DE19721031A1 - Substituted pyridylpyrazoles - Google Patents

Abstract

The invention relates to novel substituted pyridylpyrazoles of general formula (I), wherein m = 0 or 1; n = 1, 2 or 3; R<1> = 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; R<2> = 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; R<3> = hydrogen, cyano, halogen or optionally cyano, halogen or C1-C4-alkoxy substituted alkyl with 1-6 C atoms and R<4> = nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the following groups: -Q-R<5>, -NH-R<5>, -NH-O-R<5>, -NH-SO2-R<5>, -N(SO2-R<5>)2, -CQ<1>-R<5>, -CQ<1>-Q<2>-R<5>, -CQ<1>-NH-R<5>, -Q<2>-CQ<1>-R<5>, -NH-CQ<1>-R<5>, -N(SO2-R<5>) (CQ<1>-R<5>), -Q<2>-CQ<1>-Q<2>-R<5>, -NH-CQ<1>-Q<2>-R<5> or -Q<2>-CQ<1>-NH-R<5>, wherein Q = O, S, SO or SO2, Q<1> and Q<2> = 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

The invention relates to new substituted pyridylpyrazoles, processes for their manufacture position and its use as a plant treatment agent, in particular as a herb zide, insecticides and acaricides.

A large number of substituted pyridylpyrazoles are already from the (patent) Literature known (see J. Med. Chem. 38 (1995), 3524-3535; DE 26 23 302; DE 195 30 606, WO 93/07138; JP 08193067 - cited in Chem. Abstracts 125: 247808). From Part of it is also the usability as a plant treatment agent, such as. B. known as fungicides, herbicides, insecticides or acaricides. These connections have not attained any particular importance.

The new substituted pyridylpyrazoles of the general formula (I) have now been found

in which
m represents the numbers 0 or 1,
n represents the numbers 1, 2 or 3,
R ^{1 represents} hydrogen, each alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, or represents alkenyl or alkynyl each having 2 to 6 carbon atoms optionally substituted by cyano or halogen,
R ² for hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thiocarbamoyl, halogen, for alkyl substituted by cyano, halogen or C ₁ -C ₄ alkoxy, or for each optionally substituted by cyano, halogen or C ₁ -C ₄ - Alkoxy substituted alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkyl sulfonyl each having 1 to 6 carbon atoms,
R ^{3 represents} hydrogen, cyano, halogen or alkyl which has 1 to 6 carbon atoms and is optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy and
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the groupings -QR ⁵ , -NH-R ⁵ , -NH-OR ⁵ , -NH-SO ₂ -R ⁵ , -N (SO ₂ -R ⁵ ) ₂ , -CQ ¹ -R ⁵ , -CQ ¹ -Q ² -R ⁵ , -CQ ¹ -NH-R ⁵ , -Q ² -CQ ¹ -R ⁵ , - NH-CQ ¹ -R ⁵ , -N (SO ₂ -R ⁵ ) (CQ ¹ -R ⁵ ), -Q ² -CQ ¹ -Q ² -R ⁵ , -NH-CQ ¹ -Q ² -R ⁵ or -Q ² -CQ ¹ -NH-R ⁵ , where Q is O, S, SO or SO ₂ , Q ¹ and Q ^{2 are} each oxygen or sulfur and
R ⁵ for optionally by cyano, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl or C ₁ -C ₄ Alkylamino-carb onyl-substituted alkyl having 1 to 6 carbon atoms,
R ⁵ furthermore for alkenyl or alkynyl each substituted by cyano, carboxy, halogen, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkoxy-carbonyl or C ₁ -C ₄ -alkylamino-carbonyl, each with 2 to 6 carbon atoms,
R ⁵ furthermore for cycloalkyl or cycloalkylalkyl, each of which is optionally substituted by cyano, carboxy, halogen, C ₁ -C ₄ -alkylcarbonyl or C ₁ -C ₄ -alkoxycarbonyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 Carbon atoms in the alkyl part,
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ Haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino or dimethylamino substituted aryl or arylalkyl with each has 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ - C ₄ alkoxy, C ₁ -C ₄ Haloalkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ haloalkyl thio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkylsulfonyl, C ₁ -C ₄ alkylamino or dimethylamino substituted 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.

The new substituted pyridylpyrazoles of the general formula (I) are obtained if hydrazine or its derivatives of the general formula (II)

H ₂ N-NH-R ¹ (II)

in which
R ^{1 has} the meaning given above,
with substituted pyridyl-1,3-dicarbonyl compounds of the general formula (III),

in which
m, n, R ² , R ³ and R ^{4 have} the meanings given above,
or with substituted pyridyl-carbonyl compounds of the general formula (IV),

in which
m, n, R ³ and R ^{4 have} the meanings given above,
Q ^{3 represents} oxygen or sulfur and
R represents hydrogen or alkyl,
and / or optionally tautomers of the compounds of the formula (IV)
if appropriate in the presence of a reaction auxiliary and if appropriate in the presence of a diluent,
and optionally on the compounds of the formula (I) thus obtained, as part of the above definition of substituents, by further conversions by customary methods.

The compounds of the general formula (I) can be converted by conventional methods into other compounds of the general formula (I) according to the above substituent definition, for example by customary alkylation, acylation or sulfonylation reactions (for example R ¹ : H → CH ₃ , CHF ₂ , C ₂ H ₅ , CH ₂ CH = CH ₂ ; R ⁴ : OH → OCH ₃ , OC ₂ H ₅ , OCHF ₂ , OCH ₂ CH = CH ₂ , OCOCH ₃ ; SH → SCH ₃ , SC ₂ H ₅ ; NH ₂ → NHC ₃ H ₇ , NHCOCH ₃ , NHSO ₂ CH ₃ ), or by electrophilic or nucleophilic substitution reactions (e.g. R ³ : H → Cl, Br; R ⁴ : F → OH, SH, NH ₂ ) - cf. also the manufacturing examples.

The new substituted pyridylpyrazoles of the general formula (I) are of interest biological properties that determine their use as plant treatment agents possible. They show strong herbicidal, insecticidal and acaricidal activity and are particularly characterized by excellent and selective herbicidal activity.

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

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

The invention preferably relates to compounds of the formula (I) in which
m represents the numbers 0 or 1,
n represents the numbers 1, 2 or 3,
R ¹ for hydrogen, for each methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, or for each optionally by cyano Fluorine, chlorine or bromine substituted propenyl, butenyl, propynyl or butynyl,
R ² for hydrogen, nitro, hydroxyl, mercapto, carboxy, cyano, thiocarbamoyl, fluorine, chlorine, bromine, for each methyl, ethyl, n- or i-propyl substituted by cyano, fluorine, chlorine, methoxy or eth oxy, n- , i-, s- or t-butyl, or for methoxy, ethoxy, n- or i-propoxy, n-, i-, s- or t-butoxy, each optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, Methoxycarbonyl, ethoxycarbonyl, methylthio, ethylthio, n- or i-propylthio, n-, i-, s- or t-butylthio, methylsulfinyl, ethylsulfinyl, n- or i-propyl sulfinyl, n-, i-, s- or t-butylsulfinyl, methylsulfonyl, ethylsulfonyl, n- or i-propylsulfonyl, n-, i-, s- or t-butylsulfonyl,
R ^{3 represents} hydrogen, fluorine, chlorine, bromine, or methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, fluorine, chlorine, bromine or for one of the groupings -QR ⁵ , -NH-R ⁵ , -NH-OR ⁵ , -NH- SO ₂ -R ⁵ , -N (SO ₂ -R ⁵ ) ₂ , -CQ ¹ -R ⁵ , -CQ ¹ -Q ² -R ⁵ , -CQ ¹ -NH-R ⁵ , -Q ² -CQ ¹ - R ⁵ , -NH-CQ ¹ -R ⁵ , -N (SO ₂ -R ⁵ ) (CQ ¹ -R ⁵ ), -Q ² -CQ ¹ -Q ² -R ⁵ , -NH-CQ ¹ -Q ² -R ⁵ or -Q ² -CQ ¹ -NH-R ⁵ , where Q is O, S, SO or SO ₂ , Q ¹ and Q ^{2 are} each oxygen or sulfur and
R ⁵ for each methyl, ethyl, n- or i-propyl, n-, i-, s, optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl - or t-butyl,
R ⁵ furthermore represents propenyl, butenyl, propenyl or butynyl which is optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylamino carbonyl or ethylaminocarbonyl,
R ⁵ further represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl,
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluorinethyl, trifluoromethyl, methoxy , Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylamino, ethylamino or dimethylamino substituted phenyl, benzyl or phenyl
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, trichloromethyl, difluorinethyl , Trifluoromethyl, chlorodifluorinethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylsulfyl, ethylsulfonylsulfyl, ethyl, methylsulfonyl, methylsulfonyl, ethylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylamino, ethylamino, n- or i-propylamino or dimethylamino substi tuiertes heterocyclyl or heterocyclylalkyl from the series oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, Pyra zolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , Oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazoly l is methyl, pyridinylmethyl, pyrimidinylmethyl.

The invention relates in particular to the compounds of the formula (I) in which
m represents the numbers 0 or 1,
n represents the numbers 1, 2 or 3,
R ¹ each represents methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R ^{2 represents} hydroxy, mercapto, fluorine, chlorine, bromine, or methyl, ethyl, methoxy, ethoxy, methylthio, ethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl, each substituted by cyano, fluorine, chlorine, methoxy or ethoxy,
R ^{3 represents} fluorine, chlorine, bromine or methyl or ethyl optionally substituted by cyano, fluorine, chlorine, methoxy or ethoxy, and
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the groupings -QR ⁵ , -NH-R ⁵ , -NH-OR ⁵ , -NH-SO ₂ -R ⁵ , -N (SO ₂ -R ⁵ ) ₂ , -CQ ¹ -R ⁵ , -CQ ¹ -Q ² -R ⁵ , -CQ ¹ -NH-R ⁵ , -Q ² -CQ ¹ -R ⁵ , - NH-CQ ¹ -R ⁵ , -N (SO ₂ -R ⁵ ) (CQ ¹ -R ⁵ ), -Q ² -CQ ¹ -Q ² -R ⁵ , -NH-CQ ¹ -Q ² -R ⁵ or -Q ² -CQ ¹ -NH-R ⁵ , where Q is O, S, SO or SO ₂ , Q ¹ and Q ^{2 are} each oxygen or sulfur and
R ⁵ for each methyl, ethyl, n- or i-propyl, n-, i-, s, optionally substituted by cyano, fluorine, chlorine, methoxy, ethoxy, methylthio, ethylthio, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl or ethylaminocarbonyl - or t-butyl,
R ⁵ furthermore represents propenyl, butenyl, propenyl or butynyl which is optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl, ethoxycarbonyl, methylamino carbonyl or ethylaminocarbonyl,
R ⁵ further represents cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl or cyclohexylmethyl, each optionally substituted by cyano, carboxy, fluorine, chlorine, bromine, acetyl, propionyl, methoxycarbonyl or ethoxycarbonyl,
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, difluoromethyl, trifluoromethyl, methoxy , Ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, difluoromethylthio, trifluoromethylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl, ethylsulfonyl, methylamino, ethylamino or dimethylamino substituted phenyl, benzyl or phenyl
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, dichloromethyl, trichloromethyl, difluorinethyl , Trifluoromethyl, chlorodifluorinethyl, fluorodichloromethyl, methoxy, ethoxy, n- or i-propoxy, difluoromethoxy, trifluoromethoxy, methylthio, ethylthio, n- or i-propylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylsulfyl, ethylsulfonylsulfyl, ethyl, methylsulfonyl, methylsulfonyl, ethylsulfonyl, methylsulfonyl, methylsulfonyl, methylsulfonyl, methylamino, ethylamino, n- or i-propylamino or dimethylamino substi tuiertes heterocyclyl or heterocyclylalkyl from the series oxiranyl, oxetanyl, furyl, tetrahydrofuryl, dioxolanyl, thienyl, tetrahydrothienyl, pyrrolyl, Pyra zolyl, imidazolyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , Oxadiazolyl, thiadiazolyl, pyridinyl, pyrimidinyl, triazinyl, pyrazolylmethyl, furylmethyl, thienylmethyl, oxazolylmethyl, isoxazolylmethyl, thiazoly l is methyl, pyridinylmethyl, pyrimidinylmethyl.

A particularly preferred group of compounds of the general formula (I) are compounds of the formula (Ia)

in which
n, R ¹ , R ² , R ³ and R ^{4 have} the meanings given above as being particularly preferred.

Another particularly preferred group of compounds of the general formula (I) are compounds of the formula (Ib)

in which
n, R ¹ , R ² , R ³ and R ^{4 have} the meanings given above as being particularly preferred.

Another particularly preferred group of compounds of the general formula (I) are compounds of the formula (Ic)

in which
n, R ¹ , R ² , R ³ and R ^{4 have} the meanings given above as being particularly preferred.

The general or priority ranges listed above nitions apply both to the end products of formula (I) and accordingly to the starting or intermediate products required for the production. This Residual definitions can be between themselves, that is, between the specified ones areas can be combined as required.

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 materials, the reaction can proceed in the process according to the invention can be outlined by the following formula:

Formula (II) provides a general definition of the hydrazine derivatives to be used as starting materials in the process according to the invention for the preparation of compounds of formula (I). In formula (II), R ¹ preferably or in particular has the meaning which has already been mentioned above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for R ¹ .

The starting materials of the general formula (II) are known synthetic chemicals.

Formula (III) generally defines the substituted pyridyl-1,3-dicarbonyl compounds to be used further as starting materials in the process according to the invention. In the formula (III), n, R ² , R ³ and R ⁴ preferably or in particular have those meanings which have been described above in connection with the description of the compounds of the formula (I) according to the invention preferably or as particularly preferred for n , R ² , R ³ and R ^{4 were} given.

The substituted pyridylcarbonyl compounds to be used further as starting materials in the process according to the invention are generally defined by the formula (IV). In the formula (IV), n, R ³ and R ⁴ preferably or in particular have those meanings which have already been described above in connection with the description of the compounds of the formula (I) according to the invention, preferably or as particularly preferred for n, R ³ and R ^{4 have been} given; Q ³ preferably represents oxygen or sulfur and R preferably represents hydrogen or C ₁ -C ₄ alkyl, in particular hydrogen, methyl or ethyl.

The starting materials of the formulas (III) and (IV) are known and / or can be according to known methods can be prepared (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. 30: 855-859 (1993); J. Med. Chem. 33: 1859-1865 (1990); J. Org. Chem. 47 (1982), 3027-3038; loc. cit. 49: 3733-3742 (1984); Pharmazie 23: 557-560 (1968);  Synthesis 1993, 290-292; DE 24 58 808; DE 40 31 798; DE 44 25 650; EP 206294; EP 306251; US 4026900; US 4980357; Manufacturing examples).

As a diluent for carrying out the process according to the invention for Production of the new compounds of formula (I) come mainly organic Solvent. These include in particular aliphatic, alicyclic or aromatic, optionally halogenated hydrocarbons, such as Petrol, benzene, toluene, xylene, chlorobenzene, dichlorobenzene, petroleum ether, hexane, Cyclohexane, dichloromethane, chloroform, carbon tetrachloride, ethers such as diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran or ethylene glycol dimethyl or -diethyl ether; Ketones, such as acetone, butanone or methyl isobutyl ketone; Carbon acids, such as B. 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, sulfoxides such as dimethyl sulfoxide, alcohols, such as methanol, ethanol, n- or i-propanol, ethylene glycol mono methyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether or di ethylene glycol monoethyl ether.

In general, reaction auxiliaries for the process according to the invention are the usual inorganic or organic bases or acid acceptors in Be dress. These preferably include alkali metal or alkaline earth metal acetates, amides, carbonates, bicarbonates, hydrides, hydroxides or alkanolates, such as for example sodium, potassium or calcium acetate, lithium, sodium, potassium or Calcium amide, sodium, potassium or calcium carbonate, sodium, potassium or Calcium hydrogen carbonate, lithium, sodium, potassium or calcium hydride, Lithium, sodium, potassium or calcium hydroxide, sodium or potassium -methanolate, -ethanolate, -n- or -i-propanolate, -n-, -i-, -s- or -t-butanolate; further also basic organic nitrogen compounds, such as trimethyl amine, triethylamine, tripropylamine, tributylamine, ethyl-diisopropylamine, N, N-Di methyl-cyclohexylamine, dicyclohexylamine, ethyl-dicyclohexylamine, N, N-dimethyl aniline, N, N-dimethyl-benzylamine, pyridine, 2-methyl, 3-methyl, 4-methyl, 2,4-di  methyl, 2,6-dimethyl, 3,4-dimethyl and 3,5-dimethyl-pyridine, 5-ethyl-2-methyl pyridine, 4-dimethylamino-pyridine, N-methylpiperidine, 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-en (DBU).

The reaction temperatures can be carried out when carrying out the process according to the invention Process can be varied over a wide range. Generally you work 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 normal pressure leads. However, it is also possible to increase the process according to the invention or reduced pressure - generally between 0.1 bar and 10 bar to lead.

To carry out the process according to the invention, the starting materials in generally used in approximately equimolar amounts. However, it is also possible Lich to use one of the components in a larger excess. The order Settlement is generally carried out in a suitable diluent and the reaction mixture is generally required for several hours stirred temperature. The workup is carried out using customary methods led (see the manufacturing examples).

The active compounds according to the invention can be used as defoliants, desiccants, herb kills Means and especially used as a weed killer. Under Weeds in the broadest sense are all plants that grow in places, where they are undesirable. Whether the substances according to the invention as total or selective Herbicides act essentially depends on the amount applied.

The active compounds according to the invention can, for. B. used in the following plants will:  

Dicotyledon weeds of the genera

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga, Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium, Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus, Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica, Abutilon, Emex, Datura, Viola, Galeopsis, Papaver, Centaurea, Trifolium, Ranunculus, Taraxacum.

Dicotyledon cultures of the genera

Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum, Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca, cucumis, cucurbita.

Monocotyledonous weeds of the genera

Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca, Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum, Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis, Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis, Alopecurus, Apera.

Monocot cultures of the genera

Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum, Saccharum, Pineapple, Asparagus, Allium.

However, the use of the active compounds according to the invention is by no means limited to these Limited genres, but extends in the same way to others Plants.

Depending on the concentration, the compounds are suitable for the total weed control z. B. on industrial and track systems and on paths and squares with and without tree cover. Likewise, the connections to weed beds fighting in permanent crops, e.g. B. forest, ornamental wood, fruit, wine, citrus, nut, Banana, coffee, tea, gum, oil palm, cocoa, berry fruit and hops plants, on ornamental and sports turf and pastures and for selective weeds fighting in annual crops.  

The compounds of formula (I) according to the invention are particularly suitable for selective control of monocotyledon and dicotyledon weeds in monocotyledons and dicotyledon cultures both pre-emergence and post-emergence.

The active compounds are suitable for controlling animal pests, preferably Arthropods and nematodes, especially insects and arachnids, which in the Agriculture, in forests, in the protection of stored goods and materials, and on hygiene sector occur. They are against normally sensitive and resistant species as well as against all or individual stages of development effective. To the pests mentioned above belong:

From the order of the Isopoda z. B. Oniscus asellus, Armadillidium vulgare, Porcellio scaber.

From the order of the Diplopoda z. B. Blaniulus guttulatus.

From the order of the Chilopoda z. B. Geophilus carpophagus, Scutigera spec.

From the order of the Symphyla z. B. Scutigerella immaculata.

From the order of the Thysanura z. B. Lepisma saccharina.

From the order of the Collembola z. B. Onychiurus armatus.

From the order of Orthoptera z. B. Blatta orientalis, Periplaneta americana, Leucophaea maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria.

From the order of the Dermaptera z. B. Auricular Forficula.

From the order of the Isoptera z. B. Reticulitermes spp. .  

From the order of the Anoplura z. B. Pediculus humanus corporis, Haematopinus spp., Linognathus spp.

From the order of the Mallophaga z. B. Trichodectes spp., Damalinea spp.

From the order of the Thysanoptera z. B. Hercinothrips femoralis, Thrips tabaci.

From the order of Heteroptera z. B. Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.

From the order of Homoptera z. B. 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, Rhopa losiphum padi, Empoasca spp., Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. Psylla spp.

From the order of the Lepidoptera z. B. 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 flainmea, 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 po dana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. 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 surinamensis, 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, Costelytra zealandica.

From the order of the Hymenoptera z. B. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.

From the order of the Diptera z. B. 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 hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

From the order of the Siphonaptera z. B. Xenopsylla cheopis, Ceratophyllus spp.

From the order of the Arachnida z. B. Scorpio maurus, Latrodectus mactans.

From the order of Acarina z. B. Acarus siro, 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., Tetranychus spp.

The plant parasitic nematodes include z. B. Pratylenchus spp., Radopholus spp., Ditylenchus spp., Tylenchulus spp., Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp., Longidorus spp., Xiphinema spp.,  Trichodorus spp., Tylenchus spp., Helicotylenchus spp., Rotylenchus spp., Tylenchulus spp.

The active ingredients can be converted into the usual formulations, such as Solutions, emulsions, wettable powders, suspensions, powders, dusts, pastes, sol Liche powder, granules, suspension emulsion concentrates, impregnated with active ingredient Natural and synthetic substances as well as very fine encapsulation in polymeric substances.

These formulations are prepared in a known manner, e.g. B. by mixing of the active ingredients with extenders, i.e. liquid solvents and / or solid carriers gerstoffe, optionally using surfactants, so Emulsifiers and / or dispersants and / or foaming agents.

In the case of the use of water as an extender, e.g. B. also organic Solvents are used as auxiliary solvents. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene, or alkyl naphthalenes, chlorinated aromatics and chlorinated aliphatic hydrocarbons, such as Chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. B. petroleum fractions, mineral and vegetable Oils, alcohols such as butanol or glycol and their ethers and esters, ketones such as Acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar Solvents such as dimethylformamide and dimethyl sulfoxide, and water.

As solid carriers come into question: B. ammonium salts and natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Mont morillonite or diatomaceous earth and synthetic rock powder, such as highly disperse Silicic acid, aluminum oxide and silicates, come as solid carriers for granules in question: e.g. B. broken and fractionated natural rocks such as calcite, marble, Pumice, sepiolite, dolomite and synthetic granules from inorganic and organic flours and granules made of organic material such as sawdust, Coconut shells, corn cobs and tobacco stems; as emulsifying and / or foam Generating funds are possible: z. B. non-ionic and anionic emulsifiers,  such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, e.g. B. alkyl aryl polyglycol ethers, alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydroly sate; as dispersants come into question: z. B. lignin sulfite and Methyl cellulose.

Adhesives such as carboxymethyl cellulose, natural, can be used in the formulations and synthetic powdery, granular or latex-shaped polymers are used, such as gum arabic, polyvinyl alcohol, polyvinyl acetate, and natural phospho lipids such as cephalins and lecithins and synthetic phospholipids. Other additives can be mineral and vegetable oils.

Dyes such as inorganic pigments, e.g. B. iron oxide, titanium oxide, ferro cyan and organic dyes such as alizarin, azo and metal phthalocyanine substances and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, Molybdenum and zinc can be used.

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

The active compounds according to the invention can be used as such or in their formulations also used in a mixture with known herbicides for weed control find, where ready formulations or tank mixes are possible.

Known herbicides are suitable for the mixtures, for example
Acetochlor, Acifluorfen (-sodium), Aclonifen, Alachlor, Alloxydim (-sodium), Ametryne, Amidochlor, Amidosulfuron, Asulam, Atrazine, Azimsulfuron, Benazolin, Benfuresate, Bensulfuron (-methyl), Bentazon, Benzofenap, Benzoylprop Bi alaphos, bifenox, bromofenoxime, bromoxynil, butachlor, butylates, cafenstrole, chlomethoxyfen, chloramben, chloridazon, chlorimuron (chlorosulfuron, chlortoluron, cinmethylin, climosulfonone) , Clopyralid, Clopyrasulfuron, Clor ansulam (-methyl), Cumyluron, Cyanazine, Cycloate, Cyclosulfamuron, Cycloxydim, Cyhalofop (-butyl), 2,4-D, 2,4-DB, 2,4-DP, Desmedipham, Diallate, Dicamba, Diclo fop (-methyl), Difenzoquat, Diflufenican, Dimefuron, Dimepiperate, Dimethachlor, Di methametryn, Dimethenamid, Dinitramine, Diphenamid, Diquat, Dithiopyr, Diuron, Dymron, EPTC, Esprocarb, Ethalfluralin, Ethamatesulfuron Ethoxyfen, etobenzanide, fenoxaprop-ethyl, Fla mprop (-isopropyl), Flamprop (-iso propyl-L), Flamprop (-methyl), Flazasulfuron, Fluazifop (-butyl), Flumetsulam, Flumi clorac (-pentyl), Flumioxazin, Flumipropyn, Fluometuron, Fluorochloridone, Fluoro glycofen (- ethyl), Flupoxam, Flupropacil, Flurenol, Fluridone, Fluroxypyr, Flur primidol, Flurtamone, Fomesafen, Glufosinate (-ammonium), Glyphosate (-isopropyl ammonium), Halosafen, Haloxyfop (-ethoxyethyl), Hexazinone, Imazamethazazam - (methyl , Imazamox, Imazapyr, Imazaquin, Imazethapyr, Imazo sulfuron, Ioxynil, Isopropalin, Isoproturon, Isoxaben, Isoxaflutole, Isoxapyrifop, Lactofen, Lenacil, Linuron, MCPA, MCPP, Mefenacet, Metamitron, Metobthiazonuron, Metazthiazuron, Metazthiazuron, Metazachiazuron, Metazachiazuron, Metazachiazuron, Metazthiazuron, Methazachloruron, Metazachiazon Met oxuron, Metsulfuron (-methyl), Metribuzin, Molinate, Monolinuron, Naproanilide, Napropamide, Neburon, Nicosulfuron, Norflurazon, Orbencarb, Oryzalin, Oxadiazon, Oxyfluorfen, Paraquat, Pendimethalin, Phenmediphamet, Piperophonos, Piperophonos, Piperophonos, Piperophonos, Piperophonos, Piperophonos, Piperophonos, Piperophonos , Prometryn, Propachlor, Propanil, Propaquizafop, Propyz amide, Prosulfocarb, Prosulfuron, Pyrazolate, Pyrazosulfuron (-ethyl), Pyrazoxyfen, Pyributicarb, Pyridate, Pyrithiobac (-sodium), Quinchlorac, Quinmerac, Quizalofopal - -tefuryl), rimsulfuron, sethoxydim, simazine, simetryn, sulco trione, sulfentrazone, sulfometuron (-methyl), sulfosate, tebutam, tebuthiuron, ter buthylazine, terbutryn, thenylchlor, thiafluamide, thiazopyr, thidiaziminobethyl, thifenon , Tiocarbazil, Tralkoxydim, Triallate, Triasulfuron, Tribenuron (-methyl), Triclopyr, Tridiphane, Trifluralin and Triflusulfuron.

Also a mixture with other known active ingredients, such as fungicides, insects ziden, acaricides, nematicides, bird repellants, plant nutrients and soil structure improvers are possible.  

The active substances can be used as such, in the form of their formulations or in the form thereof application forms prepared by further dilution, such as ready-to-use solder solutions, suspensions, emulsions, powders, pastes and granules. The application is done in the usual way, e.g. B. by pouring, spraying, spraying, Scatter.

The active compounds according to the invention can be used both before and after emergence of the plants are applied. They can also be planted in the soil before sowing be working.

The amount of active ingredient used can vary over a wide range. she depends essentially on the type of effect desired. In general the application rates are between 1 g and 10 kg of active ingredient per hectare of soil area, preferably between 5 g and 5 kg per ha.

The manufacture and use of the active compounds according to the invention are based on following examples.

Manufacturing examples

example 1

20.2 g (89 mmol) of 3- (6-chloro-pyridin-3-yl) -3-oxo-propionic acid are dissolved in 40 ml of acetic acid and dropwise at an internal temperature of about 40 ° C. 5.8 g (126 mmol) of methylhydrazine were added. Then the mixture is approx. Heated for 90 minutes at 90 ° C to 100 ° C, whereby a brownish solid precipitates. The cooled mixture is poured onto 300 ml of water, the precipitated solid filtered off, washed with water and dried in vacuo at 50 ° C.

13.6 g (73% of theory) of 5- (6-chloro-pyridin-3-yl) -2-methyl-2H-pyrazole are obtained. 3-ol from melting point 220 ° C.

Example 2

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 is added in succession to 8.0 g (160 mmol) of hydrazine hydrate and 16.3 g (160 mmol) acetic anhydride. The reaction mixture is one hour heated to 90 ° C to 100 ° C and the cooled mixture on 800 ml of ice water  carry. The precipitated solid is filtered off, washed with water and in Vacuum dried at 50 ° C.

29.8 g (90% of theory) of 2-chloro-5- (5-trifluoromethyl-1H-pyrazol-3-yl) are obtained. pyridine, melting point 183 ° C.

Example 3

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 are mixed with 16.5 g of potassium carbonate and heated to 50 ° C for about 60 minutes. Then at a temperature between 60 ° C and 70 ° C about 30 g (0.35 mol) of chlorodifluoromethane within one hour directs. The reaction mixture is cooled to room temperature, to 1.3 liters Discharged water and acidified with 2N hydrochloric acid. The precipitated solid is suction filtered, dissolved in dichloromethane, successively with saturated aqueous sodium hydrogen carbonate solution and saturated aqueous sodium chloride solution, dried with magnesium sulfate and filtered. The filtrate is in a water jet vacuum concentrated and the residue by column chromatography with toluene / ethyl acetate ester (vol .: 1: 1) separated.

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

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 dichloromethane is added at room temperature (approx. 20 ° C) with stirring 2.2 g (1.63 mmol) of sulfuryl chloride. The mix turns three Stirred at about 20 ° C for hours, diluted with 20 ml dichloromethane, with saturated aqueous sodium bicarbonate solution and with saturated aqueous cook salt solution washed, dried with magnesium sulfate and filtered. From the filtrate the solvent is carefully distilled off in a water jet vacuum.

4.05 g (99% of theory) of 2-chloro-5- (4-chloro-5-difluoromethoxy-1-methyl- 1H-pyrazol-3-yl) pyridine, melting point 42 ° C.

If an appropriate solution of bromine is used instead of sulfuryl chloride Dichloromethane gives 2-chloro-5- (4-bromo-5-difluoro) in a similar yield methoxy-1-methyl-IH-pyrazol-3-yl) pyridine ("Example 11") melting at 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 mmol) of potassium carbonate in 150 ml of acetonitrile are added  approx. 20 ° C within approx. two minutes 18.3 g (129 mmol) iodomethane. The reak tion mixture is stirred for 3 hours at 40 ° C and after cooling in water jet vacuum concentrated. The residue is dissolved in 100 ml dichloromethane and 200 ml Water added, the organic phase separated, washed with water, with Magnesium sulfate dried and filtered. The filtrate is in a water jet vacuum concentrated and the residue by column chromatography with n-hexane / acetic acid ethyl ester (vol .: 2: 1) separated.

6.6 g (50.5% of theory) of 2-chloro-5- (1-methyl-5-trifluoromethyl-1H- pyrazol-3-yl) pyridine, melting point 95 ° C.

Example 6

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 is passed in at 75 ° C. to 85 ° C. with stirring 10 g (141 mmol) of chlorine gas within 2 hours. The reaction mixture is cooled, poured onto 100 ml of ice water and extracted with ethyl acetate. The separated organic phase is successively saturated with aqueous Sodium bicarbonate solution and saturated aqueous sodium chloride solution wash, dry with magnesium sulfate and filter. The filtrate is in the water jet vacuum concentrated.

2.05 g (91% of theory) of 2-chloro-5- (4-chloro-1-methyl-5-trifluoromethyl- 1H-pyrazol-3-yl) pyridine, melting point 55 ° C.  

Example 7

To a solution of 23.0 g (88.6 mmol) of 1- (6-chloropyridin-3-yl) -3,3-bis-methylthio- 2-propen-1-one in 145 ml acetonitrile is added at approx. 20 ° C to 10.3 g (224 mmol) Methylhydrazine. The reaction mixture is refluxed for 120 minutes and then poured onto ice water. The precipitated solid is suctioned off with Washed water and dried in vacuo.

17.9 g (84% of theory) of 3- (6-chloropyridin-3-yl) -1-methyl-5-methylthio- 1H-pyrazole, melting point 93 ° C.

Example 8

To a solution of 3.8 g (16 mmol) of 3- (6-chloro-pyridin-3-yl) -1-methyl-5-methyl thio-1H-pyrazole in 30 ml of diethyl ether is added in succession to a drop at 0 ° C. Acetic acid and 1.8 g (9 mmol) of 1,3-dichloro-5,5-dimethyl-hydantoin. The reaction mixture is stirred for 18 hours at room temperature (approx. 20 ° C) and in succession mixed with 20 ml of water and 20 ml of ethyl acetate. The organic phase is removed  separates, successively with saturated aqueous sodium bicarbonate solution and saturated aqueous sodium chloride solution, dried with magnesium sulfate and filtered. The filtrate is concentrated in a water jet vacuum.

3.8 g (87% of theory) of 4-chloro-3- (6-chloropyridin-3-yl) -1-methyl-5- are obtained. methylthio-1H-pyrazole 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) -1-methyl-5- methylthio-1H-pyrazole in 30 ml dichloromethane is added at 0 ° C with stirring 7.5 g (30 mmol) 3-chloro-perbenzoic acid. The reaction mixture is at 18 hours Room temperature (about 20 ° C) stirred, the precipitated solid is filtered off and Filtrate successively with saturated sodium thiosulfate, with saturated sodium hydrogen carbonate solution and saturated sodium chloride solution, washed with mag dried and filtered. The filtrate is immersed in a water jet vacuum tight.

2.0 g (81% of theory) of 4-chloro-3- (6-chloro-1-oxy-pyridin-3-yl) -1-methyl- 5-methylsulfonyl-1H-pyrazole as an amorphous residue.

Analogously to the preparation examples 1 to 9 and in accordance with the general description of the preparation process according to the invention, for example the compounds of the formula (I) listed in Table 1 below can also be prepared.

Table 1: Examples of the compounds of the formula (I)

Starting materials of formula (III)

Example (III-1)

To a mixture of 89.3 g (0.525 mol) of potassium monoethyl malonate in 500 ml Acetonitrile is added in succession at 10 ° C to 15 ° C 50.5 g (0.5 mol) of triethylamine and 58.8 g (0.617 mol) of anhydrous magnesium chloride. The mixture will be 150 mi grooves stirred at approx. 20 ° C, cooled to -10 ° C to -5 ° C and at this temperature successively with 88.0 g (0.50 mol) of 2-chloro-pyridine-5-carboxylic acid chloride and 5.05 g (0.05 mol) triethylamine added. The reaction mixture is 18 hours at about Stirred at 20 ° C and then concentrated. The residue is mixed with 500 ml of toluene stirred and slowly mixed with 240 ml of 33% hydrochloric acid. Stir for 3 hours Room temperature, filtered off the precipitated solid and separated from the filtrate organic phase. It is washed with dilute hydrochloric acid and with water, dried with magnesium sulfate and filtered. The filtrate is in a water jet vacuum concentrated and the residue by column chromatography with dichloromethane / methanol (Vol .: 9: 1) separated.

The main fraction obtained is 82.9 g (73% of theory) 3- (6-chloropyridin-3-yl) -3- oxo-propionic acid ethyl ester with a melting point of 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 is concentrated in succession with 40 ml of water and 7.5 ml. Added sulfuric acid and then heated to approx. 80 ° C for 90 minutes. You leave cool the reaction mixture to room temperature and transfer it to 600 ml of ice water out. The resulting suspension is neutralized with dilute sodium hydroxide solution and extracted with dichloromethane. The organic phase is saturated with aq ger saline solution washed, dried with magnesium sulfate and filtered. From Filtrate, the solvent is carefully distilled off in a water jet vacuum.

21.4 g (78% of theory) of 5-acetyl-2-chloropyridine of melting point are obtained 98 ° C.  

Level 2

To a solution of 17.4 g (0.112 mol) of 5-acetyl-2-chloropyridine in 200 ml of diethyl ether, 20.7 g (0.146 mol) of trifluoroacetic acid are added in succession at about 20 ° C. acid ethyl ester and then at -5 ° C 30.2 g (0.168 mol) of 30% methanolic Sodium methylate solution. The reaction mixture is stirred at 0 ° C. for two hours, then poured onto 200 ml of ice water and adjusted to pH with 1N hydrochloric acid set between 2 and 3. The organic phase is then separated off with ge saturated saturated sodium chloride solution, dried with magnesium sulfate and filtered. The solvent is carefully removed from the filtrate in a water jet vacuum distilled.

27.1 g (96% of theory) of 1- (6-chloropyridin-3-yl) -4,4,4-trifluorobutane-1,3- are obtained. dione with a melting point of 54 ° C.

Example (III-3)

To a suspension of 33.6 g (0.3 mol) of potassium t-butoxide in 210 ml of tetrahydrofuran a solution of 23.3 g is added dropwise at -40 ° C. within 15 minutes (0.15 mol) 5-acetyl-2-chloro-pyridine in 50 ml of tetrahydrofuran. The mixture turns 30 Minutes stirred at -40 ° C and then ver with 11.4 g (0.15 mol) of carbon disulfide puts. After a further 30 minutes, 42.6 g (0.3 mol) of methyl iodide are added and the mixture is left the reaction mixture come to room temperature within two hours. The The reaction mixture is poured onto 1.5 l of ice water, with 1N hydrochloric acid to pH 2 adjusted to 3 and extracted with 1.5 liters of ethyl acetate. The organic phase will washed with brine, dried over magnesium sulfate and in vacuo freed from the solvent. The crude product obtained is with about 100 ml of diethyl stirred ether, the precipitated solid was filtered off and dried.

24.3 g (62% of theory) of 1- (6-chloro-pyridin-3-yl) -3,3-bis-methylthio-2- are obtained. propen-1-one as a crystalline light yellow solid with a melting point of 145 ° C.  

Examples of use Example A Pre-emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

Seeds of the test plants are sown in normal soil. After about 24 hours the soil is poured with the active ingredient preparation. You keep the water quantity per unit area expediently constant. The drug concentration in the preparation does not matter, only the application rate of the Active ingredient per unit area.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 4 show 6 and 7 at application rates of 60 to 2000 g / ha and good tolerance against about crops, such as. B. Cotton (0%), very strong against weeds ter such as Digitaria (100%), Sorghum (95%), Amaranthus (100%); Chenopodium  (100%), Solanum (100%), Avena factua (80-100%), Setaria (100%), Abutilon (100%), Galium (90-100%), and Sinapis (80-100%).  

Example B Post emergence test

Solvent: 5 parts by weight of acetone
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent, gives the specified Amount of emulsifier and dilute the concentrate with water to the desired level Concentration.

With the active ingredient preparation, test plants are sprayed, which have a height of 5-15 cm, so that the desired amounts of active ingredient per unit area be applied. The concentration of the spray liquor is chosen so that in 1000 l of water / ha the desired amounts of active ingredient are applied.

After three weeks, the degree of damage to the plants is rated in% damage compared to the development of the untreated control.

It means:
0% = no effect (like untreated control)
100% = total annihilation.

In this test, for example, the compounds according to Preparation Example 4 show 6 and 7 at application rates of 15 to 2000 g / ha and good tolerance against about crops, such as. B. wheat (10%), very potent against weeds, such as Alopecurus (100%), Avena fatua (100%), Setaria (100%), Abutilon (100%), Amaranthus (100%), Galium (100%), Ipomoea (100%), Polygonum (100%) as well Solanum (100%).  

Example C Tetranychus test (OP-resistant / immersion treatment)

Solvent: 3 parts by weight of dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To prepare a suitable preparation of active compound, 1 Ge is mixed most of the active ingredient with the specified amount of solvent and the specified Amount of emulsifier and dilute the concentrate with water to the desired Concentrations.

Bean plants (Phaseolus vulgaris) which are strong from all stages of common spinning mite (Tetranychus urticae) are infested in an active ingredient preparation of the ge wished concentration immersed.

After the desired time, the effect is determined in%. 100% means that all spider mites have been killed; 0% means that there are no spider mites were killed.

In this test, e.g. B. the compound according to Production Example 1 in a Drug concentration of 0.01% and a degree of kill of 95% after 7 days.  

Example D Spodoptera frugiperda test / artificial feed

Solvent: 100 parts by weight of acetone
1900 parts by weight of methanol

To prepare a suitable preparation of active compound, 1 Ge is mixed important part of the active ingredient with the specified amount of solvent and dilutes the Concentrate with methanol to the desired concentrations.

A specified amount of active ingredient preparation of the desired concentration is pipetted onto a standardized amount of synthetic feed. After the methanol has evaporated, a larva (L ₂ -L ₃ ) of the army worm (Spodoptera frugiperda) is placed on the feed in triplicate.

After the desired time, the effect is determined in%. 100% means that all animals were killed; 0% means that no animals have been killed.

In this test, e.g. B. the compound according to Production Example 2 in a Drug concentration of 0.05% and a degree of killing of 100% after 7 Days.

Claims (7)

1. Substituted pyridylpyrazoles of the general formula (I),
in which
m represents the numbers 0 or 1,
n represents the numbers 1, 2 or 3,
R ^{1 represents} hydrogen, each alkyl having 1 to 6 carbon atoms optionally substituted by cyano, halogen or C ₁ -C ₄ -alkoxy, or represents alkenyl or alkynyl each having 2 to 6 carbon atoms optionally substituted by cyano or halogen,
R ² for hydrogen, nitro, hydroxy, mercapto, carboxy, cyano, thio carbamoyl, halogen, for alkyl substituted by cyano, halogen or C ₁ -C ₄ alkoxy, or for each optionally substituted by cyano, halogen or C ₁ -C ₄ Alkoxy-substituted alkoxy, alkoxycarbonyl, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms,
R ^{3 represents} hydrogen, cyano, halogen or alkyl having 1 to 6 carbon atoms and optionally substituted by cyano, halogen or C ₁ -C ₄ alkoxy and
R ⁴ for nitro, cyano, carboxy, carbamoyl, thiocarbamoyl, hydroxy, mercapto, amino, hydroxyamino, halogen or for one of the groupings -QR ⁵ , -NH-R ⁵ , -NH-OR ⁵ , -NH-SO ₂ -R ⁵ , -N (SO ₂ - R ⁵ ) ₂ , -CQ ¹ -R ⁵ , -CQ ¹ -Q ² -R ⁵ , -CQ ¹ -NH-R ⁵ , -Q ² -CQ ¹ -R ⁵ , - NH-CQ ¹ -R ⁵ , -N (SO ₂ -R ⁵ ) (CQ ¹ -R ⁵ ), -Q ² -CQ ¹ -Q ² -R ⁵ , -NH-CQ ¹ -Q ² -R ⁵ or -Q ² -CQ ¹ -NH-R ⁵ , where Q is O, S, SO or SO ₂ , Q ¹ and Q ^{2 are} each oxygen or sulfur and
R ⁵ for optionally by cyano, halogen, C ₁ -C ₄ alkoxy, C ₁ -C ₄ alkylthio, C ₁ -C ₄ alkylcarbonyl, C ₁ -C ₄ alkoxycarbonyl or C ₁ - C ₄ Alkylamino-carbonyl-substituted alkyl having 1 to 6 carbon atoms,
R ⁵ furthermore represents alkenyl or alkynyl, each substituted by cyano, carboxy, halogen, C ₁ -C ₄ -alkylcarbonyl, C ₁ -C ₄ -alkoxy-carbonyl or C ₁ -C ₄ -alkyl, each with 2 in each is up to 6 carbon atoms,
R ⁵ furthermore for cycloalkyl or cycloalkylalkyl, each of which is optionally substituted by cyano, carboxy, halogen, C ₁ -C ₄ alkylcarbonyl or C ₁ -C ₄ alkoxycarbonyl, each having 3 to 6 carbon atoms in the cycloalkyl group and optionally 1 to 4 Carbon atoms in the alkyl part,
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ Haloalkoxy, C ₁ -C ₄ alkyl thio, C ₁ -C ₄ haloalkylthio, C ₁ -C ₄ alkylsulfinyl, C ₁ -C ₄ alkyl sulfonyl, C ₁ -C ₄ alkylamino or dimethylamino substituted aryl or arylalkyl each with 6 or 10 carbon atoms in the aryl group and optionally 1 to 4 carbon atoms in the alkyl part, or
R ⁵ further for each optionally by hydroxy, mercapto, amino, cyano, carboxy, carbamoyl, thiocarbamoyl, C ₁ -C ₄ alkyl, C ₁ -C ₄ haloalkyl, C ₁ -C ₄ alkoxy, C ₁ -C ₄ -Halogenalkoxy, C ₁ -C ₄ -alkyl thio, C ₁ -C ₄ -haloalkylthio, C ₁ -C ₄ -alkylsulfinyl, C ₁ -C ₄ -alkylsulfonyl, C ₁ -C ₄ -alkylamino or dimethylamino substituted hetero cyclyl 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. 2. Process for the preparation of substituted pyridylpyrazoles of the general formula (I)
in which
m, n, R ¹ , R ² , R ³ and R ^{4 have} the meanings given in claim 1, characterized in that hydrazine or its derivatives of the general formula (II)
H ₂ N-NH-R ¹ (II)
in which
R ^{1 has} the meaning given above,
with substituted pyridyl-1,3-dicarbonyl compounds of the general formula (III),
in which
m, n, R ² , R ³ and R ^{4 have} the meanings given above,
or with substituted pyridyl-carbonyl compounds of the general formula (IV),
in which
m, n, R ³ and R ^{4 have} the meanings given above,
Q ^{3 represents} oxygen or sulfur and
R represents hydrogen or alkyl,
- and / or optionally tautomers of the compounds of formula (IV) - implemented. 3. Herbicides, insecticides and acaricides, characterized by a content on at least one substituted pyridylpyrazole of the formula (I) according to the Claim 1 4. Process for combating undesirable plants, thereby characterized in that substituted pyridylpyrazoles of the formula (I) according to claim 1 to undesirable plants and / or their habitat can act. 5. Use of substituted pyrdylpyrazoles of the formula (I) according to the Claim 1 for controlling unwanted plants, insects or Acarids.   6. Process for the preparation of herbicidal, insecticidal or acaricidal Agents, characterized in that substituted pyridylpyrazoles of Formula (I) according to claim 1 with extenders and / or surfaces mixed active substances. 7. A method for controlling animal pests, thereby records that substituted pyridylpyrazoles of the formula (I) according to Claim 1 affect animal pests and / or their habitat leaves.