the stated amount of emulsi-fier is added and the concentrate is diluted with water to the desired concentration.
Test plants which have a height of 5 - 15 cm are sprayed with the preparation of ac-tive compound such that the particular desired amounts of active compound are ap-plied per unit area . The concentration of the spray liquor is chosen so that the par-ocular desired amounts of active compound are applied in 10001 of water/ha.
After three weeks, the degree of damage to the plants is rated in % damage in com-parison with the development of the untreated control.
The figures denote:
0% - no effect (like untreated control) 100% - total destruction In this test, for example, the compounds of Preparation Examples 4, 6 and 7 exhibit, at application rates from 15 to 2000 g/ha, very strong activity against weeds, such as Alopecurus (100%), Avena fatua (100%), Setaria (100%), Abutilon (100%), Ama-ranthus (100%), Galium (100%), Ipomoea (100%), Polygonum (100%) and Solanum (100%), and they are tolerated well by crop plants, such as, for example, wheat ( 10%).

Le A 32 417-Foreign Countries Example C
Tetranychus test (OP resistant/dip treatment) Solvent: 3 parts by weight of dimethylformamide Emulsifier: 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and the stated amount of emul-sifter, and the concentrate is diluted with water to the desired concentrations.
Bean plants (Phaseolus vulgaris) which are heavily infested by all stages of the greenhouse red spider mite (Tetranychus urticae) are dipped into a preparation of active compound of the desired concentration.
After the desired period of time, the effect in % is determined. 100% means that all spider mites have been killed; 0% means that none of the spider mites have been killed.
In this test, for example, the compound of Preparation Example 1 exhibits, at an ac-tive compound concentration of 0.01%, a kill of 95% after 7 days.

Le A 32 417-Foreign Countries Example D
Spodoptera frugiperda test/synthetic feed Solvent: 100 parts by weight of acetone 1900 parts by weight of methanol To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with methanol to the desired concentrations.
A stated amount of the preparation of active compound of the desired concentration is pipetted onto a standardized amount of synthetic feed. After the methanol has evaporated, in each case one larvae (L2-L3) of the army worm (Spodoptera fru-giperda) is placed onto the feed, in three replications.
After the desired period of time, the effect in % is determined. 100% means that all animals have been killed; 0% means that none of the animals have been killed.
In this test, for example, the compound of Preparation Example 2 exhibits, at an ac-tive compound concentration of 0.05%, a kill of 100% after 7 days.

Claims (7)

claims

1. Substituted pyridylpyrazoles of the general formula (I), in which m represents the number 0 or 1, n represents the number 1, 2 or 3, R1 represents hydrogen, represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms, or represents in each case optionally cyano- or halogen-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, R2 represents hydrogen, nitro, hydroxyl, mercapto, carboxyl, cyano, thiocarbamoyl, halogen, represents cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms or represents in each case optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkoxy, alkoxycarbonyl, alkylthio, alkylsulphinyl or alkylsulphonyl having in each case 1 to 6 carbon atoms, R3 represents hydrogen, cyano, halogen or represents optionally cyano-, halogen- or C1-C4-alkoxy-substituted alkyl having 1 to 6 carbon atoms and R4 represents nitro, cyano, carboxyl, carbamoyl, thiocarbamoyl, hydroxyl, mercapto, amino, hydroxyamino, halogen or represents one of the groupings -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-CQ-R5, -N(SO2-R5)(CQ1-R5), -Q2-CQ1-Q2-R5, -NH-CQ1-Q2-R5 or -Q2-CQ1-NH-R5, where Q represents O, S, SO or SO2, Q1 and Q2 each represent oxygen or sulphur and R5 represents optionally cyano-, halogen-, C1-C4-alkoxy-, C1-C4-alkylthio-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkyl having 1 to 6 carbon atoms, R5 furthermore represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl-, C1-C4-alkoxy-carbonyl- or C1-C4-alkylamino-carbonyl-substituted alkenyl or alkinyl having in each case 2 to 6 carbon atoms, R5 furthermore represents in each case optionally cyano-, carboxyl-, halogen-, C1-C4-alkyl-carbonyl- or C1-C4-alkoxy-carbonyl-substituted cycloalkyl or cycloalkylalkyl having in each case 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 carbon atoms in the alkyl moiety, R5 furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C5-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted aryl or arylalkyl having in each case 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl moiety, or R5 furthermore represents in each case optionally hydroxyl-, mercapto-, amino-, cyano-, carboxyl-, carbamoyl-, thiocarbamoyl-, C1-C4-alkyl-, C1-C4-halogenoalkyl-, C1-C4-alkoxy-, C1-C4-halogenoalkoxy-, C1-C4-alkylthio-, C1-C4-halogenoalkylthio-, C1-C4-alkylsulphinyl-, C1-C4-alkylsulphonyl-, C1-C4-alkylamino- or dimethylamino-substituted heterocyclyl or heterocyclylalkyl having 2 to 6 carbon atoms and 1 to 3 nitrogen atoms and/or 1 or 2 oxygen atoms and/or one sulphur atom in the heterocyclyl group and optionally 1 to 4 carbon atoms in the alkyl moiety.

2. Process for preparing substituted pyridylpyrazoles of the general formula (I) in which m, n, R1, R2, R3 and R4 are each as defined in Claim 1, characterized in that hydrazine or its derivatives of the general formula (II) H2N-NH-R1 (II) in which R1 is as defined above, are reacted with substituted pyridyl-1,3-dicarbonyl compounds of the general formula (III), in which m, n, R2 , R3 and R4 are each as defined above, or with substituted pyridyl-carbonyl compounds of the general formula (IV) in which m, n, R3 and R4 are each as defined above, Q3 represents oxygen or sulphur and R represents hydrogen or alkyl, - and/or, if appropriate, tautomers of the compounds of the formula (IV)-.

3. Herbicidal, insecticidal and acaricidal compositions, characterized in that they comprise at least one substituted pyridylpyrazole of the formula (I) according to Claim 1.

4. Method for controlling undesirable plants, characterized in that substituted pyridylpyrazoles of the formula (I) according to Claim 1 are allowed to act on undesirable plants and/or their habitat.

5. Use of substituted pyridylpyrazoles of the formula (I) according to Claim 1 for controlling undesirable plants, insects or acarides.

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

7. Method for controlling animal pests, characterized in that substituted pyridyl-pyrazoles of the formula (I) according to Claim 1 are allowed to act on animal pests and/or their habitat.