HRP931151A2 - Indazole derivatives - Google Patents

Description

The invention relates to compounds of the formula

[image]

where

R1 means hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl,

R2 is hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl, benzyl, -CHO, -CH2-O-D, -CO-D, -CO-O-D, -CO-CO-O-D, -S-Y, -SO-Y or -SO2-Y,

R3 and R4 are independently hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or C1-C4-haloalkyl,

E, independently of each other, means halogen, C1-C4-alkylthio, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkylthio, cyano or nitro,

n number zero, one, two or three,

X stands for oxygen or sulfur

A phenyl, naphthyl, substituted phenyl or substituted naphthyl,

D C1-C10-alkyl, phenyl or substituted phenyl,

Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl,

[image]

phenyl or substituted phenyl,

Z is hydrogen, C1-C10-alkyl, C1-C4-haloalkyl, C1-C10-alkyl, [image] phenyl, phenoxyl, substituted phenyl or unsubstituted phenoxyl,

R14 and R15 independently of each other mean C1-C4-alkyl or C3-C6-cycloalkyl,

R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl,

R18 C1-C4-alkyl or C3-C6-cycloalkyl, a

R19 and R20 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl, in free form or in the form of salts, a process for the production and application of these compounds, an agent for destroying pests whose active substance is selected from these compounds in free form or in the form of agrochemically applicable salts, the procedure for the production and application of these agents, plants treated with these agents and the procedure for destroying pests.

Certain 3-carbamoylpyrazole derivatives have been proposed in the literature as active substances in means for destroying pests, which have acaricidal, insecticidal and fungicidal effects. However, the biological properties of these known compounds in the field of pest destruction are not fully satisfactory, which is why there is a need to make available further compounds with pest-killing properties, especially for the destruction of insects, representatives of the acarine order, nematodes and phytopathogenic fungi, while according to the invention, this task is solved using the subject compounds I.

Compounds I, which have at least one basic center, can, for example, form acid addition salts. They are formed, for example, with strong inorganic acids such as mineral acids, e.g. perchloric, sulfuric, nitric, nitrous acid, with phosphoric acid or hydrohalic acid, with strong organic carboxylic acids such as halogen-substituted C1-C4-alkanecarboxylic acid, e.g. acetic acid as possibly unsaturated dicarboxylic acids, e.g. oxalic, malonic, succinic, maleic, fumaric or phthalic acid, as hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid or benzoic acid or with organic sulfonic acids as possibly e.g. halogen substituted C1-C4-alkanoic or aryl-sulfonic acids, eg methane or p-toluenesulfonic acid. Furthermore, compounds I can form a strain with bases with at least one acid group. Suitable salts with bases are, for example, metal salts such as alkali or alkaline earth salts, e.g. sodium, potassium or magnesium salts or salts with ammonia or an organic ammonium such as morpholine, piperidine, pyrrolidine, mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propylamine or mono-, di- or trihydroxy-lower alkylamine, eg mono-di- or triethanolamine. Furthermore, appropriate internal salts can eventually be formed. Within the scope of the invention, agrochemically applicable salts are recommended; however, agrochemical applications that are harmful are also covered, for example, salts that are toxic to bees or fish, that are used for isolation or purification of free compounds I or their agrochemically applicable salts. Due to the close connection between compounds I in free form and in the form of their salts, in the above and further text under free compounds I or their salts should possibly mean corresponding salts or free compounds I.

In the above and further text, the general terms used have, unless otherwise defined, the following meanings.

In particular, the above definition of the radical A must be understood so that A in the preferred form of embodiment stands for phenyl, naphthyl or stands for phenyl or naphthyl substituted by zero, one, two or three residues from the halogen group, C1-C4-alkyl, C1-C4- Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyloxy, C1-C4-Alkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylsulfonyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl, C1-C4-alkylsulfonyloxyl, halo-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloalkoxycarbonyl, wherein two vicinal residues can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH-2-O- or -O-CF2-CFz-O and zero or one radical -Y-R5 substituted phenyl or naphthyl, where Y means oxygen, sulfur or a bridge chain -SO-, -SO2-, -CO-, -CR6R7-, NR8- or a direct single bond, R5phenyl, naphthyl or pyridyl or zero, one, two or three residues from the halo group ene, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyloxy, C1-C4-haloalkyloxy, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, Substituted by C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloenalkoxycarbonyl phenyl, naphthyl or pyridyl, whereby two of these residues in the vicinal position can form a bridge of the structure -O-CH2-O, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2- CF2-O-. R 6 and R 7 independently of each other mean hydrogen or C 1 -C 4 -alkyl, and R 8 hydrogen, C 1 -C 4 -alkyl, formyl, C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxycarbonyl.

The halogen atoms that come into consideration as substituents are both fluorine and chlorine, as well as bromine and iodine, whereby fluorine, chlorine and bromine are preferred. Halogen is considered to be an independent substituent or part of a substituent as in haloalkyl, haloalkyl, haloalkylthio, haloalkylsulfinyl, haloalkylsulfonyl, haloalkylcarbonyl or haloalkylcarbonyl.

Alkyl, alkyl and alkyl radicals can be straight-chain or branched. Examples of such alkyls are alkyl, methyl, ethyl, propyl, isopropyl, butyl, i-butyl, secondary butyl, heptyl and its isomers, n-octyl and n-dodecyl. Examples of suitable alkyl radicals include: methoxyl, ethoxyl, propoxyl. isopropoxyl, butoxyl and their isomers, as well as n-hexoxyl and n-octyloxyl. Examples of alkylthio are methylthio, ethylthio, propylthio, as well as the four isomers of butylthio.

The alkylsulfinyl and alkylsulfonyl residues are derived from the corresponding alkylthio residues and differ from each other only by the degrees of oxidation of the sulfur atom.

If the alkyl, alkylthio or alkoxyl groups that come into consideration as substituents are substituted by halogen, they can only be partially halogenated or even perhalogenated. The above definitions apply to halogen, alkyl, alkylthio and alkyl. Examples of alkyl elements of these groups are methyls substituted one to three times by fluorine, chlorine and/or bromine, such as CHF2 or CF3; one- to five-fold fluorine-, chlorine- and/or bromine-substituted ethyl such as CH2CF3, CF2CF3, CF2CCl3, CF2CHCl2, CF2CHF2, CF2CHF2, CF2CFCl2, CF2CHBr3, CF2CHClF, CF2ClBrF or CClFCClD; propyl or isopropyl substituted one- to seven-fold with fluorine, chlorine and/or bromine such as CH2CHBrCH2Br, CF2CHCFCF3, CH2CF2CF3, CF2CF2CF3 or CH(CF3)2; one- to nine-fold fluorine-, chlorine- and/or bromine-substituted butyl or one of its isomers, for example CF(CF3)CHFCF3, -(CF2)3CF3 or CH2(CF2)2CF3.

The cycloalkyl residues that come into consideration as substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.

Examples of alkoxycarbonyl radicals are methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl or tert. butoxycarbonyl. Alkylcarbonic stands for acyl, propionyl, butyroyl or butylcarbonyl.

If two of the substituents of residue A or residue R5 together form the mentioned bridges, they are formed as new basic bodies with bicyclic structures benzodioxoles, dioxolpyridines, benzodioxins, dioxynopyridines, naphthodioxoles or naphthodioxins. As substituents of the radical A and the residue R5, the enumerated groups can independently have the same or different meanings.

With compounds of formula I, we distinguish two groups. The first group summarizes such compounds where R2 has a different meaning than hydrogen, C1-C4-alkyl, benzyl and C3-C6cycloalkyl. Compounds of formula I are particularly recommended here, in which or

a) D means C1-C10-alkyl, phenyl, C1-C4-alkylphenyl or halophenyl,

Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, C1-C4-alkylphenyl, halophenyl,

[image]

Z is hydrogen, C1-C4-alkyl, phenyl, C1-C4-alkylphenyl, halophenyl, C1-C10-alkoxy, phenoxyl, C1-C4-alkylphenoxyl, halophenoxyl or

[image]

R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl. phenyl, C1-C4-alkylphenyl or halophenyl, a

R19 and R20 independently of each other mean C1-C4-alkyl, while in this subgroup, those compounds in which

D means C1-C10-alkyl, phenyl or 4-chlorophenyl,

Y C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl,

[image]

Z stands for hydrogen, C1-C4-alkyl, phenyl, 4-chlorophenyl, C1-C10-alkoxy, phenoxy, 4-chlorophenoxyl or

[image]

R14 and R15 independently of each other mean C1-C4-alkyl,

R16 C1-C4-alkyl, phenyl, 4-chlorophenyl,

R17 methyl, a

R 18 means alkyl-alkyl or cyclopropyl or

b) R1 is methyl or ethyl, and R3 and R4 are hydrogen or

c) A means a possibly substituted phenoxyphenyl group of the formula

[image]

where

R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4-alkyl, C1-C4 -Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl . ,

R11 and R12 independently of each other mean hydrogen, fluorine, chlorine or trifluoromethyl,

R13 stands for hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkylthio, C1-C4- alkylsulfonyl, C1-C4-alkylsulfonyloxyl, halogen-C1-C4-alkylsulfonoloxyl, fluorine, chlorine, bromine cyano, or nitro, and R12 and R13 together mean -O-CH2O- especially the compounds where R11 and R12 independently one of the second is hydrogen, fluorine, chlorine or trifluoromethyl, R13 is hydrogen, C1-C4-alkyl, fluorine, chlorine, bromine, cyano, methoxy, methylthio, trifluoromethyl, methylsulfonyl, methylsulfonyloxyl or trifluoromethylsulfonyloxyl, and R12 and R13 together are -O-CH2- O-, while n means the number zero, one or two, and the substituents E independently of each other mean halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, R1 is methyl or ethyl, and R3 and R4 mean hydrogen.

In another group, those compounds of formula I, where R2 means hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or benzyl, are summarized, whereby such compounds should be emphasized here, where A stands for phenyl, naphthyl or zero , one or two residues from the halogen group. C1-C4-Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Alkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1- C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4- haloalkoxycarbonyl, whereby two vicinal residues can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O- or the radical -Y -R5 substituted phenyl or naphthyl, where Y means oxygen, sulfur or a bridge chain -SO-, -SO2, -CO-, -CR6R7-, -NR8 or a direct bond, R5 means phenyl, naphthyl or pyridyl or zero, one or two residues from the group halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxyl, C1-C4-alkoxyl, C1-C4-halogenalkoxyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1- C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfinyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxyl , halo-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloalkoxycarbonyl substituted phenyl, naphthyl or pyridyl, wherein both of these residues in the vicinal position can form a bridge structure -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O-, R6 and R7 independently one of the second one is hydrogen or C1-C4-alkynyl, and R8 is hydrogen, C1-C4-alkyl, formyl, C1-C4-alkylcarbonyl or C1-C4-alkoxycarbonyl,

whereby in these subgroups such compounds are particularly preferred, in which the defined naphthyl radicals are connected in the 1- or 2-position, and the defined pyridyl radicals are in the 1-, 3- or 4-position.

On the other hand, with this second group of compounds of formula I according to the invention, such substances deserve attention, in which

d) n stands for the numbers zero, one or two, and the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl or

e) R1 stands for methyl or ethyl, and R2, R3 and R4 for hydrogen or

f) A stands for a possibly substituted phenoxyphenyl group of the formula

[image]

where

R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4-alkyl, C1-C4 -Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl, C1-C4-Alkylsulfonyloxy, Halogen-C1-C4 -alkylsulfonyloxy, cyano or nitro.

Among the compounds of subgroup f), such derivatives are preferred, in which R9, R10, R11 and R12 are hydrogen, and R13 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4- alkoxyl, C1-C4-halogenalkoxyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, cyano or nitro, and especially those compounds in which R13 means hydrogen, halomethyl, haloethyl, cyano, nitro, methylthio, ethylthio , methylsulfonyl, ethylsulfonyl, methylsulfonyloxy or trifluoromethylsulfonyloxy.

The group of active substances according to the invention, which should be particularly highlighted due to its good biological properties, is distinguished by the fact that n stands for the number zero, two or three, the substituents Ene, depending on each other, stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-Alkoxyl, R1 for methyl or ethyl, R2, R3 and R4 hydrogen, and A for a group of the formula

[image]

in which R9, R10, R11, R12 independently of each other mean halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-halogenalkoxyl or C1-C4-alkyl, and R13 is hydrogen, halogen, C1-C4- Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, cyano or nitro.

The group of compounds of formula I, in which n stands for the numbers zero, one or two, the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyl, C1-C4-halogenalkoxyl; R 1 stands for methyl or ethyl; R2, R3, R4 stand for hydrogen, and A for phenyl, naphthyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfinyl, C^ C^ C1-C4-halogenalkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen- C1-C4-alkylsulfonyloxy, formyl, cyano, nitro, C1-C4-alkylcarbonyl, C1-C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-haloalkoxycarbonyl, substituted phenyl or naphthyl, wherein two of these residues in the vicinal position can stand for -O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or –O-CF2-CF2-O-.

Finally, we must mention the group of compounds of formula I, in which n stands for the number zero, one or two, the substituents E independently of each other for halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-halogenalkoxyl or C1-C4-Alkoxyl, R1 for methyl or ethyl, R2, R3 and R4 for hydrogen, and A for one group of the formula

[image]

where

R 13 means hydrogen, halogen, C1-C4-alkyl, halomethyl, haloethyl, C1-C4-alkoxy, halomethoxy, halogenethoxy, C1-C4-alkylsulfinyl, methylsulfonyl, ethylsulfonyl, halomethylsulfonyl, methylsulfonyloxy, trifluoromethylsulfonyloxy, cyano or nitro. In this group, compounds in which R13 means hydrogen, halogenmethyl, halogenethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl are particularly preferred.

In the context of the invention, they are particularly preferred

2-methyl-2H-indazole-3-carboxylic acid-(4-tert.-butyl-benzyl)-amide,

2-methyl-2H-indazole-3-carboxylic acid-(4-(4-fluorophenoxyl)-benzyl)-amide,

2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxyl)-benzyl)-amide,

2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)-amide,

2-methyl-2H-indazole-3-carboxylic acid-(4-(4-methylthiophanoxyl)-benzyl)-amide,

2-methyl-2H-indazole-3-carboxylic acid-(4-(2-chloro-4-trifluoromethylphenoxyl)-benzyl)-amide,

N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxyl)-benzyl)-amide,

N-(tert.-butoxyoxaly)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl)-amide,

N-(3,3-dipropyl-1-methylureido-1-sulfenyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxyl)-benzyl)-amide and

N-(2-ethylhexanoyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)-amide.

Compounds of formula I according to the invention can be obtained according to known procedures. The compound of formula I in which R2 means hydrogen, C1-C4-alkyl, benzyl or C1-C4-cycloalkyl, and R1, R3, R4, A, E, n and x have the aforementioned meaning is obtained, for example, by first or

a) 2H-indazole-3-carboxylic acid of formula II

[image]

in which E, n and R1 have the meaning as in formula I, condenses with an amine of formula III

[image]

in which R2 means hydrogen, C1-C4-alkyl, benzyl or C1-C4-cycloalkyl, and R3, R4 and A have the meaning given in formula I, or

b) 2H-indazole-3-carboxylic acid of formula II is converted into acid halide, imidazolide or alkyl ester of formula IV

[image]

in which R1, E and n have the meaning given in formula I, and Q stands for chlorine, chromium, 1-imidazolyl, methoxyl or ethoxyl, this activated derivative is reacted with an amine of formula III and, if desired, 3-carbamoyl-2H-indazole is obtained derivative of subformula Ia

[image]

in which R2 means hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meaning given in formula I, by treatment with a thionating agent it is converted into a compound of subformula Ib

[image]

in which R 2 is hydrogen, C 1 -C 4 -alkyl, benzyl or C 1 -C 4 -cycloalkyl, and R 1 , R 3 , R 4 , A, E and n have the meaning given in formula I and/or optionally the compound of formula I obtained by invention or in some other way, in free form or in the form of a salt, converted into another compound of formula I, the mixture of isomers obtained according to the process is separated and the desired isomers are isolated and/or the free compound of formula I obtained according to the process or in some other way, it is converted into a salt or a salt of one compound of formula I which is obtained according to the invention or in some other way, is converted into a free compound of formula I or into another salt.

In a further procedure (variant c), a compound of formula I is obtained, in which R2 has a different meaning than hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, whereby first the compound of subformula Ic

[image]

in which R1, R3, R4, A, E and n have the meanings given in Formula I in the presence of one base reacts with the compound Hal-CH2-O-D, Hal-CHO, Hal-CO-D, Hal-CO-O-D, Hal-CO -CO-D, Hal-CO-CO-O-D, Hal-S-Y, SO-Y or Hal-SO2-Y, where hal means a chlorine, bromine or iodine atom, and D and Y have the meanings given in formula I and optionally is the obtained 3-carbamoyl-2H-indazole derivative of subformula Ia, in which R2 has a meaning other than hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meanings given in formula I, with a thionating agent is converted into a compound of subformula Ib, in which R2 means -CH2-O-D, -CHO, -CO-D, -CO-O-D, -CO-CO-D, CO-CO-O-D, -S-Y, -SO-Y or -SO2-Y, where D and Y as well as R1, R3, R4, A, E and n have the meanings given in formula I, and optionally the compound of formula I in free form or in the form of a salt, which can be obtained according to the process or in some other way, converted into another compound of formula I, the mixture of isomers obtained according to the process is separated and the desired isomers are isolated and/or combined the point compound of formula I obtained according to the process is converted into a salt or the salt of one compound of formula I obtained according to the invention is converted into a free compound of formula I or into another salt.

In procedure variant a) (II + III - Ia), the reaction is carried out in the presence of water-splitting reagents, which are usually used for amidation, for example in the presence of carbodiimide (dicyclohexylcarbodiimide (DCC)) or 1-alkyl-2-halogen pyridinium salts as 1-methyl-2-chloropyridinium iodide. This is done in the presence of a reaction-inert solvent or solvent mixture at temperatures from -30ºC to +70°C, preferably at 10ºC to +50°C. The process is carried out in the presence of one base, for example in the presence of an organic amine such as trialkylamine (trimethylamine, triethylamine, tripropylamine or diisopropylethylamine), pyridine (pyridine itself, 4-dimethylaminopyridine or 4-pyrrolidinopyridine), morpholine (N-methylmorpholine) or N, N-dialkylaniline (N,N-dimethylaniline or N-methyl-N-ethylaniline). Suitable solvents here are, for example, aliphatic and aromatic hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether), tert.-butylmethylether, etc.) anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile esters such as ethylacetate (ethyl ester of acetic acid), propylacetate or butylacetate, and mixtures of such solvents with each other.

In process variant b) (II - IV and IX+III - Ia), the first step of converting free acids of formula I into a reaction-activated derivative of formula IV is performed according to the usual procedure for halogenating carboxylic acids using halogenating agents such as thionyl chloride, oxalyl chloride, phosphorus oxychloride, phosphorus pentachloride, phosphorus oxybromide or phosgene, for amidation with 1H-imidazole, and for esterification with lower alkyl alcohols. If desired, halogenation is applied, whereby chlorination with thionyl chloride or solvent-free phosgene is especially preferred in the technique. If solvents are used, they are mainly selected from hydrocarbons such as hexane, pentane, cyclohexane, benzene, toluene or xylene; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride or tetrachloroethylene; ether as diethylether, diisopropylether, tert. butylmethylether, tetrahydrofuran, dioxane, dimethoxyethylene glycol or anisole; or nitriles such as acetonitrile or propionitrile. Reaction temperatures are generally between -15°C and 100°C, preferably between 0°C and +50°C. The second reaction step of variant b) (IV-UUU - Ia) is mainly carried out in an inert solvent without hydroxyl groups, in the presence of an organic base, such as pyridine, 4-dimethylaminopyridine, lutidine, collidine, trialkylamine, N,N-dialkylaniline or bicyclic non-nucleophilic bases such as 1,4-diazabicyclo(2-2-2)-octane (DABCO), 1,5-diazabicyclo(4.30)non-5-ene (OBN) or 1,8-diazabicyclo(5.4.0)- undec-7-ene(1,5-5)(DBU). The reaction is usually carried out at temperatures from -30°C to +70°C, preferably from -10°C to +50°C. It is purposefully done in the presence of a reaction-inert solvent or solvent mixture. Aliphatic and aromatic hydrocarbons such as benzene, toluene, xylene, petroleum ether, hexane are suitable for this; halogenated hydrocarbons such as chlorobenzene, methylene chloride, ethylene chloride, chloroform, carbon tetrachloride, tetrachloroethylene; ether and ether compounds such as dialkylether (diethylether, diisopropylether, tertbutylmethylether, etc.), anisole, dioxane, tetrahydrofuran; nitriles such as acetonitrile, propionitrile; an ester such as ethyl acetate (ethyl acetate), propyl acetate or butyl acetate; ketones such as acetone, diethyl ketone, methyl ethyl ketone; compounds such as dimethylsulfoxide (DMSO), dimethylformamide (DMF) and mixtures of such solvents with each other.

In procedure variant c) (Ic - I), the reaction is carried out in the presence of a strong base such as sodium hydride, potassium hydride, potassium tert.butylate, sodium ethylate, sodium methylate or butyllithium. This is done in an inert solvent at -10ºC to +60ºC, preferably at 0ºC to 30°C. Suitable solvents are, for example, aliphatic and aromatic hydrocarbons such as methylene chloride, ethylene chloride, chlorobenzene or ortho-dichlorobenzene; ether and ethereal solvents such as diethylether, diisopropylether, tert.butylmethylether, tetrahydrofuran, dioxane, dimethoxyethane, dimethoxymethane; nitriles such as acetonitrile and propionitrile; esters such as acetic acid ethyl ester, acetic acid methyl ester, acetic acid propyl ester and acetic acid butyl ester, and mixtures of such solvents with each other. The starting material of formula Ic, which is required for this procedure, can be obtained according to the variants of procedure a) and b).

The optional conversion of the 2H-indazol-3-amide of the carboxylic acid of the formula Ia into the corresponding 2H-3-amide of the thiocarboxylic acid of the formula Ib is carried out under the conditions usual for this type of reaction. The process according to the invention is carried out in the presence of an inert organic solvent. Suitable solvents are aromatic solvents such as benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, pyridine or tetralin; chlorinated hydrocarbons such as methylene chloride, chloroform, tetrachloro hydrocarbon, ethylene chloride, trichloroethane or tetrachloroethane; or an ether such as dioxane, tetrahydrofuran or dimethylethylene glycol. Reaction temperatures are usually between 0ºC and +150°C. A temperature range between +20ºC and +120°C is recommended, where the boiling point of the reaction mixture should be emphasized. The reaction according to the invention is also supported by the fact that the thionation reaction is carried out with the use of ultrasound, and the temperature is chosen between +20° and the boiling point of the mixture. The use of an ultrasound source to assist thionation reactions is described in an analogous procedure in J. Org. Chem. 46, 3558 (1981).

Means of thionation have already been mentioned many times in the literature. Most of these means can be used in the process according to the invention. O,O-diethyldithiophosphoric acid (C2H5O)2PS2H, boron sulfide B2S3 or B2S5, phosphorus pentasulfide P2S5 or 2,4-bis-(4-methoxyphenyl)-1,3-dithia-2,4-diphosphetane- 2,4-disulfide (Lawesson's reagent).

The starting products of the formula are either described in the literature or can be obtained according to the production process described there. Of the starting compounds of formula II, some individual compounds are known from DE-OS 1948793, and most of them have not yet been described. Likewise, the starting products of the formulas Hal-CH2O-O, Hal-CHO, Hal-CO-D, Hal-CO-OD, Hal-CO-CO-D, Hal-CO-CO-O-D, Hal -S-Y, Hal-SO-Y and Hal-SO2-Y, where hal means chlorine, bromine or iodine, especially chlorine or bromine. For now, still new starting materials can be obtained analogously to known procedures. Some products can already be bought on the market.

The starting materials of formula II can be synthesized according to the following reaction sequence. The compounds are obtained in such a way that 2-nitrobenzaldehyde of the formula V

[image]

in which E and n have the meaning stated in formula I, possibly in the presence of an acid, condenses with the amine of formula VI

H2N-R1 (VI)

wherein R 1 has the meaning given in formula I, the resulting Schiff base of formula VII

[image]

in which R1, E and n have the meaning given under formula I, by treatment with alkali cyanide in the presence of an organic acid cyclizes to 3-cyano-2H-indazole-1-oxide of formula VIII

[image]

in which R1, E and n have the meanings given under formula I, this intermediate is deoxygenated and the resulting 3-cyano-2H-indazole of formula IX

[image]

in which R 1 and N have the meanings given under formula I, is saponified.

For the condensation step (V+VI -VII), an inert organic solvent is selected from among aromatic, aliphatic or cycloaliphatic hydrocarbons such as benzene, toluene, xylene, hexane or cyclohexane at temperatures between 0° and +150°C, mostly +25°C and 100° C, but especially at the boiling temperature of the reaction mixture. Adding a catalytic amount of an acid such as hydrochloric acid, sulfuric acid, toluenesulfonic acid, trifluoroacetic acid or methanesulfonic acid has a good effect on the reaction rate.

For the cyclization step (VII - VIII) a polar organic solvent from alcohol or carboxylic acids such as methanol, ethanol, isopropanol, acetic acid or propionic acid is used. As alkali cyanides, mainly sodium cyanide or potassium cyanide come into consideration. Equivalent amounts of organic acid such as acetic acid or trifluoroacetic acid are added to these salts in the reaction solution. It can also be advantageous if this acid is added in excess, so that it can act simultaneously as a solvent. Reaction temperatures generally range between -15ºC and +100ºC, preferably between 0ºC and +50ºC.

For the deoxygenation step (VIII - IX), phosphorus trichloride and phosphorus tribromide are mainly used as deoxygenation reagents. This reaction step is well performed in a hydrocarbon or chlorinated hydrocarbon as a solvent, at temperatures between 0°C and +150°C, especially between +25°C and +100°C. Suitable solvents are, for example, benzene, toluene, xylene, hexane, cyclohexane, methylene chloride, chloroform or carbon tetrachloride.

The saponification step (IX - II) can be carried out both under acidic and basic conditions in an aqueous medium. Solvents include water, alcohols and water-miscible ethers. It is particularly good to use aqueous solvents or solvent mixtures. Examples of suitable solvents are water, tetrahydrofuran, dioxane, methanol, ethanol or isopropanol. Acidic saponification catalysts include, for example, sulfuric acid, hydrochloric acid or hydrobromic acid, and sodium chloride or potassium chloride as basic saponification catalysts. The reaction temperatures for the saponification reaction are generally between 0°C and +150°C, especially between +25°C and 100°C.

Compound I, which can be obtained according to the process or in some other way, can be converted into another compound in a known manner, whereby one or more substituents of the starting compounds I are replaced in the usual way by other substituents according to the invention.

For example, you can:

- replace hydrogen R1 and/or R2 with alkyl R1 and/or R2 or

- introduce halogen E into the unsubstituted position of the indazole ring.

Depending on the choice of suitable reaction conditions of the starting materials, it is possible in one step of the reaction to replace only one substituent with another substituent according to the invention, or in one step of the reaction several substituents can be replaced with other substituents according to the invention.

Salts of compounds I can be obtained in a known manner. Thus, for example, addition salts of acids are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent.

Salts of compounds I can be converted in the usual way into free compounds I, addition salts of acids, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent, and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent.

Salts of compounds I can actually be converted in the usual way into other salts of compounds I, acid addition salts, for example into other acid addition salts, for example by treating a salt of an inorganic acid, for example a hydrochloride, with a suitable metal salt, such as sodium, barium or silver salt, of one acid, eg with silver acetate, in a suitable solvent in which the inorganic salt, eg silver chloride, is insoluble and thus separated from the reaction mixture.

According to the type of procedure or under the reaction conditions, compounds I with salt-forming properties can be obtained, in free form or in the form of salts.

Compounds I, in free form or in the form of a salt, can possibly be found in the form of one of the possible isomers or as a mixture of them, for example according to the number of absolute and relative configurations of asymmetric carbon atoms that may appear in the molecule and/or according to the configuration of non-aromatic double bonds which possibly occur in the molecule, as pure isomers, as antipodes and/or diastereomers or as a mixture of isomers, as a mixture of enantiomers, eg racemates, mixtures of diastereomers or mixtures of racemates; the invention refers both to pure isomers and to all possible mixtures of isomers, and the above and further text should be understood accordingly even when stereochemical details will not be specifically mentioned in any case.

Mixtures of diastereomers and racemates of compounds I, which can be obtained according to the invention or in some other way in the free form or in the form of salts - depending on the choice of starting materials and method of operation, can be separated into pure diastereomers or racemates based on the physico-chemical differences of the constituent parts, for example by fractional crystallization, distillation and/or chromatography.

Mixtures of enantiomers that can be obtained in a suitable way, as racemates, can be separated into optical antipodes according to known methods, for example by recrystallization of an optically active solvent, by chromatography on chiral adsorbents, for example by high-pressure liquid chromatography on acetyl cellulose, by means of suitable microorganisms, by fission with specific, immobilized enzymes, via the formation of insertion compounds, e.g. using a chiral crown ether, whereby only one enantiomer is complexed, or by conversion to diastereomeric salts, e.g. reaction of a basic racemate product with an optically active acid such as carboxylic acid, e.g. .camphoric, tartaric or malic acid or sulphonic acid, e.g. camphor sulphonic acid and separating the thus obtained mixture of diastereomers, e.g. on the basis of their different solubilities by fractional crystallization into diastereomers, from which the desired enantiomer can be released by the action of suitable, e.g. basic means And.

In addition to dividing the appropriate mixtures of isomers, pure diastereomers or enantiomers according to the invention can also be obtained by well-known diastereoselective methods or enantioselective syntheses, for example so that the process according to the invention is carried out with educts with correspondingly suitable stereochemistry.

Biologically effective isomers, e.g. enantiomers and diastereomers or mixtures of isomers, e.g. a mixture of enantiomers or diastereomers can be isolated or synthesize, if individual components have different biological effectiveness.

Compounds I, in free form or in the form of salts, can also be obtained in the form of their hydrates and/or include other, for example, solvents used for crystallization of compounds that are in solid form.

The invention refers to all those forms of carrying out the process, according to which the starting point is a compound that is obtained at any stage of the process as a starting product or an intermediate product and all or some of the missing steps are carried out or the starting substance is used in the form of a derivative, for example a salt and / or its racemates or antipodes or are especially created under reaction conditions.

In the process of the subject invention, such starting substances and intermediate products are used, in free form or in the form of salts, which lead to compounds I or of their salts, which were described at the beginning as particularly valuable.

The invention specifically relates to the production process described in examples H1 to H5.

Starting substances and intermediate products, in free form or in the form of salts, used according to the invention to obtain compounds I or their salts, which are new, the process for their production and their use as starting materials and intermediates for obtaining compounds I are also the subject of the invention.

The compounds according to the invention are in the field of destroying insects - if they are well tolerated by warm-blooded animals, fish and plants, even at low concentrations they can be used preventively and/or curatively. Active substances with a very favorable biocidal spectrum. The active substances according to the invention are effective in all developmental stages of normally sensitive but also resistant animal pests such as insects, nematodes and representatives of the acarina order and phytopathogenic fungi. The insecticidal, nematocidal and/or acaricidal effect of the active substances according to the invention can be demonstrated directly. in the deadening of the pest, which occurs immediately or only after some time, for example when removing the skin, or indirectly, for example, in reduced egg laying and/or reduced hatching speed, whereby a good effect corresponds to a mortality of at least 50 to 60%.

The mentioned animal pests include, for example:

From the order of lepidoptera, for example

acleris spp., adoxophyes spp., agrotis spp., alabama argillaceae, amylois spp., anticarsia gemmatalis, archips spp.. argyrotaenia spp., autographa spp., busseula fusca, cadra cautrlia, carposina nipponensis, chilo spp., choristoneura spp. , clysia ambiguella, cnaphalocrocis spp., cnephasia spp., cochylis spp., colephora spp., crocidolomia binotalis, cryptophlebia leucotreta, cydia spp., diatraea spp., diparopsis castanea, earias spp., ephestia spp., eucosma spp., eupoecilia ambiguella, euproctis spp., euxoa spp., grapholita spp., hedya nubiferana, heliothis spp, hellula undalis, hyphantria cunea, keiferia lycopersicella, leucoptera scitella, lithocollethis spp., lobesia botrana, lymantria spp., lyonetia spp., malacosoma spp. , mamestra brassicae, manduca sexta, operophtera spp., ostrinia nubilalis, pammene spp., pandemis spp., panolis flammea, pectinophora gosszpiella, phthorimaea operculella, pieris rapae, pieris spp., plutella xylostella, prays spp., scirpophaga spp., sesamia spp., sp arganothis spp., spodoptera spp., synanthedon spp., thaumetopoea spp., tortrix spp., trichoplusia ni and yponomeuta spp;

from the order of coleoptera for example

agriotes spp., anthonomus spp., atomaria linearis, chaetocnema tibialis, cosmopolites spp., curculio spp., dermestes spp., diabrotica spp., epilachna spp., eremnus spp., leptinotarsa decemlineata, lissorhoptrus spp., melolontha spp., orycaephilus spp., otiorhynchus spp., phlyctinus spp., popillia spp., psylliodes spp., rhizopertha spp., scarabeidae, sitophilus spp., sitotroga spp., tenebrio spp., tribolium spp. and trogoderma spp.;

from the order of Orthoptera, for example

blatta spp., blatella spp., gryllotalpa spp., leucophae maderae, locusta spp., periplaneta spp. and schistocerca ispp.;

from the order of isopters for example

reticulitermes spp.;

from the order of psocopters for example

liposcelis spp.;

from the order Anoplura for example

haematopinus spp., linognathus spp., pediculus spp., pemphigus spp. and phylloxera spp.;

from the order mallophaga for example

damalinea spp. and trichodectes spp.;

from the order thysanoptera for example

frankliniella spp., hercinothrips spp., taeniothrips spp., thrips palmi, thrips tabaci and scirtothrips aurantii;

from the genus Heteroptera for example

cimex spp., distantielia theobroma, dysdercus spp., euchistus spp., eurygaster spp., leptocorisa spp., nezara spp., piesma spp., rhodnius spp., sahlbergella singularis, scotinophara spp. and triatoma spp.;

from the order of homoptera for example

aleurothrixus floccosus, alloyrodes brassicae, aonidiella spp., aphididae, aphis spp., aspidiotus spp., bemisia tabaci, ceroplaster spp., dhrysomphalus aonidium, chrysomphalus dictyospermi, coccus hesperidum, empoasca spp., eriosoma larigerum, erythroneura spp., gascardia spp. , laodelphax spp., lecanium corni, lepidosaphes spp., macrosiphus spp., myzus spp., nephotettix spp., nilaparvata spp., paratoria spp., pemphigus spp., planococcus spp., pseudaulacaspis spp., pseudococcus spp., psylla spp. ., pulvinaria aethiopica, quadraspidiotus spp., thopalosiphum spp., saissetia spp., scaphoideus spp., schizaphis spp., sitobion spp., trialeurodes vaporariorum, trioza erytreae and unaspis citri;

from the order of hymenoptera for example

acromyrmex, atta spp., cephus spp., diprion spp., diprionidae, gilpinia polytoma, hoplocampa spp., lasius spp., monomnrium pharaonis, neodiprion spp., neodiprion spp., solenopsis spp. and vespa spp.;

from the Diptera order for example

aedes spp., antherigona soccata, bibio hortulanus, calliphora erythrocephala, ceratitis spp., chrysomyia spp., culex spp., cuterebra spp., dacus spp., drosophila melanogaster, fannia spp., garstrophilus spp., glossina spp., hypoderma spp. ., hyppobosca spp., liriomyza spp., luculia spp., melanagromyza spp., musca spp., oestrus spp., orseolia spp., oscinella frit, pegomyia hyoscyami, phorbia spp., rhagoletis pomonella, sciara spp., stomoxys spp. , tabanus spp., tannia spp. and onion spp.;

from the siphonaptera order for example

ceratophyllus spp. and xenopsylla cheopis;

from the order thysanura for example

lepisma saccharin;

from the order of acarina for example

acarus siro, aceria sheldoni, aculus schlechtendali, amblyomma spp., argas spp., boophilus spp., brevipalpus spp., bryobia praetiosa, calipitrimerus spp.. chorioptes spp., dermanyssus gallinae, eotetranychus carpini, eriophyes spp., hyalomma spp., ixodes spp., olygonychus pratensis, ornithodoros spp., panonychus spp., phyllocoptruta oleivora, polyphagotarsonemus latus, psoroptes spp., rhipicephalus spp., rhizoglyphus spp., sarcoptes spp., tarsonemus spp. and tetranychus spp., and

from classes; nematodes for example

plant root pests, e.g. heterodera spp. and globodera spp. (cyst-forming nematodes), meloidogyne spp. (plant root nematodes), radopholus spp., pratylenchus spp., tylenchulus spp., longidorus spp., tricnodorus spp. and xiphinema spp.,

nematodes that attack the petiole, e.g. Ditylenchus spp.,

nematodes that attack leaves, eg aphelenchoides spp. i

nematodes that attack flowers, eg anguina spp..

The aforementioned phytopathogenic fungi include, for example:

from the class fungi imperfecti for example

botrytis spp., pyricularia spp., helminthosporium spp., fusarium spp., septoria spp., cercospora spp. and alternaria spp.;

from the class basidiomycetta for example

rhicoctonia spp., hemileia spp. and puccinia spp.;

from the ascomyceta class for example

venturia spp., erysiphe spp., podosphaera spp., monilinia spp. and uncinula spp. and

from the oomyceta class for example

phytophthora spp., pythium spp. and plasmopara spp..

With the active substances according to the invention, in particular, they can be destroyed or control pests of the above species on useful and ornamental plants in agriculture, horticulture and forestry or parts of plants such as fruits, flowers, crowns; petioles, bulbs or roots, while partially and later grown plant parts are still protected from these pests.

As target crops, grains such as wheat, barley, rye, oats, rice, corn or sugar beet are particularly suitable; canola such as sugar canola or canola; fruits such as stone fruits or berries, apples, pears, plums, peaches, almonds, cherries or, for example, strawberries, raspberries or blackberries; legumes such as beans, lentils, peas or soybeans; oilseeds such as rapeseed, mustard, poppy, olive, sunflower, coconut, castor, cocoa or peanut; pumpkin, cucumbers, or melons; fibrous plants such as cotton, flax or hemp; citrus fruits such as oranges, lemons or tangerines; vegetables such as spinach, lettuce, asparagus, carrots, onions, tomatoes, potatoes or peppers; laurels such as avocado, cinnamon or camphor, as well as tobacco, walnuts, coffee, eggplants, sugar cane, tea, pepper, vines, hops, bananas, natural rubber and ornamental plants.

The active substances according to the invention are particularly suitable for destroying insects, nematodes and representatives of the acarina order, especially insects that eat plants, such as anthonomus grandi, diabrotica balteata, heliothis virescens-larvae, plutella xylostella and spodoptera littoralis-larvae, insects that suck the sap of plants such as aphis craviccora and bemisia tabaci, insects that attack the lower part of the plant that is in the ground such as diabrotica balteata, soil nematodes that attack the plant root such as meloidogyne incognita and heterodera glycines, and mites such as tetranychus spp. in crops of cotton, fruit, corn, soy, canola, citrus fruits and vegetables.

Further areas of use of active substances according to the invention are the protection of stocks or warehouses or materials in the hygiene sector, especially the protection of domestic and useful animals from pests of the mentioned type.

Therefore, the invention also refers to agents for destroying pests that can be chosen as needed from emulsifying concentrates, suspension concentrates, solutions that are sprayed directly or diluted before application, spreading pastes, diluted emulsions, dusting powders, soluble powders, dispersing powders, wetting powders, sprinklers, granules or polymeric substances containing at least one of the active substances according to the invention.

The active substance is placed in these means in its pure form, a solid substance such as, for example, in a special core size or together with at least one of the auxiliary substances common in the formulation technique, such as active fillers, for example, solvents or solid carrier substances or such as surface active compounds (surfactants).

Potentially partially hydrogenated aromatic hydrocarbons, preferably fractions of C8 to C-12 alkylbenzols such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons such as paraffins or cyclohexane, alcohols such as ethanol, propanol or butanol, glycols can be used as solvents. as well as their ethers and esters such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol mono-methyl or -ethyl ether, ketones such as cyclohexanone, isophorone or diacetone alcohol, strong polar solvents such as N-methylpyrrolid-2-one, dimethylsulfoxide or N,N-dimethylformamide , water, possibly epoxidized vegetable oils, such as possibly epoxidized rape, castor, coconut or soybean oil, and silicone oils.

As a rule, natural stone flours such as calcite, talc, kaolin, montmorillonite or attapulgite are used as solid carriers, for example dusting agents and dispersing powders. To improve the physical properties, highly dispersed silicic acids and highly dispersed polymers with absorbency can be added. Porous types such as pumice, broken brick, sepiolite or bentonite can be used as granulate adsorption carriers, and calcite or sand as non-sorptive carrier materials. In addition, many granular materials of an inorganic or organic nature can be used, especially dolomite or crushed plant residues.

As surface-active compounds, depending on the type of active substances being formulated, cationic and/or anionic surfactants or mixtures of surfactants with good emulsifying, dispersing and cross-linking properties come into consideration. The following surfactants are given only as examples; many suitable surfactants used in the formulation technique are described in the known literature.

As nonionic surfactants, derivatives of polyglycols of aliphatic or cycloaliphatic alcohols, saturated and unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycolether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon residue and 6 to 18 carbon atoms, come into consideration as nonionic surfactants. in the alkyl residue of alkylphenol. Water-soluble polyethylene oxide adducts containing 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol with 1 to 10 carbon atoms in the alkyl chain are also suitable. These compounds usually contain 1 to 5 units of ethylene glycol per unit of propylene glycol. Examples include nonylphenol polyethoxyethanol, castor oil polyglycol ether, polypropylene-polyethylene oxide adduct, tributylphenoxypolyethoxyethanol: Further, fatty acid esters of polyoxyethylenesorbitan such as polyoxyethylenesorbitan-trioleate come into consideration.

Cationic surfactants are primarily quaternary ammonium salts, which have as substituents one alkyl residue with 8 to 22 C atoms, and as further substituents low, possibly halogenated alkyl, benzyl or low hydroxyalkyl residues. Salts are found mainly as halides, methylsulfates or ethylsulfates. Examples are stearyl-trimethyl-ammonium chloride and benzyl-di-(2-chloroethyl)-ethyl-ammonium bromide.

Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds, suitable as soaps are alkaline, alkaline earth and possibly substituted ammonium salts of higher fatty acids (C10-C22) such as sodium or potassium salts of oleic or stearic acids or a mixture of natural fatty acids that can be obtained, for example, from coconut oil; we also mention the salt: methyl-taurine fatty acids. However, synthetic surfactants are more often used, especially sulfonates of fatty acids, sulfates of fatty acids, sulfonated benzimidazole derivatives or alkylaryl sulfonates. Fatty acid sulfonates and sulfates are mostly found as anal, alkaline earth or possibly substituted ammonium salts and mostly have one alkyl residue with 8 to 22 C-atoms, whereby alkyl also includes the alkyl part of acyl residues; as examples, we cite the sodium or calcium salt of ligninsulfonic acid of dodecyl-sulfuric acid ester or a mixture of fatty alcohol sulfates obtained from natural fatty acids. This also includes salts of sulfuric acid esters and sulfonic acids of fatty alcohol ethylene oxide adducts. Sulfonated benzimidazole derivatives contain 2 sulfonic acid groups and one fatty acid residue with about u to 22 C-atoms. Alkylaryl sulfonates are, for example, the sodium, calcium or ammonium salts of triethanolammonium dodecyl benzenesulfonic acid, dibutylnaphthalenesulfonic acid or the formaldehyde condensation product of naphthalenesulfonic acid. Furthermore, suitable phosphates such as phosphoric acid ester salts of p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids come into consideration.

As a rule, the means contain 0.1 to 99%, especially 0.1 to 95% of active substances and 1 to 99.9%, especially 5 to 99.9% of at least one solid or liquid auxiliary substance, whereby as a rule 0 to 25 %, especially 0.1 to 20% of the agent can be surfactants (% always means percentage by weight). While concentrated means can be obtained over the counter, as a rule, the end user uses diluted means that have a much lower concentration of the active substance. The most used means consist of the following (% = weight percentage):

Emulsifying concentrates:

active substance: 1 to 90%, mostly 5 to 20%

surfactant: 1 to 30%, mostly 10 to 20%

solvent: 5 to 98%, mostly 70 to 85%

Detergents:

active substance: 0.1 to 10%, mostly 0.1 to 1%.

solid carrier: 99.9 to 90%, mostly 99.9 to 99%

Suspension concentrates:

active substance: 3 to 75%, mostly 10 to 50%

water: 94 to 24%, mostly 88 to 30%

surfactant: 1 to 40%, mostly 2 to 30%

Wetting powder:

active substance: 0.5 to 90%, mostly 1 to 80%

surfactant: 0.5 to 20%, mostly 1 to 15%

solid carrier: 5 to 99%, mostly 15 to 98%

Granules:

active substance: 0.5 to 30%, mostly 3 to 15%

solid carrier: 99.5 to 70%, mostly 97 to 85%

The action of the agents according to the invention can be greatly expanded and adapted to the given circumstances by the addition of other insecticidal, nettocidal, acaricidal and/or fungicidal active substances. As additional active substances, e.g. representatives of the following classes of active substances: organic phosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons and preparations of bacillus thuringiensis. The agents according to the invention may also contain further solid or liquid auxiliary substances as stabilizers, e.g. epoxidized vegetable oils (e.g. epoxidized coconut, canola or soybean oil), release agents, e.g. silicone oil, preservatives, viscosity regulators, binders and/or adhesion agents , as well as artificial fertilizers or other active substances for achieving special effects, eg bactericides, molluscicides or selective herbicides.

The agents according to the invention are obtained in a known manner, without excipients, for example by grinding and/or sieving a solid active substance or a mixture of active substances, e.g. to a certain grain size, and in the presence of at least one auxiliary substance, e.g. by mixing and/or grinding the active substance well or mixtures of active substances with auxiliary/auxiliary substance/substances. This process for the production of agents according to the invention and the use of compounds I for the production of these agents also form the subject of the invention.

The method of applying means, i.e. the method for destroying pests of the mentioned species, according to the desired goals and given circumstances, which can be spraying, fogging, dusting, coating, etching, sprinkling or watering, and the application of means for destroying pests of the mentioned species is a further subject of the invention. Typical concentrations for application are in the range between 0.1 and 1000 ppm, mainly between 0.1 and 500 ppm of the active substance. Amounts per hectare are generally 1 to 2000 g of active substance per hectare, especially 10 to 1000 g/ha, 20 to 600 g/ha is recommended.

The application procedure that is recommended in the field of plant protection is application to the leaves of the plant (leaf application), whereby the frequency of application and the required amount can be adjusted according to how much of the plant is attacked by the pest in question. The active substance can also reach the plant through the root (systemic effect), whereby the place where the plants grow is soaked with a liquid agent or the active substance is placed in a solid form in the soil where the plant grows, for example in the form of granules (application to the soil). In the case of rice crops, such granules can be placed in a flooded rice field. Destruction of nematodes is done primarily by application to the ground or ground.

The agents according to the invention are also suitable for the protection of plant growth, for example fruit, bulbs or grains or seedlings, against fungal infections and animal pests. Plant growth can be treated with an agent before germination, seeds can be etched before germination, for example. Active substances according to the invention can also be applied to the seeds (coating), whereby the grains are either soaked in a liquid agent or a layer of solid agent is applied to them. The product can be applied to the place of sprouting and when the plants have already sprouted, for example around the plants. The process of processing plant growth and the plant growth treated in this way are a further subject of the invention.

The following examples serve to explain the invention. They do not limit the invention. Temperatures are given in degrees Celsius.

Production examples

Example H1:

2-methyl-2H-indazole-3-carboxylic acid

a) 2-nitrobenzylidene-methylamine.

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110.5 g of 2-nitrobenzaldehyde is dissolved in 850 ml of benzene. 24.8 g of methylamine is added to this solution and the reaction mixture is boiled on a water separator until 17 ml of water is separated. The reaction mixture is cooled, concentrated and the crude product is dried under high vacuum. Thus, 2-nitrobenzylidene-methylamine with a melting point of 30°C is obtained.

b) 3-cyano-2-methyl-2H-indazole-1-oxide

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17.9 g of potassium cyanide is added to a solution of 120 g of 2-nitrobenzylidene-methylamine in 600 ml of methanol that has been cooled to a temperature between +5ºC and +10ºC. Finally, 44.1 g of glacial acetic acid is slowly added. During the exothermic reaction, the mixture is kept at a temperature of around +10ºC by cooling with ice. After half of the specified amount of glacial acetic acid has been added, the product crystallizes. A further 200 ml of methanol was added to the reaction mixture, and the remaining glacial acetic acid was added dropwise. The fractional mixture is stirred for 0.5 hours at room temperature, and then cooled to +10°C. The precipitated product is filtered. The product is washed with a little ethanol, then with hexane, and then cooled. Thus, 3-cyano-2-methyl-2H-indazole-1-oxide with a melting point of 156-158°C is obtained.

c) 3-cyano-2-methyl-2H-indazole

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120 g of phosphorus trichloride was slowly added to a solution of 64.7 g of 3-cyano-2-methyl-2H-indazole-1-oxide in 500 ml of chloroform. The reaction temperature is kept at +40ºC with ice cooling. After the addition is complete, the reaction mixture is refluxed for 1 hour, cooled and poured into 1 liter of ice water. A 30 percent solution of caustic soda is added until the solution becomes alkaline. It is extracted three times with 200 ml of chloroform. The combined chloroform extracts are washed twice with water and once with a saturated solution of table salt, dried over sodium sulfate, filtered and concentrated. The crude product is recrystallized from acetic acid ester/hexane. Thus, 3-cyano-2 methyl-2H-indazole with a melting point of 98-100ºC is obtained.

d) 2-methyl-2H-indazole-3-carboxylic acid

[image]

A mixture of 70 g of 3-cyano-2-methyl-2H-indazole and 1.75% sulfuric acid is stirred for 2.5 hours at +110ºC (bath temperature). Finally, the reaction mixture is cooled and poured onto 2 kg of ice, and extracted with acetic acid ester. The acetic acid ester phase is separated, washed once with water, once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The residue is slurried in not very cold acetic acid ester, filtered and dried in a vacuum. This gives 2-methyl-2H-indazole-3-carboxylic acid with a melting point of 233-235ºC (decomposition).

In an analogous way, it is obtained from

-5-chloro-2-nitrobenzaldehyde and methylamine 5-chloro-2-methyl-2H-indazole-3-carboxylic acid with a melting point of 247-248ºC;

-5-methyl-2-nitrobenzaldehyde and methylamine 2,5-dimethyl-2H-indazole-3-carboxylic acid with a melting point of 240-241°C;

-3-methyl-2-nitrobenzaldehyde and methylamine 2,7-dimethyl-2H-indazole-3-carboxylic acid with a melting point of 224-225ºC;

-2-nitrobenzaldehyde and cyclopropylamine 2-cyclopropyl-2H-indazole-3-carboxylic acid, with a melting point of 187-189ºC.

Example H2:

2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxy)-benzyl)-amide

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3.2 g of oxalyl chloride and 5 drops of dimethylformamide were added to a solution of 4 g of 2-methyl-2H-indazole-3-carboxylic acid in 50 ml of tetrahydrofuran, and the reaction mixture was stirred for 0.5 hours at room temperature. At the end, the reaction mixture is thickened, and the residue is dissolved in 50 ml of toluene. A solution of 4.9 g of 3-(4-fluorophenoxy)-benzylamine and 2.0 g of pyridine in 10 ml of toluene is added dropwise to this solution, which has been cooled to a temperature between 0ºC and +5ºC. After the addition is complete, the reaction mixture is stirred for 1 hour at room temperature and diluted with acetic acid ester. That mixture is twice; washed with water, once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The crude product is purified by column chromatography over silica gel with acetic acid ester/hexane (1:1). Thus, the amide 2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxy)-benzyl) with a melting point of 91-93°C is obtained.

Example H3:

amide N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)

[image]

To a suspension of 0.5 g of sodium hydride (55% in oil) in 40 ml of dimethoxyethane, 5.0 g of amide 2-methyl-2H-indazole-3-carboxylic acid-(4-trifluoromethylphenoxy)-benzyl) dissolved in 20 ml of dimethoxyethane. The mixture is stirred for another 15 minutes. Then, at room temperature, 1.0 g of acetyl chloride is added dropwise to 10 ml of dimethoxyethane. At the end, it is stirred for one hour. The mixture is concentrated on a rotary evaporator, and the residue is diluted with ethyl acetate. The mixture is washed twice with water and once with a saturated solution of table salt, dried over sodium sulfate, filtered and evaporated on a rotary evaporator. The residue is purified by column chromatography over silica gel with acetic acid ester/hexane (1:1). This gives the amide N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxy)-benzyl) with a melting point of 89-91°C.

In an analogous way, amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl) and amide 2-chloride of ethylcaproic acid N-(2-ethylenehexanoyl)-2-methyl- 2H-Indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl; with a melting point of 97-98°C.

Example H4

amide N-(tert.butoxyoxalyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl)

[image]

of dimethoxyethane, 5.0 g of amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl), dissolved in 20 ml of dimethoxyethane, is added dropwise at room temperature. The mixture is stirred for another 15 minutes. Then 2.0 g of tert.-butoxyoxalyl chloride dissolved in 10 ml of dimethoxyethane is added dropwise at room temperature. Then it is mixed for one hour. The reaction mixture is filtered through diatomaceous earth and the filtrate is evaporated on a rotary evaporator. The obtained crude product is purified as a liquid agent by column chromatography over silica gel with acetic acid ester/hexane (1:3). This gives the amide N-(tert.butoxyoxalyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxyl)-benzyl), melting point 107-108°C.

2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl) and amide N,N-dipropyl-N'-methyl-N'-sulfonylchloridurea N- (3,3-dipropyl-1-methylureido-1-sulphenyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxy)-benzyl) with a melting point of 110-111ºC.

Example H5:

In an analogous way, the compounds of tables 1 to 7 can be obtained,

Table 1

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Table 2

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Table 3

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Table 4

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Table 5

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[image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image] [image]

Table 6

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Table 7

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Formulation examples (% = weight percentage)

Example F1:

emulsion concentrates a) b) c)

Active substance no. 5,117 25% 40% 50%

Ca-dodecylbenzosulfonate 5% 8% 6%

Polyethylene glycol ether of castor oil (36 mol AEO) 5% - -

Tributylphenol polyethylene glycol ether (30 mol AEO) - 12% 4%

Cyclohexanone - 15% 20%

Mixture 65% 25% 20%

Emulsions of any desired concentration can be obtained from such concentrates by diluting them with water.

Example F2:

Solutions a) b) c) d)

Active substance no. 3.20 80% 10% 5% 95%

Ethylene glycol monomethyl ether 20% - - -

Polyethylene glycol MG 400 - 70% - -

N-methyl-2-pyrrolidone - 20% - -

Epoxidized coconut oil - - 1% 5%

Gasoline (boiling point 160-190ºC) - - 94% -

Solutions are suitable for application in the form of the smallest droplets.

Example F3:

Granules a) b) c) d)

Active substance no. 4.27 5% 10% 8% 21%

Kaolin 94% - 79% 54%

Highly dispersed silicic acid 1% - 13% 7%

Attapulgite - 90% - 18%

The active substance is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is finally evaporated in a vacuum.

Example F4:

Dusting agent a) b)

Active substance no. 5,117 2% 5%

Highly dispersed silicic acid 1% 5%

Talc 97% -

Kaolin - 90%

By mixing the carrier substances well with the active substance, a ready-to-use dusting agent is obtained.

Example F5:

spray powder a) b) c)

Active substance no. 2.05 25% 50% 75%

Na-lignmsultonate 5% 5% -

Na-lauryl sulfonate 3% - 5%

Na-diisobutylene naphthalene sulfonate - 6% 10%

Octylphenol polyethylene glycol ether (7 - 8 mol AeO) - 2% -

Highly dispersed silicic acid 5% 10% 10%

Kaolin 62% 27% -

The active substance is mixed with additional substances and the mixture is ground well in a suitable mill. A spray powder is obtained, which can be diluted with water into suspensions of any desired concentration.

Example F6:

emulsion concentrate:

Active substance no. 2,113 10%

Octylphenol polyethylene glycol ether (4-5 mol Aeu) 3%

Ca-dodecylbenzenesulfonate 3%

Castor oil polyglycol ether (36 mol AeO) 4%

Cyclohexanone 30%

Xylene mixture 50%

Emulsions of any desired concentration can be obtained from this concentrate by diluting it with water.

Example F7:

detergent a) b)

Active substance no. 2.08 5% 8%

Talc 95% -

Kaolin - 92%

Ready-to-use dusting agents are obtained by mixing the active substance with the carrier and grinding the mixture in a suitable mill.

Example F8:

Extruder granulate

Active substance no. 4.19 10%

Na-ligninsulfonate 2%

Carboxymethylcellulose 1%

Kaolin 87%

The active substance is mixed with additional substances, the mixture is ground and moistened with water. The wet mixture is extruded and granulated, and the resulting granulate is finally dried in a stream of air.

Example F9:

envelope granu1at

Active substance no. 1.02 3%

Polyethylene glycol (MG 200) 3%

Kaolin 94%

The finely ground active substance is evenly applied to kaolin moistened with polyethylene glycol in a mixer. In this way, dust-free coating granulate is obtained.

Example F10:

suspension concentrate

Active substance no. 2.95 40%

Ethylene glycol 10%

Nonylphenol polyethylene glycol ether (15 mol AeO) 6%

Na-ligninsulfonate 10%

Carboxymethylcellulose 1%

Silicone oil in the form of a 75% aqueous emulsion 1%

Water 32%

The finely ground active substance is well mixed with additional substances. In this way, a suspension concentrate is obtained, from which, by diluting with water, suspensions of any desired concentration can be obtained.

Biological examples

Example B1

Action against nilaparvata lugens

The rice plants are treated with an aqueous emulsion for spraying, which contains 400 ppm of the active substance: after drying the sprayed layer, 2nd and 3rd stage cricket larvae are placed on the rice plants. After 21 days, a numerical calculation is performed. From the comparison of the number of surviving crickets on treated plants with those on untreated ones, the percentage reduction of the population (% effect) is determined.

The compounds of Tables 1 to 7 show good activity against Nilaparvata lugens in this test. Especially the compounds 1.02, 2.05, 5.153 and 5.706 show activity above 80%.

Example B2

This/larvicidal action on heliothis virescens

Heliothis virescens eggs deposited on cotton are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After 8 days, a numerical calculation of the percent hatching of the eggs and the survival rate of the caterpillars is performed in comparison with untreated control eggs (% population reduction).

The compounds according to Tables 1-7 in this test show good activity against Heliothis virescens. Especially the compounds 1.02, 1.20, 2.05 and 5.706 show an activity of more than 80%.

Example 83:

Action against Heliothis virescens caterpillars

Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit dries, 10 caterpillars of the first stage of heliothis virescens are placed on the soybean plants and placed in a plastic container. After 6 days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% effect).

The compounds of tables 1 to 7 show good activity against heliothis virescens in this test. Especially the compounds 1.02, 1.20, 2.05 and 5.155 show an activity greater than 80%.

Example 84:

Action against Spodoptera littoralis caterpillars

Young soybean plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit dries, 10 caterpillars of the third stage of spodoptera littoralis are placed on soybean plants and everything is placed in a plastic container. After three days, a numerical calculation is performed. From the comparison of the number of dead caterpillars and the damage caused by gnats on the treated plant mass and the untreated ones, the percentage reduction of the population is determined, then the percentage reduction of the damage caused by gnats (% effect).

The compounds of tables 1 to 7 in this test show good activity against Spodoptera littoralis. Especially the compounds 2.05 and 5.155 show a good effect of more than 80%.

Example B5

Action against aphis craccivora

Pea sprouts are infected with aphis craccivora, sprayed with an emulsion containing 400 ppm of the active substance and incubated at 20ºC. After 3 and 6 days, a numerical calculation is performed. From the comparison of the number of dead aphids on treated with those on untreated plants, the percentage reduction of the population (% effect) is determined.

The compounds of tables 1 to 7 in this test show good activity against aphis craccivora. Especially compounds 2.05, 4.04 and 5.706 show a good activity above 80%.

Example B6

Action against crocidolomia binotalis caterpillars

Young kale plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit has dried, 10 caterpillars of the third stage of crocidolomia binotalis are placed on the kale plants and everything is placed in a plastic container. After three days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% effect).

The compounds of tables 1 to 7 show good activity against crocidolomia binotalis in this test, above 80%. Especially the compounds 1.02 and 1.20 show activity above 80%.

Example B7

Action against tetranychus urticae

A mixed population of tetranychus urticae is placed on the young bean plants and 1 day later they are sprayed with an aqueous emulsion containing 400 ppm of the active substance. The plants are incubated for 6 days at 25ºC, and then a numerical calculation is made. From the comparison of the number of dead eggs, larvae and adults on treated with those on untreated plants, the percentage reduction of the population (% effect) is determined.

The compounds of tables 1 to 7 show in this test an activity of Above 80% against tetranychus urticae.

Example B8:

Ovicidal effect on heliothis vilescens

Eggs of Heliothis virescens deposited on filter paper are briefly dipped in an acetone-water test solution containing 400 ppm of the active substance. After the test solution has dried, the eggs are incubated in a Petri dish. After 6 days, the percentage hatching of eggs is calculated in comparison with untreated control groups (% hatching reduction). The compounds according to tables 1 to 7 in this test show good activity against heliothis virescens. Especially the compounds 1.02, 1.20, 2.05, 5.155 and 5.706 show activity above 80%.

Example B9:

Action against Bemisia tabaci

Bush leguminous plants are placed in gauze cages and adult bemisia tabaci (whitefly) are placed on them. After laying the eggs, all adults are removed and 10 days later the plants on which the cocoons are located are treated with an aqueous emulsion containing the active substances being tested (concentration 400 ppm). Numerical calculation of % hatching is performed 14 days after the application of the active substance by comparison with untreated control groups.

The compounds according to tables 1 to 7 show good activity against bemisia tabaci in this test. Especially the compounds 1.02 and 1.20 show activity above 80%.

Example B10:

Action against the larvae of diabrotica balteata

Corn sprouts are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the emulsion layer has dried, 10 larvae of the second stage of diabrotica balteata are placed on the corn sprouts and everything is placed in a plastic container. After 6 days, a numerical calculation is performed. From the comparison of the number of dead larvae on treated with those on untreated plants, the percentage reduction of the population (% action) is determined. The compounds of tables 1 to 7 show good activity against diabrotica balteate in this test. Especially the compounds 1.02, 1.20, 2.05, 4.01, 4.03, 5.155 and 5.706 show activity above 80%.

Example B11:

Action against Plutella xylostella caterpillars

Young kale plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the deposit has dried, 10 caterpillars of the third stage of plutella xylostella are placed on the kale plants and everything is placed in a plastic container. After 3 days, a numerical calculation is performed. The percentage reduction of the population or percentage reduction of bite damage (% chipping).

The compounds of tables 1 to 7 show good activity against Plutella xylostella in this test. Especially the compounds 1.02 and 1.20 show activity above 80%.

Example B12:

Action against adult anthonomus grandis

Young cotton plants are sprayed with an aqueous emulsion containing 400 ppm of the active substance. After the layer has dried, 10 adult anthonomus grandis are placed on the cotton plants and everything is placed in a plastic container. 3 days later the numerical calculation is done. The percentage reduction of the population or. percentage reduction of bite damage (% effect).

The compounds of tables 1 to 7 show good activity against anthonomus grandis in this test. Especially the compounds 1.02, 1.20, 2.05, 5.155 and 5.706 show activity above 80%.

Example B13:

Action against puccinia graminis on wheat

a) residual protective effect:

Seven days after germination, wheat plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension containing uredospores of the fungus. After incubation for 48 hours at 95-100% relative humidity and at a temperature of about 20ºC, the infected plants are placed in a greenhouse with a temperature of about 22ºC. The assessment of the development of rust spots is made 12 days after infection.

b) Systemic action:

5 days after germination, the wheat plants are sprinkled with an emulsion obtained from the spray powder (0.006% of the active substance in relation to the soil volume). After 48 hours, the treated plants are infected with a suspension of uredospores of the fungus. After incubation for 48 hours at 96-100% relative air humidity and at about 20ºC, the infected plants are placed in a greenhouse with a temperature of about 22ºC. The assessment of the development of rust spots is made 12 days after infection.

The compounds from tables 1 to 7 show good activity against puccinia fungi. Especially the compound 1.02 shows an activity of more than 80%. Untreated but infected control plants were infected with puccinia 100%.

Example B14:

Action against Phythophthora infestans on tomatoes

a) residual protective effect:

After three weeks of breeding, the tomato plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension of fungal sporangia. Evaluation of fungal infection was performed after incubation of infected plants for 5 days at 90-100% relative air humidity and at 20ºC.

b) systemic action:

After three weeks of breeding, the tomato plants were watered with an emulsion obtained from the powder of the active substance (0.006% of the active substance in relation to the volume of the soil). In doing so, care must be taken that the emulsion does not come into contact with the parts of the plant above the ground. After 48 hours, the treated plants were infected with a suspension of fungal sporangia. Assessment of fungal infection is performed after incubation of infected plants for 5 days at 90-100% relative humidity and at 20ºC.

The compounds from tables 1 to 7 show good protective activity against the fungus phytophthora. Especially compounds 1.02, 1.20, 1.164, 4.04 and 4.06 show a good activity above 80%. Untreated but infected control plants were 100% infected with phytophthora.

Example B15:

Action against cercospora arachidicola on peanut plants

10-15 cm tall peanut plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance) and 48 hours later they are infected with a suspension of fungal conidia. Infected plants are incubated for 72 hours at around 21ºC and with high air humidity, and after the appearance of typical spots on the leaves, they are placed in a greenhouse. The evaluation of the fugicidal action is performed 12 days after infection, based on the number and size of spots. Compared to untreated but infected control plants (number and size of spots = 100%), peanut plants that were treated with the active substances from Tables 1 to 7 show reduced cercospora infection. In particular, compound 4.01 shows an activity greater than 80%.

Example B16:

Action against Plasmopara viticola on vines

a) residual - protective effect:

At the stage with 4 - 5 leaves, the vine grown from the seed is sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). after 24 hours, the treated plants are infected with a suspension of fungal sporangia. After incubation for 6 days at 95-100% relative air humidity and at 20ºC, infection with the fungus is assessed.

b) curative effect:

The vines grown from the seeds in the stage with 4 leaves are infected with a suspension of fungal sporangia. After incubation for 24 hours in a humid chamber at 95-100% relative air humidity and at 20ºC, the infected plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After the deposit has dried, the treated plants are again placed in the humid chamber. Assessment of fungal infection is performed 6 days after infection.

The compounds from tables 1 to 7 show good activity against Plasmopara viticola. Especially the compound 1.02 shows activity above 80%. Untreated but infected control plants, on the other hand, had 100 percent contamination with plasmopara.

Example B17:

Action against pyricularia oryzae on rice plants

a) residual protective action

After two weeks of breeding, the rice plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 48 hours, the treated plants are infected with a suspension of fungal conidia. After 5 days of incubation at 96-100% relative air humidity and at about 22º'C, fungal infection is evaluated.

b) systemic action

2-week-old rice plants are watered with an emulsion obtained from the powder of the active substance (0.006% of the active substance in relation to the volume of the soil). Then the pots are filled with water so much that the bottom parts of the stalks of the rice plants stand in the water. After 96 hours, the treated plants are infected with a suspension of fungal conidia. After incubation of infected plants for 5 days at 95-100% relative air humidity and at about 24ºC, fungal infection is assessed.

Rice plants that are treated with an emulsion based on the active substances of Tables 1 to 7 show only a small fungal infection compared to untreated control plants. Especially the compound 1.02 shows activity above 80%.

Example B18:

residual protective effect against venturia inaegualis on apple shoots

Apple seedlings with 10-20 cm long fresh shoots are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 24 hours, the treated plants are infected with a suspension of fungal conidia. The plants are incubated for 5 days at 90-100% relative air humidity, after which they are placed in a greenhouse with a temperature of 20-24ºC for 10 days. Infection with the fungus is assessed 15 days after infection.

The compounds from Tables 1 to 7 show good protective action against venturi. In particular, compound 1.02 shows an activity greater than 80%.

Example B19:

Action against erysipha graminis on barley

a) residual protective action

About 8 cm tall barley plants are sprayed with an emulsion obtained from the powder of the active substance (0.02% of the active substance). After 3-4 hours, the treated plants are dusted with fungal conidia. Infected barley plants are placed in a greenhouse with a temperature of about 22ºC and fungal infection is evaluated after 10 days.

b) systemic action

About 8 cm tall barley plants are watered with an emulsion obtained from the powder of the active substance (0.002% of the active substance in relation to the volume of the soil). Care was taken to ensure that the emulsion did not come into contact with the above-ground parts of the plant. After 48 hours, the treated plants were dusted with fungal conidia. Infected barley plants were placed in a greenhouse with a temperature of about 22ºC, and fungal infection was evaluated after 10 days.

Compounds Formulas from Tables 1 to 7 show good activity against erysipelas fungi. Untreated but infected control plants show 100% fungal infection. Especially the compound 11.02 shows an activity of more than 80%.

Example B20:

Action against Meloidogyne incognita on tomatoes

Meloidogyne incognita eggs are mixed into the sand. This mixture is placed in clay pots of 200 ml (5000 eggs per pot). On the same day, one 3-week-old tomato plant is planted in each pot and the formulated active substance is placed in the pots using a "drench" application (0.0006% of the active substance in relation to the soil volume). Potted plants are placed in a greenhouse at a temperature of 26 ±1ºC 1 relative humidity of 60%. After 4 weeks, the plants are evaluated by examining the formation of nodules on the roots according to the so-called root knot index ("Root-Knot Index"). Many root nodules were formed on untreated infected control plants (=100%). In contrast, compounds from Tables 1 to 7 show good activity (less than 20% infected).

Example B21:

Action against heterodera glycines on soybean

Sandy soil is infested with heterodera glycines eggs, about 6000 eggs per pot. Finally, the substances to be tested are mixed in appropriate concentrations. Treated and infested soil is placed in pots (180 cc) and three soybeans (cv. Maple Arrow) are sown in each pot. Each treatment is repeated three times. The pots are incubated at 27ºC for four to five weeks in a greenhouse. Then the plants are carefully removed from the pots, the roots are washed and the number of cysts is determined.

The compounds from Tables 1 to 7 show good activity against heterodera glycines, which can be seen in the almost complete reduction of cyst formation.

Claims (35)

1. Compounds Form indicated by, yes [image] R1 means hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, R2hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl, benzyl, -CHO, -CH2-O-D, -CO-D, -CO-O-D, -CO-CO-O-D, -S-Y, -SO-Y or - SO2-Y, R3 and R4 independently of each other mean hydrogen, C1-C4-alkyl, C3-C6-cycloalkyl or C1-C4-haloalkyl, E, independently of each other, means halogen, C1-C4-alkylthio, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-haloalkylthio, cyano or nitro, n number zero, one, two or three, X stands for oxygen or sulfur A phenyl, naphthyl, substituted phenyl or substituted naphthyl, D C1-C10-alkyl, phenyl or substituted phenyl, Y C1-C4-haloalkyl, C1-C4-cyanoalkyl, [image] phenyl or substituted phenyl, Z stands for hydrogen, C1-C10-alkyl, C1-C4-haloalkyl, C1-C10-alkyl, [image] phenyl, phenoxyl, substituted phenyl or unsubstituted phenoxyl, R14 and R15 independently of each other mean C1-C4-alkyl or C3-C6-cycloalkyl, R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl, R18 means C1-C4-alkyl or C3-C6-cycloalkyl, a R19 and R20 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl or substituted phenyl, in free form or in salt form. 2. Compounds according to claim 1 characterized in that D means C1-C10-alkyl, phenyl, C1-C4-alkylphenyl or halophenyl, Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, C1-C4-alkylphenyl, halophenyl, [image] [image] Z stands for hydrogen, C1-C4-alkyl, phenyl, C1-C4-alkylphenyl, halophenyl, C1-C10-alkoxy, phenoxyl, C1-C4-alkylphenoxyl, halophenoxyl or [image] R16 and R17 independently of each other mean C1-C4-alkyl, C3-C6-cycloalkyl, phenyl, or halophenyl, and R19 and R20 independently of each other mean C1-C4-alkyl. 3. Compounds according to claim 1, characterized in that D means C1-C10-alkyl, phenyl or 4-chlorophenyl, Y means C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-cyanoalkyl, phenyl, 4-methylphenyl, 4-chlorophenyl, 3,4-dichlorophenyl, [image] Z stands for hydrogen, C1-C4-alkyl, phenyl, 4-chlorophenyl, C1-C10-alkoxy, phenoxyl, 4-chlorophenoxyl or [image] R14 and R15 independently of each other mean C1-C4-alkyl, R16 C1-C4-alkyl, phenyl, 4-chlorophenyl, R17 methyl, a R 18 means C 1 -C 4 -alkyl or cyclopropyl. 4. Compounds according to claim 1, characterized in that R1 is methyl, and R3 and R4 are hydrogen. 5. Compounds according to claim 1, indicated by the fact that A stands for phenyl, naphthyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyl, C1- C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1- C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-halogenalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-halogenalkoxycarbonyl, where both vicinal residues can stand for –OH-CH2-O- , -O-CH2-CH2-O- or O-CF2-CH2, and phenyl or naphthyl substituted by zero or one radical -Y-R5, where Y means oxygen, sulfur or a bridge chain –SO-, -SO2-, - CO-, -CR6R7-, or a direct single bond, R5 phenyl, naphthyl or pyridyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyl, C1 -C4-halogenalkoxyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsul phenyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfinyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4- haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-halogenalkoxycarbonyl substituted phenyl, naphthyl or pyridyl, whereby two of these residues in the vicinal position can form a bridge of the structure –O-CH2-O-, -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O-, R6 and R7 independently of each other mean hydrogen or C1-C4-alkyl, and R8 means hydrogen, C1-C4-alkyl, formyl, C1 -C4-alkylcarbonyl or C1-C4-alkoxycarbonyl. 6. Compounds according to claim 1, characterized in that A stands for a possibly substituted phenoxyphenyl group of the formula [image] where R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4-alkyl, C1-C4 -Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl , C1-C4-alkylsulfonyloxy, halogen-C1-C4-alkylsulfonyloxy, cyano or nitro, and R12 and R13 together mean –O-CH2-O-. 7. Compounds according to claim 6, characterized in that R9 and R10 are hydrogen, R11 and R12 independently of each other are hydrogen, fluorine, chlorine or trifluoromethyl, R13 means hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkoxy, C1-C4-haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfonyl, C1-C4- alkylsulfonyloxy, halogen-C1-C4-alkylsulfonyloxy, fluorine, chlorine, bromine, cyano or nitro, and R12 and R13 together mean –O-CH2-O-. 8. Compounds according to claim 6, characterized in that R9 and R10 are hydrogen R11 and R12 independently of each other are hydrogen, fluorine, chlorine or trifluoromethyl, R13 is hydrogen, C1-C4-alkyl, fluorine, chlorine, bromine, cyano, methoxyl, methylthio, trifluoromethyl, methylsulfonyl, methylsulfonyloxyl or trifluoromethylsulfonyloxyl, and R12 and R13 together mean –O-CH2-O-. 9. Compounds according to claim 8, characterized in that n stands for the numbers zero, one or two, and the substituents E independently of each other for halogen, C1-C4-alkyl, C1-C4-halogenoalkyl or C1-C4-alkyl, R1 for methyl or ethyl, and R3 and R4 for hydrogen. 10. 3-carbamoyl-2H-indazoles according to claim 1, characterized in that R1 means hydrogen, C1-C4-alkyl or C3-C6-cycloalkyl, R2 hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, R3 and R4 independently of each other are hydrogen, C1-C4-alkyl, C1-C4-cycloalkyl or C3-C6-haloalkyl, E, independently of each other, means halogen, C1-C4-alkyl, C1-C4-alkyl, C1-C4-alkylthio, C1-C4-halogenalkyl, C1-C4-halogenalkyl, C1-C4-halogenalkylthio, cyano or nitro, n numbers zero, one, two or three, X oxygen or sulfur, a A means phenyl, naphthyl, substituted phenyl or substituted naphthyl. 11. Compounds according to claim 10, indicated by the fact that A is phenyl, naphthyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyl, C1-C4 -haloalkyl, C1-C4-alkylthio, C1-C4-haloalkylthio, C1-C4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-haloalkylsulfinyl, C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1-C4 -alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, and C1-C4-halogenalkylcarbonyl, C1-C4-alkoxylcarbonyl or C1-C4-halogenalkoxycarbonyl, where both vicinal residues can stand for -O-CH2-O- , -O-CF2-O-, -O-CH2-CH2-O- or -O-CF2-CF2-O- and phenyl or naphthyl substituted by zero or one radical –Y-R5, where Y means oxygen, sulfur or bridge chain -SO-, SO2-, -CO-, -CR6R7-, -NR8- or direct bond, R5 phenyl, nityl or pyridyl or zero, one, two or three residues from the halogen group, C1-C4-alkyl, C1 -C4-Hyalogenalkyl, C1-C4-Alkoxyl, C1-C4-Halogenalkoxyl, C1-C4-Alkylthio, C1-C4-Halogenalkylthio, C1-C 4-alkylsulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfinyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxyl, formyl, nitro, cyano, C1-C4-alkylcarbonyl, C1-C4-alkylsulfonyl C4-haloalkylcarbonyl, C1-C4-alkoxycarbonyl or C1-C4-haloalkoxycarbonyl substituted phenyl, naphthyl or pyridyl, whereby two of these residues in the vicinal position can form a bridge of the structure -O-CH2-O-, -O-CF2-O -, -O-CH2-CH2-O- or -O-CF2-CF2-O-, R6 and R7 independently of each other mean hydrogen or C1-C4-alkyl, and R8 means hydrogen, C1-C4-alkyl, formyl , C 1 -C 4 -alkylcarbonyl or C 1 -C 4 -alkoxycarbonyl. 12. Compounds according to claim 11, characterized in that the defined naphthyl radicals are attached in the 1- or 2-position, and the defined pyridyl radicals are attached in the 2-, 3- or 4-position. 13. Compounds according to claim 10, characterized in that n stands for the numbers zero, one or two, and the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl. 14. Compounds according to claim 10, characterized in that R stands for methyl or ethyl, and R2, R3 and R4 stand for hydrogen. 15. Compounds according to claim 10, characterized in that A stands for an optionally substituted phenoskyphenyl group of the formula [image] where R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, and R13 hydrogen, halogen, C1-C4-alkyl, C1-C4- Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkylthio, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl, C1-C4-Haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1-C4-alkylsulfonyloxy, cyano or nitro. 16. Compounds according to claim 15, characterized by the fact that R9, R10, R11 and R12 are hydrogen, and R13 is hydrogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-alkyl, C1-C4-halogenalkoxyl, C1 -C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, cyano or nitro. 17. Compounds according to claim 16, characterized in that R13 means hydrogen, halogenmethyl, halogenethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl, ethylsulfonyl, methylsulfonyloxyl or trifluoromethylsulfonyloxyl. 18. Compounds according to claim 10, indicated by the fact that n stands for the numbers zero, one or two, the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-haloalkyl or C1-C4-alkyl, R1 for methyl or ethyl, and R2, R3 and R4 for hydrogen, and A stands for a group of the formula [image] where R9, R10, R11, R12 independently of each other mean hydrogen, halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-halogenalkoxyl or C1-C4-alkyl, and R13 means hydrogen, halogen, C1-C4 -Alkyl, C1-C4-Haloalkyl, C1-C4-Alkoxyl, C1-C4-Haloalkyl, C1-C4-Haloalkylthio, C1-C4-Alkylthio, C1-C4-Alkylsulfinyl, C1-C4-Alkylsulfonyl, C1-C4-Haloalkylsulfinyl , C1-C4-haloalkylsulfonyl, C1-C4-alkylsulfonyloxy, halo-C1-C4-alkylsulfonyloxy, cyano or nitro. 19. Compounds according to claim 10, indicated by the fact that n stands for the numbers zero, one or two, the substituents E independently of each other for halogen, C1-C4-alkyl, C1-C4-haloalkyl, C1-C4-haloalkyl or C1- C4-Alkoxyl, R1 for methyl or ethyl, R2, R3 and R4 for hydrogen, and A for the group of the formula [image] where R13 means hydrogen, halogen, C1-C4-alkyl, halomethyl, haloethyl, C1-C4- alkoxy, halomethoxy, halogenethoxy, C1-C4-alkylthio, C1-C4-alkylsulfinyl, methylsulfonyl, ethylsulfonyl, halogenmethylsulfonyl, methylsulfonyloxy or trifluoromethylsulfonyl, cyano or nitro. 20. Compounds according to claim 19, characterized in that R13 means hydrogen, halogenmethyl, halogenethyl, cyano, nitro, methylthio, ethylthio, methylsulfonyl or ethylsulfonyl. 21. Compounds according to claim 10, indicated by the fact that n stands for the numbers zero, one or two, the substituents E independently of each other stand for halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyl, C1 -C4-halogenalkoxyl; R 1 stands for methyl or ethyl; R1, R3, R4 stand for hydrogen, and A for phenyl, naphthyl or zero, one, two or three residues from the group halogen, C1-C4-alkyl, C1-C4-halogenoalkyl, C1-C4-alkyl, C1-C4- haloalkyl, C1-C4-alkylthio, C1-C4-halogenalkylthio, C1-C4-alkylsulfinyl, C1-C4-halogensulfinyl, C1-C4-alkylsulfonyl, C1-C4-halogenalkylsulfonyl, C1-C4-alkylsulfonyloxy, halogen-C1-C4- alkylsulfonyloxyl, formyl, cyano, nitro, C1-C4-alkylcarbonyl, C1-C4-halogenalkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-halogenalkylcarbonyl, C1-C4-alkoxycarbonyl, C1-C4-halogenalkoxycarbonyl, substituted phenyl or naphthyl, at and two of these residues in the vicinal position can stand for –O-CH2-O-, –O-CF2-O-, –O-CH2-CH2-O- or –O-CF2-CF2-O-. 22. Compounds according to claim 1 of the formula, characterized in that it is selected from the group consisting of compounds 2-methyl-2H-indazole-3-carboxylic acid-(4-tert-butyl-benzyl)-amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-fluorophenoxy)-benzyl)-amide 2-methyl-2H-indazole-3-carboxylic acid-(3-(4-fluorophenoxy)-benzyl)-amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)benzyl)-amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(4-methylthiophenoxy)-benzyl)-amide 2-methyl-2H-indazole-3-carboxylic acid-(4-(2-chloro-4-trifluoromethylphenoxy)-benzyl)-amide N-acetyl-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethyl-phenoxy)-benzyl)-amide N-(tert-butoxyoxaly)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl)-amide, N-(3,3-dipropyl-1-methylureido-1-sulfenyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl)-amide N-(2-ethylhexanoyl)-2-methyl-2H-indazole-3-carboxylic acid-(4-(4-trifluoromethylphenoxy)-benzyl)-amide, 23. Process for the production of compounds of the formula I according to claim 1, in which R2 means hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R2, R3, R4, A, E, X and n have the meaning given under the formula And indicated by that, yes a) 2H-indazole-3-carboxylic acid of formula II [image] in which E, n and R1 have the meaning given by formula I, condenses with an amine of formula III [image] in which R2 means hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R3, R4 and A have the meaning given under formula I or b) 2H-indazole-3-carboxylic acid of formula II is converted into acid halide, imidazolide or alkyl ester of formula IV [image] in which R1, E and n have the meaning given under formula I, and Q stands for chlorine, bromine, 1-imidazolyl, methoxyl or ethoxyl, which reacts with the amine of the formula or, optionally, the obtained 3-carbamoyl-2H-indazole-derivative of the subformula Ia [image] wherein R2 is hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meaning given in claim 1, by treatment with a thionating agent it is converted into a compound of subformula Ib [image] in which R2 means hydrogen, C1-C4-alkyl, benzyl or C3-C6-cycloalkyl, and R1, R3, R4, A, E and n have the meaning given under formula I and/or optionally the compound of formula I is obtained according to the process or in some other way, in free form or in the form of a salt, converted into another compound of formula I, the mixture of isomers that can be obtained according to the process is separated and the desired isomers are isolated and/or the free compound of formula I that can be obtained according to the process or in some other way, is converted into a salt or a salt of a compound of formula I which can be obtained according to the process or in some other way, is converted into a free compound of formula I or into another compound. 24. Process for the production of compounds of formula I according to claim 1, in which R2 has a meaning other than hydrogen, C1-C4-alkyl, benzyl and C3-C6-cycloalkyl, characterized in that the compound of formula Ic, [image] wherein R1, R3, R4, A, E and n have the meaning given in claim 1, in the presence of one base with the compound Hal-CH2-O-D, Hal-CHO, Hal-CO-D, Hal-CO-O-D, Hal-CO -CO-D, Hal-CO-CO-O-D, Hal-S-Y, Hal-SO-Y or Hal-SO2-Y, in which Hal is a chlorine, bromine or iodine atom and D and Y have the meaning given under formula I , and that, if desired, the obtained 3-carbamoyl-2H-indazole derivative of subformula Ia according to claim 23, in which R2 has a meaning other than hydrogen, C1-C4-alkyl, benzyl and C3-C6-cycloalkyl, and R1, R3, R4 . D, -CO-CO-O-D, -S-Y, -SO-Y or –SO2 Y as well as D, Y, R1, R3, R4, A, E and n have the meaning given under formula I and/or optionally, the compound of the formula I which can be obtained according to the process or in some other way, in free form or in the form of a salt, is converted into another compound of the formula I, the mixture of isomers obtained according to the process is separated and the desired and isomers are isolated and/or the free compound of formula I obtainable according to the process or in some other way is converted into a salt or the salt of the compound of formula I obtainable according to the process or in some other way is converted into the free compound of the formula And or in some other salt. 25. Means for destroying pests, characterized by the fact that as an active substance it contains at least one compound according to claim 1 of formula I, in free form or in the form of agrochemically usable salts and possibly at least one auxiliary substance. 26. Agent according to claim 25, characterized in that it is used, nematodes, representatives of the acarina order and/or phytopathogenic fungi. 27. The method for the production of means according to claim 25, characterized by the fact that it contains at least one active substance, that the active substance is mixed well with the auxiliary substance/substances and/or ground. 28. Application of the compound according to claim 1 of formula I, characterized by the fact that in free form or in the form of agrochemically usable salts, for the production of means according to claim 25. 29. Application of the agent according to claim 25, characterized in that it is used to destroy pests. 30. Application according to claim 29, characterized by the fact that it is used to suppress or destruction of insects, nematodes, representatives of the acarine order and/or phytopathogenic fungi. 31. Application according to claim 29, characterized in that it is used for the protection of plant growth. 32. Procedure for destroying pests, characterized in that the agent according to claim 25 is applied to pests or to their environment. 33. The method according to claim 32, characterized in that it is used for the destruction of insects, nematodes, representatives of the acarine order and/or phytopathogenic fungi. 34. The method according to claim 32, for the protection of plant growth, characterized in that the plant growth is treated at the point of sprouting. 35. Plant growth, indicated by the fact that it is treated according to the procedure described in claim 34.