DE19548370A1 - New imino:oxy-substituted phenyl:acetic acid derivatives - Google Patents

Abstract

2-(2-(Iminooxy)-phenyl)-2-(methoxyimino, methoxymethylene or ethylidene)-acetic acid amide or methyl ester derivatives of formula (I) and their salts are new. R<1> = (a) -C(=NOMe)-COOMe, (b) -C(=NOMe)-CONHMe, (c) -C(=NOMe)-CONH2, (d) -C(=CHOMe)-COOMe or (e) -C(=CHMe)-COOMe; R<2> = CN, NO2, CF3, halogen, 1-4C alkyl or 1-4C alkoxy; m = 0-2; R<3> = H, OH, cyclopropyl, halogen, 1-4C alkyl, CN, 1-4C alkoxy or 1-4C alkylthio; R<4> = 1-8C alkyl, 2-8C alkenyl, 2-8C alkynyl, 3-8C cycloalkyl, aryl or heteroaryl (all optionally partially or completely halogenated or substituted by 1-3 of CN, NO2, OH, SH, NH2, COOH, CONH2, CSNH2, halogen, alkyl, haloalkyl, alkylsulphonyl, alkylsulphoxyl, 3-6C cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, mono- or dialkylamino, mono- or dialkylaminocarbonyl, mono- or dialkylaminothiocarbonyl, alkenyl, alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, heteroaryl and heteroaryloxy); or R<5>-Y-N=C(R<6>)-; R<5> = (i) H; (ii) 1-10C alkyl, 3-6C cycloalkyl, 2-10C alkenyl, 3-10C alkynyl, (1-10C) alkylcarbonyl, (2-10C) alkenylcarbonyl, (3-10C) alkynylcarbonyl or (1-10C) alkylsulphonyl (all optionally partially or completely halogenated or substituted by 1-3 of CN, NO2, OH, SH, NH2, COOH, CONH2, CSNH2, halogen, alkyl, haloalkyl, alkylsulphonyl, alkylsulphoxyl, 3-6C cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, mono- or dialkylamino, mono- or dialkylaminocarbonyl, mono- or dialkylaminothiocarbonyl, alkenyl, alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy and heteroarylthio (where aromatic or heteroaromatic moieties are themselves optionally partially or completely halogenated or substituted by 1-3 of CN, NO2, OH, SH, NH2, COOH, CONH2, CSNH2, halogen, alkyl, haloalkyl, alkylsulphonyl, alkylsulphoxyl, 3-6C cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, mono- or dialkylamino, mono- or dialkylaminocarbonyl, mono- or dialkylaminothiocarbonyl, alkenyl, alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, heteroaryl, heteroaryloxy, heteroarylthio and -C(=NOR<7>)-An-R<8>)); or (iii) aryl, heteroaryl, arylcarbonyl, heteroarylcarbonyl, arylsulphonyl or heteroarylsulphonyl (all optionally partially or completely halogenated or substituted by 1-3 of CN, NO2, OH, SH, NH2, COOH, CONH2, CSNH2, halogen, alkyl, haloalkyl, alkylcarbonyl, alkylsulphonyl, alkylsulphoxyl, 3-6C cycloalkyl, alkoxy, haloalkoxy, alkoxycarbonyl, alkylthio, mono- or dialkylamino, mono- or dialkylaminocarbonyl, mono- or dialkylaminothiocarbonyl, alkenyl, alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, heteroaryl, heteroaryloxy and -C(=NOR<7>)-An-R<8>); A = O, S, NH or N(alkyl); n = 0 or 1; R<7>,R<8> = H or alkyl; R<6> = H, OH, halogen or as R<3>; Y = O or NR<9>; R<9> = H or alkyl; unless specified otherwise alkyl moieties have 1-6C and alkenyl moieties 2-6C. Intermediates of formulae (IV) and (IIA) are also new. R<31> = 1-8C alkyl; X = F or other nucleofugeous leaving group.

Description

The present invention relates to new iminoxy-substituted Phenylacetic acid derivatives that facilitate mitochondrial respiration from Pil zen, inhibit insects and spider mites and the antifungal, in Secticidal and acaricidal effects and in particular fungicidal we against phytopathogenic fungi.

The present invention further relates to processes for the manufacture preparation of such compounds and intermediates for their manufacture position as well as processes and agents for use as fungicides, Antifungals, insecticides and acaricides, these phenylacetic use or contain acid derivatives.

Phenylacetic acid derivatives for pest control are from the literature fighting known (EP-A 370 629, EP-A 463 488, EP-A 460 575, WO-A 95/21154, WO-A 95/21153, WO-A 95/18789).

The present invention has provided new compounds with improvements effect as a task. Subject of the present Er invention are iminoxy-substituted phenylacetic acid derivatives of general formula 1

in which the substituent and the index have the following meanings to have:

R² cyano, nitro, trifluoromethyl, halogen, C₁-C₄-alkyl or C₁-C₄-alkoxy
m is 0, 1 or 2, it being possible for the radicals R 2 to be different if m is 2;
R³ is hydrogen, hydroxy, cyclopropyl, halogen, C₁-C₄ alkyl, cyano, C₁-C₄ alkoxy or C₁-C₄ alkylthio;
R⁴ C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₃-C₈-cycloalkyl, aryl or hetaryl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: Cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁- C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylamino carbonyl, di-C₁-C₆-alkylaminocarbonyl , C₁-C₆-alkylaminothio carbonyl, di-C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, and hetaryloxy
or the group R⁵-YN = C (R⁶) -, in which
R⁵ is hydrogen or C₁-C₁₀-alkyl, C₃-C Cycl-cycloalkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-alkynyl, C₁-C₁₀-alkylcarbonyl, C₂-C₁₀-alkenylcarbonyl, C₃-C₁₀-alkynylcarbonyl or C₁-C₁₀- Alkylsulfonyl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothio carbonyl, halogen, C₁-C₆-alkyl, C₁-C₆- Haloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxy, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino, Di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylaminothiocarbonyl, di-C₁-C₆-alkylaminothio carbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl , Benzyl oxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, the aromatic and heteroa Romatic residues can in turn be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, halogen, aminothio carbonyl, C₁-C₆-alkyl, C₁- C₆-haloalkyl, C₁-C₆-alkyl sulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkylthio, C₁-C₆ -Alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkylaminothiocarbonyl- di-C₁-C₆-alkylaminothio carbonyl, C₂-C₆-alkenyl, C₂-C₆- Alkenyloxy, benzyl, benzyl oxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy, het arylthio or C (= NOR⁷) -A _n -R⁸ or
Aryl, hetaryl, arylcarbonyl, hetarylcarbonyl, aryl sulfonyl or hetarylsulfonyl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen , C₁-C₆-alkyl, C₁-C₆-halogeno alkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkyl thio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkyl aminocarbonyl, di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkyl aminothiocarbonyl, di -C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR⁷) -A _n -R⁸, where
A represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or C₁-C₆-alkyl;
n 0 or 1;
R⁷ is hydrogen or C₁-C₆ alkyl and
R⁸ is hydrogen or C₁-C₆-alkyl,
and in which
R⁶ has hydrogen, hydroxy, halogen or one of the meanings mentioned for R³
and
Y represents O or NR⁹, where R⁹ is hydrogen or C₁-C₆-alkyl,
as well as their salts.

The group R¹ in Formula 1 is usually used by us as a pharmaco called phor, the group R³ (R⁴) C = N-O- as a side chain.

The compounds of formula 1 according to the invention can Lich their C = N or C = C double bonds appear as E / Z isomers ten, with respect to the respective double bond in the pharmacophore R¹ basically the E isomers biologically more active and preferred are.

Regarding the R³ (R⁴) C = N-O double bonds within the iminoxy side chains E / Z isomers can also occur; this applies also for any further C = N or C = C double bonds in the Side chain. Because of the usually better accessibility usually the E isomers (these are generally the "trans" or "anti" isomers) preferred, which are often under the action of protonic acids or Lewis acids or under Form light from the other isomers.

The isomers can by conventional methods such. B. Kristallisa tion or chromatography. For the fiction according applications as fungicidal, acaricidal, insecticidal or antifungal agents are generally, but not in the E or "trans" isomers are preferred in each individual case. Provided Separation is required in the synthesis of isomer mixtures  but not absolutely necessary since the individual isomers partly during the practical application according to the invention (e.g. as fungicides under field conditions) deln z. B. under the influence of light, acid or base also in vivo.

Both the individual isomers and their mixtures are from the invention comprises and are biologically active, especially in vivo.

In the definitions of compounds 1 given at the outset the collective terms used that are generally representative of the following groups:

Halogen: fluorine, chlorine, bromine and iodine;
Alkyl: straight-chain or branched alkyl groups with 1 to 4, 6 or 10 carbon atoms, e.g. B. C₁-C₆-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl, 1,1-dimethylethyl, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2, 2-dimethylpropyl, 1-ethylpropyl, hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2 -Dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl , 1-ethyl-1-methyl propyl and 1-ethyl-2-methyl propyl;
Alkylamino: an amino group which carries a straight-chain or branched alkyl group having 1 to 6 carbon atoms as mentioned above;
Dialkylamino: an amino group which carries two independent, straight-chain or branched alkyl groups each having 1 to 6 carbon atoms as mentioned above;
Alkylcarbonyl: straight-chain or branched alkyl groups with 1 to 10 carbon atoms, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkylsulfonyl: straight-chain or branched alkyl groups with 1 to 6 or 10 carbon atoms, which are bonded to the skeleton via a sulfonyl group (-SO₂-);
Alkylsulfoxyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via a sulfoxyl group (-S (= O) -);
Alkylaminocarbonyl: alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
Dialkylaminocarbonyl: dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkylaminothiocarbonyl: Alkylamino groups with 1 to 6 carbon atoms as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
Dialkylaminothiocarbonyl: dialkylamino groups each having 1 to 6 carbon atoms per alkyl radical as mentioned above, which are bonded to the skeleton via a thiocarbonyl group (-CS-);
Haloalkyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms in these groups can be partially or completely replaced by halogen atoms as mentioned above, e.g. B. C₁-C₂-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and penta fluoroethyl;
Alkoxy: straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via an oxygen atom (-O-), e.g. B. C₁-C₆ alkoxy such as methyloxy, ethyloxy, propyloxy, 1-methylethyloxy, butyloxy, 1-methylpropyloxy, 2-methylpropyloxy, 1,1-dimethylethyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy, 3-methylbutyloxy, 2nd , 2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy, 1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 1-methylpentyloxy, 2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy, 1,1-dimethylbutyloxy, 1 , 2-dimethylbutyloxy, 1,3-dimethylbutyloxy, 2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 3,3-dimethylbutyloxy, 1-ethylbutyloxy, 2-ethylbutyloxy,
Alkoxycarbonyl: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, which are bonded to the skeleton via an oxycarbonyl group (-OC (= O) -);
Haloalkoxy: straight-chain or branched alkyl groups with 1 to 6 carbon atoms, in which groups the hydrogen atoms can be partially or completely replaced by halogen atoms as mentioned above, and where these groups are bonded to the structure via an oxygen atom;
Alkylthio: straight-chain or branched alkyl groups with 1 to 4 or 6 carbon atoms as mentioned above, which are bonded to the skeleton via a sulfur atom (-S-), e.g. B. C₁-C₆-alkyl thio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio, 1,1-dimethylethylthio, pentylthio, 1-methylbutylthio, 2-methylbutylthio, 3-methylbutylthio, 2,2-dimethylpropylthio, 1-ethylpropylthio, hexylthio, 1,1-dimethylpropylthio, 1,2-dimethylpropylthio, 1-methylpentylthio, 2-methylpentylthio, 3-methylpentylthio, 4-methylpentylthio, 1,1-dimethylbutylthio, 1,2- Dimethylbutylthio, 1,3-dimethylbutylthio, 2,2-dimethylbutylthio, 2,3-dimethylbutylthio, 3,3-dimethylbutylthio, 1-ethylbutylthio, 2-ethylbutylthio, 1,1,2-trimethylpropylthio, 1,2,2-trimethylpropylthio , 1-ethyl-1-methylpropylthio and 1-ethyl-2-methylpropylthio;
Cycloalkyl: monocyclic alkyl groups with 3 to 6 carbon ring members, e.g. B. cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl;
Alkenyl: straight-chain or branched alkenyl groups with 2 to 6 or 10 carbon atoms and a double bond in any position, e.g. B. C₂-C₆ alkenyl such as ethenyl, 1-propenyl, 2-propenyl, 1-methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1-propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3- Methyl-1-butenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl, 3-butenyl, 3-methyl- 3-butenyl, 1,1-dimethyl-2-propenyl, 1,2-dimethyl-1-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1-pentenyl, 4-methyl-1- pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2-pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3-pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4-penteny 1,4-methyl-4-pentenyl, 1 , 1-dimethyl-2-butenyl, 1,1-dimethyl-3-butenyl, 1,2-dimethyl-1-butenyl, 1 , 2-dimethyl-2-butenyl, 1,2-dimethyl-3-butenyl, 1,3-dimethyl-1-butenyl, 1,3-dimethyl-2-butenyl, 1,3-dimethyl-3-butenyl, 2nd , 2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1-butenyl, 3rd , 3-Dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2nd -Ethyl-3-butenyl, 1,1,2-trimethyl-2-propenyl, 1-ethyl-1-methyl-2-propenyl, 1-ethyl-2-methyl-1-propenyl and 1-ethyl-2-methyl -2-propenyl;
Alkenyloxy: straight-chain or branched alkenyl groups with 2 to 6 carbon atoms and a double bond in any position, which are bonded to the skeleton via an oxygen atom (-O-);
Alkenylcarbonyl: straight-chain or branched alkenyl groups with 2 to 10 carbon atoms and a double bond in an arbitrary position, which are bonded to the skeleton via a carbonyl group (-CO-);
Alkynyl: straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in any position, e.g. B. C₃-C₆-alkynyl such as 2-propynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1- Methyl-3-butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 2-hexynyl, 3-hexynyl, 4-hexynyl, 5-hexynyl, 1- Methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4-pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl- 3-methyl-4-pentynyl, 4-methyl- 2-pentinyl, 1,1-dimethyl-2-butynyl, 1,1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 1-ethyl-2- butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl and 1-ethyl-1-methyl-2-propynyl;
Alkynylcarbonyl: straight-chain or branched alkynyl groups with 3 to 10 carbon atoms and a triple bond in an arbitrary position, which are bonded to the skeleton via a carbonyl group (-CO-);
Aryl or aryloxy, arylthio, arylcarbonyl and arylsulfonyl: aromatic mono- or polycyclic hydrocarbon radicals which are directly or (aryloxy) via an oxygen atom (-C-) or (arylthio) a sulfur atom (-S-), (arylcarbonyl) via a carbonyl group (-CO-) or (arylsulfonyl) via a sulfonyl group (-SO₂-) are bound to the structure, for. B. phenyl, naphthyl and phenanthrenyl or phenyloxy, naphthyloxy and phenanthrenyl oxy and the corresponding carbonyl and sulfonyl radicals;
Hetaryl or hetaryloxy, hetarylthio, hetarylcarbonyl and hetarylsulfonyl: aromatic mono- or polycyclic radicals, which in addition to carbon ring members may additionally contain one to four nitrogen atoms or one to three nitrogen atoms and one oxygen or one sulfur atom or one oxygen or one sulfur atom and which directly or (hetaryloxy) via an oxygen atom (-O-) or (hetarylthio) a sulfur atom (-S-), (hetarylcarbonyl) via a carbonyl group (-CO-) or (hetaryl sulfonyl) via a sulfonyl group (-SO₂- ) are bound to the scaffold, e.g. B.

• - 5-membered heteroaryl containing one to three nitrogen atoms: 5-ring heteroaryl groups, which in addition to carbon atoms contain one to three nitrogen atoms as ring members can, e.g. B. 2-pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl and 1,3,4-triazol-2-yl;
• - 5-membered heteroaryl containing one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or Oxygen atom or an oxygen or a sulfur atom: 5-ring heteroaryl groups, which in addition to carbon atoms one to four nitrogen atoms or one to three stick atoms of matter and a sulfur or oxygen atom or a May contain oxygen or sulfur atom as ring members NEN, e.g. B. 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2-pyrrolyl, 3-pyrrolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-iso thiazolyl, 4-isothiazolyl, 5-isothiazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,2,4-tri azol-3-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl, 1,3,4-triazol-2-yl;
• - Benzo-condensed 5-membered heteroaryl containing a up to three nitrogen atoms or one nitrogen atom and / or one Oxygen or sulfur atom: 5-ring heteroaryl groups, wel in addition to carbon atoms, one to four nitrogen atoms or one to three nitrogen atoms and one sulfur or acid substance atom or an oxygen or a sulfur atom as Ring members can contain, and which two adjacent Carbon ring members or a nitrogen and an adj  beard carbon ring member by a buta-1,3-diene-1,4-di yl group can be bridged;
• - Contain 5-membered heteroaryl bound via nitrogen tend one to four nitrogen atoms or over nitrogen bound benzo-fused 5-membered heteroaryl tend one to three nitrogen atoms: 5-ring heteroaryl groups, which besides carbon atoms one to four nitrogen atoms or contain one to three nitrogen atoms as ring members can, and in which two adjacent carbon ring limbs or a nitrogen and an adjacent coal ring member by a buta-1,3-diene-1,4-diyl group can be bridged, these rings over one of the stick fabric ring links are bound to the scaffold;
• - 6-membered heteroaryl containing one to three or one to four nitrogen atoms: 6-ring heteroaryl groups, which next to Carbon atoms one to three or one to four nitrogen may contain atoms as ring members, for. B. 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl;
• - Benzo-condensed 6-membered heteroaryl containing a up to four nitrogen atoms: 6-ring heteroaryl groups, in which Chen two adjacent carbon ring members by one Buta-1,3-diene-1,4-diyl group may be bridged, e.g. B. Quinoline, isoquinoline, quinazoline and quinoxaline,

or the corresponding oxy-, thio-, carbonyl- or sulfonyl groups.

The statement "partially or completely halogenated" is intended to end bring pressure that in the groups so characterized the Hydrogen atoms partially or completely by the same or ver different halogen atoms can be replaced as mentioned above nen.

Part of the invention include, in particular, Verbin in which the pharmacophore R¹ complies with (b), (c) and (d) groups mentioned. Such structures often have systemic properties.

Part of the invention are also ins special connections in which m = 0.  

Part of the invention are also ins special compounds in which R³ is C₁-C₄-alkyl, especially ethyl, Isopropyl, n-propyl and very particularly preferably methyl or cyclopropyl.

Part of the invention are also ins special compounds in which R⁴ is optionally substituted Alkyl, optionally substituted aryl, optionally Hetaryl, optionally substituted aralkyl or the group R⁵-Y-N = C (R⁶) - means.

The synthesis of the compounds of formula 1 according to the invention can carried out according to the synthesis steps given in Scheme 1 will.

The side chain is introduced by means of a nucleophilic substitution of X on the activated aromatic compound of a compound of formula 2 by the oxime 3 or its anion. The substitution reaction can be carried out under conditions customary for this type of reaction in the presence of a base and a suitable, preferably dipolar, aprotic solvent. Be noteworthy is the chemoselectivity under certain reaction conditions (see Preparation Examples), which does not affect the ester groups COOR³¹, wherein R³¹ is C₁-C₈-alkyl, preferably methyl, leads directly to keto esters 4. However, the reaction conditions can, if appropriate, also be chosen such that a further S _N reaction to the oxime ether-oxime ester 5 follows. 5 can then optionally be subjected to the further synthesis steps towards the end products of formula 1 (or 7 or 8) in an analogous manner to 4.

Fluorine is suitable as the nucleofugic leaving group X. but other groups such. B. triflate in question (X = CF₃SO₂O-). The Intermediate product of formula 2 according to the invention, in which X = F and R³¹ = CH₃, is based on the following, known synthesis Sequence produced (see manufacturing examples):

Scheme 2

Starting from 2, 4 or 5 are then produced. The in scheme 1 specified alkyl keto esters 4 and 5 or the oxime keto esters can then by aminolysis with ammonia or methylamine according to standard methods in the ketoamides of formula 7, in which R³² is hydrogen or methyl means to be converted.

By reaction with O-methylhydroxylamine according to standard methods This gives compounds 8 in which R³² is hydrogen or Is methyl and = U represents the group = N-OCH₃; these are then end products of formula 1c or 1b.

End products of the formula 1c or 1b can also be prepared by starting from 4 or 5, the order of the just ge called reaction steps interchanged. To do this, the first some keto function with O-methylhydroxylamine to oxime ether 6 or 6A, in which = U stands for = N-OCH₃, converted and then eating aminolyzed to 8.

End products of formula 1a are compounds of formula 6 in Scheme 1 in which R³¹ is methyl. You will be like already said by reacting keto esters of formula 4 in which R³¹ Methyl means made with O-methylhydroxylamine.

End products of formula 1d or 1e are by Wittig olefin tion according to standard methods from keto esters of formula 4 in which R³¹ Methyl means manufactured. Implementations with Wit tig reagents of the type H₃C-HC⊖-P⊕R₃ to the croton esters 1e and Wittig reagents of the type H₃CO-HC⊖-P⊕R₃ to the enol ethers 1d. Ana Logical implementations are in several patent applications on the Stro biluring area described (see e.g. EP-A 178 826, EP-A 280 185, EP-A 513 580).

For the individual steps in scheme 1, see also the manufacturer examples. The production of oximes of formula 3 is flat if described (see e.g. EP-A 370 629, EP-A 463 488, EP-A 460 575, WO-A 95/21154, WO-A 95/2/153, WO-A 95/18789).

Manufacturing examples 1. Preparation of the intermediate of formula 2 with X = F and R³¹ = CH₃

• a) For the suspension of 179 g of potassium cyanide in 500 ml of diethyl ether is first added dropwise with stirring at room temperature 171 g of 2-fluorobenzaldehyde, then with ice cooling in a solution of 148 g of ammonium chloride within 5 minutes  in 600 ml of water. After stirring for 2 h at room temperature the phases separated, the ether phase once with ver thinner NaCl solution and washed three times with H₂O, ge dries and evaporates. 191 g (91%) of oily are obtained Formula 9 product.
• b) 235 g of cyanohydrin 9 are in 1000 ml of diethyl ether and 100 g of methanol dissolved. To do this, use ice cooling within 15 min 126 g of a 55 percent. HCl solution added dropwise in ether (69 g HCl). After standing for 20 hours The precipitate is filtered off at room temperature and Blown nitrogen flow dry. Yield 108 g 10.
• c) The imino ester hydrochloride 10 (108 g) is half Heated in 450 ml of H₂O with stirring to reflux. After cooling, the mixture is extracted three times with ether Dried ether phase and concentrated. You get 77 g of 2-fluoromandelic acid methyl ester 11.
• d) To 77.1 g 11 in 700 ml CH₂Cl₂ there are 3.2 g KBr, 8.7 g Na₂HPO₄, 7.6 g NaH₂PO₄ · 2H₂O, 2.8 g 2,2,6,6-tetramethyl piperidine N-oxide and 600 ml of H₂O. About this mix are with stirring at 20 ° C within 1/2 h 343 g 12.5 percent NaOCl solution added dropwise. The mixture is stirred for 1 h continue. The organic phase is separated off, the water phase extracted once with CH₂Cl₂. The United organic phases are washed three times with H₂O, ge dries and evaporates. 72.3 g of the intermediate are obtained products of formula 2, in which X is fluorine and R³¹ methyl indicates: 2-fluorophenylglyoxalic acid methyl ester 1 H-NMR (CDCl₃): 3.97 (3H, s), 7.18 (1H, pseudotriplet), 7.32 (1H, Ps.-tr.), 7.67 (1H, m), 7.93 ppm (1H, further increased column Ps.-tr.).

2. Production of end products of formula 1

• a) For mixing 4.0 g of 3-methyl acetophenone oxime in 20 ml N, N-dimethylacetamide (DMA) is added at 20 ° C 3.0 g of potassium um-tert-butanolate, allowed to stir for 1/2 hour and dripped then at 15 ° C a mixture of 5.9 g of 2-fluorophenylglyoxal acid methyl ester in 20 ml of DMA. After 3 hours at 20 ° C is enough methyl tert-butyl ether and aqueous NH₄Cl solution added, the phases separated and the org. Phase washed three times with NH₄Cl solution, then dry net and constricted. This is obtained after column chromatography  4.1 g of ketoester of the formula 4 on silica gel with R³¹ = CH₃, R³ = CH₃ and R⁴ = 3-methylphenyl.
• b) 0.8 g of the keto ester thus prepared are in 7 ml CH₃OH with 0.24 g of o-methylhydroxylamine hydrochloride and 0.23 g pyridine stirred at 50 ° C for 1 hour. After that it will Methanol in vac. removed and the residue with vinegar acid ethyl ester added, with dil. HCl and then with Washed water, dried and concentrated. Raw yield 6.3 g, which gradually crystallize. After pillars chromatographic purification is isolated on the two ten fraction 2.2 g oxime ether of formula 6 with R³¹ = CH₃, R³ = CH₃ and R⁴ = 3-methylphenyl of mp. 90 ° C.
• c) 0.5 g of this oxime ether in 4 ml of THF are at reflux temperature in portions 2.9 ml 40 percent. aqueous methyla min solution added. The mixture continues overnight stirred, then i. Vac. concentrated, taken up in ethyl acetate men, washed with NaCl solution, dried and concentrated. 0.4 g of pale yellow crystals of mp 109-111 ° C. which according to 1 H-NMR and 13 C-NMR are the E / E isomers of formula 8 with R³² = CH₃, R³ = CH₃ and R⁴ = 3-methylphenyl.

3. Preparation of an intermediate of formula 4 and End products of formulas 6 (formulas 1a and 1c) and 8 (of formula 1b)

• a) Add 18.7 g of (E) -diacetylmonoxime in 100 ml of methanol 43.8 g of pyridine and then 17 g dropwise with stirring o-Methylhydroxylamine hydrochloride, dissolved in 50 ml metha nol too. After 3 hours, the mixture is evaporated to dryness, the residue taken up in ether and with dil. salt acid washed, then the ether phase dried and constricted. 24 g of E / E-2-methoximino-3-hydroximi are obtained nobutan.
• b) 2.3 g of the latter compound are added to 15 ml of DMA it is stirred with 2.0 g of potassium tert-butanolate for 1/2 hour and then drop 3 g of the above 2-fluorophenyl at 20 ° C glyoxalic acid methyl ester of formula 2 (X = F, R³¹ = CH₃), dissolved in 6 ml of DMA, taking the temperature through ice cooling is kept at 20 ° C. Then after 2 hours which further stirred. The reaction is worked up added mixture to NH₄Cl solution and the aqueous phase extracted several times with ether. The united organi phases are washed with ammonium chloride solution, dried and concentrated. 3.9 g of impure product are obtained  Product of the formula - (R³¹ = CH₃, R³ = CH₃, m = O, R⁴- = H₃CON = C (CH₃) -).
• c) 3 g of this crude product in 20 ml of methanol 0.83 g of o-methylhydroxylamine reacted at room temperature. After 3 hours the solvent i. Vac. dressed and the residue of column chromatography on silica gel with mobile phase cyclohexane / ethyl acetate 15: 1 subzo The second fraction was 1.3 g of a crystalline Substance isolated from mp. 93 ° C: compound of formula 1a with R³ = CH₃ and R⁴- = H₃CON = C (CH₃) -, E / E / E isomer, m = O.
• d) The latter compound (0.6 g) in 10 ml THF with 3.6 g 40 percent. aq. Methylamine solution overnight Room temperature stirred. After removing the THF i. Vac. and Adding water remained a crystalline precipitate, the suctioned off and in vac. dried (0.3 g, Mp 122-123 ° C): compound of formula 8 with R³² = CH₃, = U = NOCH₃, R³ = CH₃ and R⁴- = H₃CON = C (CH₃) -, E / E / E isomer, m = O.
• e) The crude product from preparation example 3.b), namely 2.4 g of which, dissolved in 10 ml of dimethylformamide (DMF), is to a mixture of 5.6 g methoxymethyltriphenylphospho nium chloride and 2.5 g 30 percent. Sodium methylate solution (in Methanol) in 20 ml of DMF. After 3 hours 30 ml of H₂O added dropwise with ice cooling and the resultant Suction filtered. After chromatography on SiO₂ with cyclohexane / ethyl acetate is isolated from the second Fraction a pale yellow solid, mp 94 ° C (1.8 g), that from the desired E / E / E isomer of the enol ether Formula 1d with m = O, R³ = CH₃ and R⁴- = H₃CON = C (CH₃) - be stands.

Preferred examples of compounds according to the invention Formula 1 are summarized in the following tables poses.

Table 1

Compounds of the general formula 1.1, in which (R²) _{m is} hydrogen and the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Table 2

Compounds of the general formula 1.2 in which (R²) _{m is} hydrogen and the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Table 3

Compounds of the general formula 1.3 in which (R²) _{m is} hydrogen and the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Table 4

Compounds of the general formula 1.4 in which (R²) _{m is} hydrogen and the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Table 5

Compounds of the general formula 1.5 in which (R²) _{m is} hydrogen and the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Preferred examples of intermediate pro Products of Formula 4.1 are shown in Table 6 below.

Table 6

Compounds of the general formula 4.1, in which R³¹ is methyl and (R²) _{m is} hydrogen and in which the combination of the substituents R³ and R⁴ for a compound corresponds in each case to one line of Table A.

Table A

Furthermore, those in Tables 7 to 21 below are together provided compounds of formula 1 with regard to their Use particularly preferred.

Table 7

Compounds of the general formula 1.7 in which (R²) _m is hydrogen and Y is oxygen and the combination of the substituents R³, R⁶ and R⁵ for a compound corresponds in each case to one line of Table B.

The substituents are in principle as set out in claim 1 Are defined; this also applies to the other tables.

Table 8

Compounds of the general formula 1.8 in which (R²) _{m is} hydrogen and Y is oxygen and the combination of the substituents R³, R⁶ and R⁵ for a compound corresponds in each case to one line of Table B.

Table 9

Compounds of the general formula 1.9 in which (R²) m is hydrogen and Y represents oxygen and the combination of the substituents R³, R⁶ and R⁵ each for a connection one line each Table B corresponds.

Table 10

Compounds of the general formula 1.10, in which (R²) _{m is} hydrogen and Y are oxygen and in which the combination of the substituents R³, R⁶ and R⁵ each represents a compound in each case one line of Table B.

Table 11

Compounds of the general formula 1.11, in which (R²) _{m is} hydrogen and Y are oxygen and in which the combination of the substituents R³, R⁶ and R⁵ each represents a compound in each case one line of Table B.

Table 12

Compounds of the general formula 1.2, those of formula 1.7 Table 7 corresponds, with the only difference that Y for NH instead of O.

Table 13

Compounds of the general formula 1.13, that of the formula 1.8 Table 8 corresponds, with the only difference that Y in each the individual compound stands for NH instead of O.

Table 14

Compounds of the general formula 1.14, which of the formula 1.9 Table 9 corresponds, with the only difference that Y in each the individual compound stands for NH instead of O.

Table 15

Compounds of the general formula 1.15, which corresponds to the formula 1.10 in Table 10, with the only difference that Y therein
15 and in each individual compound stands for NH instead of O.

Table 16

Compounds of the general formula 1.16; that of formula 1.11 the Table 11 corresponds, with the only difference that Y is in it and stands for NH instead of O in each individual compound.

Table 17

Compounds of the general formula 1.17, those of the formula 1.7 Table 7 corresponds, with the only difference that Y is in it and in each individual compound defined by Table B for N (CH₃) instead of O is.

Table 18

Compounds of the general formula 1.18, those of the formula 1.8 Table 8 corresponds, with the only difference that Y is in it and in each individual compound defined by Table B for N (CH₃) instead of O is.

Table 19

Compounds of the general formula 1.19, which of the formula 1.9 Table 9 corresponds, with the only difference that Y is in it and in each individual compound defined by Table B for N (CH₃) instead of O is.

Table 20

Compounds of the general formula 1.20, those of the formula 1.10 Table 10 corresponds, with the only difference that Y is in it and in each individual compound defined by Table B for N (CH₃) instead of O is.

Table 21

Compounds of the general formula 1.21, those of the formula 1.11 Table 11 corresponds, with the only difference that Y is in it and in each individual compound defined by Table B for N (CH₃) instead of O is.

Table 22

As intermediates according to the invention of the formula 4.2, in which (R²) _m denotes hydrogen and in which the combination of the substituents R³, R⁶ and R⁵ each stands for an individual compound in one row of table B and in which Y always stands for oxygen, the Compounds in Table 22 as they have just been defined.

Table 23

Intermediates of the general formula 4.3, those of the formula 4.2 corresponds to Table 22, with the only difference that Y therein and in each individual compound defined by Table B. represents NH instead of O.

Table 24

Intermediates of general formula 4.4, those of formula 4.2 corresponds to Table 22, with the only difference that Y therein and in each individual compound defined by Table B. represents N (CH₃) instead of O.

More synthesis examples

The regulations for the Synthesis examples have been modified accordingly Starting compounds for the production of further compounds of Formula 1 used. The compounds thus obtained are in the closing tables with physical information.

Table Ia

Compounds of formula 1a

Table Ib

Compounds of formula 1b

Table Id

Compounds of formula 1d

Table if

Compounds of formula 4 in which R³¹ is methyl (keto esters as intermediates)

Mitochondrial respiratory inhibitors of Mushrooms can be used as fungicides, e.g. B. Antimycin (see U.S. Rieske in: M. Erecinska, D.F. Wilson (ed.), "Inhibitors of Mitochondrial Function", Pergamon Press, Oxford, 1981, p. 110). The practical application of antimycin are available but various drawbacks in the way, e.g. B. the difficult and on agile manufacturing and insufficient stability under the conditions of outdoor use.

Compounds 1 according to the invention inhibit mitochondrial Respiration of mushrooms (see examples of effects) and can be used as a fungi zide can be used.

Mitochondrial respiration is essential for the metabolism. In The mitochondria is used to breathe energy in the form of Adenosine triphosphate (ATP) stored. Inhibition of breathing mitochondrial respiratory inhibitors ultimately leads to inhibition of ATP formation. This makes it z. B. in mushrooms with the Phenylacetic acid derivatives according to the invention were treated for Succumb to ATP or energy dependent metabolic processes and thus stagnating growth or dying.

In addition, the compounds of the invention can also be used as Animal or human antifungals are used because the mito chondrial respiration of animal pathogenic or human pathogenic fungi is inhibited. Some of the compounds also show activity against Insects and spider mites, since the mito chondrial breathing is inhibited.  

Effect example Effect of the compounds as inhibitors of mitochondrial At mung

To the effect of the compounds of the invention on the mito To determine chondrial respiration, the mitochondria must first be determined be isolated from the organisms to be examined. To do this in the case of the yeast Saccharomyces cerevisiae a 30 to 40% cell suspension of the fungus in an aqueous solution of 0.6 M mannitol + 0.01 M tris [hydroxymethyl] aminomethane + 0.002 M Ethylene diamine tetraacetic acid disodium salt (pH 6.8) with a Glass ball mill unlocked and the extract by differen fractional centrifugation at 1000 × g and 12000 × g. The mitochondria are in the precipitate of the 12000 × g centrifugation.

Similarly, mitochondria can be isolated from other fungi the, e.g. B. from the phytopathogenic fungus Drechslera sorokiniana (synonym Helminthosphorium sativum), from the human pathogenic Dermatophyte Trichophyton mentagrophytes as well as from other organs nisms, e.g. B. from the housefly (musca domestica) as an insect or from the spider mite Tetranychus urticae.

The effect of the compounds on the respiratory chain is determined by adding to a suspension of mitochondria in an aqueous solution of 0.01 M tris [hydroxymethyl] aminomethane + 0.65 M sorbitol + 0.01 M KH₂PO₄ + 0.01 M KCl + 0.0004 M ethylenediaminetetraacetic acid disodium salt + 0.3% bovine serum albumin + 0.0007 M KCN + 6 × 10 ^-6 ubiquinone-50 + 0.01 M Na succinate + 0.15% cytochrome c (pH 7.5) a solution of the compound to be investigated is given in dimethyl sulfoxide and the rate of reduction of the cytochrome c is determined photometrically on the basis of the increase in extinction at 546 nm. A batch with the corresponding amount of pure DMSO serves as a control. The inhibitory value for the active substance concentration specified in each case is then calculated as follows.

where ΔE is the change in extinction, Δt is the change in time,

The following table shows for a number of the invention Compounds whose effect as a respiratory inhibitor on the mitochon three of the yeast Saccharomyces cerevisiae, the phyto pathogenic fungus Drechslera sorokiniana and the house fly musca domestica.

The inhibition of mitochondrial respiration is in each case as I₅₀ value given (this is the concentration of test substance, at which 50% inhibition occurs) and as an F value, this is a rela tive value, which is defined as follows:

The standard substance is the so-called enol ether stilbene with fol gender formula:

It runs with every test for standardization.  

Table II

Inhibition of mitochondrial respiration by compounds of formula 1 from Tables Ia-Id

The compounds 1 are suitable as fungicides. You stand out due to good tolerance for plants and other non-target organisms out.

The compounds 1 are distinguished by an excellent action against a wide range of phytopathogenic fungi, especially from the class of Ascomycetes and Basidiomycetes, out. Some of them are systemically effective and can be used as leaf and Soil fungicides are used.

They are particularly important for combating a large number of mushrooms on various crops such as wheat, rye, Barley, oats, rice, corn, grass, cotton, soy, coffee, sugar pipe, wine, fruit and ornamental plants and vegetables such as cucumbers, Beans and pumpkin plants, as well as on the seeds of these plants.

They are particularly suitable for combating the following plant diseases units: Erysiphe graminis (powdery mildew) in cereals, Erysiphe cichoracearum and Sphaerotheca fuliginea on squash, Podosphaera leucotricha on apples, Uncinula necator on vines, Puccinia species on cereals, Rhizoctonia species on cotton and Lawn, Ustilago species on cereals and sugar cane, Venturia inaequalis (scab) on apples, Helminthosporium species on Ge Treide, Septoria nodorum on wheat, Botrytis cinerea (gray chim mel) on strawberries, vines, Cercospora arachidicola on peanuts, Pseudocercosporella herpotrichoides on wheat, barley, Pyricularia oryzae on rice, Phytophthora infestans on potatoes and tomatoes, Fusarium and Verticillium species on various Plants, Plasmopara viticola on vines, Alternaria species on Ge vegetables and fruit.  

Compounds 1 are applied by using the mushrooms or the plants, seeds, materia to be protected from fungal attack lien or the soil with a fungicidally effective amount of Active substances treated. The application takes place before or after the In fection of materials, plants or seeds by fungi.

They can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The form of application depends on the respective purpose; in any case, it should ensure a fine and uniform distribution of the ortho-substituted benzyl ester of a cyclopropanecarboxylic acid. The formulations are prepared in a known manner, e.g. B. by stretching the active substance with solvents and / or carriers, if desired using emulsifiers and dispersants, and in the case of water as a diluent other organic solvents can also be used as auxiliary solvents. The following are essentially considered as auxiliary substances:
Solvents such as aromatics (e.g. xylene), chlorinated aromatics (e.g. chlorobenzenes), paraffins (e.g. petroleum fractions), alcohols (e.g. methanol, butanol), ketones (e.g. cyclohexanone), Amines (e.g. ethanolamine, dimethylformamide) and water; Carriers such as natural rock powder (e.g. kaolins, clays, talc, chalk) and synthetic rock powder (e.g. highly disperse silica, silicates); Emulsifiers such as nonionic and anionic emulsifiers (e.g. polyoxyethylene fatty alcohol ether alkyl sulfonates and aryl sulfonates) and dispersants such as lignin sulfite waste liquors and methyl cellulose.

The fungicidal compositions generally contain between 0.1 and 95, preferably between 0.5 and 90% by weight of active ingredient.

The application rates depend on the type of effect desired between 0.01 and 2.0 kg of active ingredient per ha.

When treating seeds, amounts of active ingredient are generally used from 0.001 to 0.1 g, preferably 0.01 to 0.05 g per kilogram Seed needed.

The agents according to the invention can be used as Fungicides are also present together with other active ingredients e.g. B. with herbicides, insecticides, growth regulators, Fungicides or with fertilizers.

When mixed with fungicides you get in many cases an increase in the fungicidal spectrum of activity.  

The following list of fungicides with which the compounds according to the invention can be used together is intended to explain, but not to limit, the possible combinations:
Sulfur, dithiocarbamates and their derivatives, such as ferridimethyl dithiocarbamate, zinc dimethyldithiocarbamate, zinc ethylene bisdithio carbamate, manganese ethylene bisdithiocarbamate, manganese-zinc-ethylene diamine-bis-dithiocarbamate, tetramethylthiuram disulfide, zinc ammonium, ammonia-bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) bis (ammonia) and ammonium bis (ammonia) bis (ammonia) bis (ammonia) bis (n) - Complex of zinc (N, N'-propylene-bis-dithiocarbamate), zinc (N, N'-propylene-bis-dithiocarbamate), N, N'-polypropylene bis- (thiocarbamoyl) disulfide;
Nitroderivatives such as dinitro- (1-methylheptyl) phenyl crotonate, 2-sec-butyl-4,6-dinitrophenyl-3,3-dimethylacrylate, 2-sec-butyl-4,6-dinitrophenyl-isopropyl carbonate, 5-nitro-isophthalate acid di-isopropyl ester;
heterocyclic substances such as 2-heptadecyl-2-imidazoline acetate, 2,4-dichloro-6- (o-chloroanilino) -s-triazine, O, O-diethyl-phthalimidophosphonothioate, 5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole, 2,3-dicyano-1,4-dithioanthraquinone, 2-thio-1,3-dithiolo [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazole-carbamic acid methyl ester, 2-methoxycarbonylamino-benz imidazole, 2- (furyl- (2)) -benzimidazole, 2- (thiazolyl- (4)) -benzimidazole, N- (1, 1,2,2-tetrachloroethylthio) tetrahydrophthalimide, N-trichloromethylthio-tetrahydrophthalimide, N-trichloromethylthio phthalimide,
N-dichlorofluoromethylthio-N ′, N′-dimethyl-N-phenylsulfuric acid diamide, 5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole, 2-rhodanemethylthiobenzothiazole, 1,4-dichloro-2,5- dimethoxybenzene, 4- (2-chlorophenylhydrazono) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide, 8-hydroxyquinoline or its copper salt, 2,3-dihydro-5-carboxanilido-6-methyl- 1,4-oxathiin, 2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin-4,4-dioxide, 2-methyl-5,6-dihydro-4H-pyran-3-carboxylic acid- anilide, 2 methyl-furan-3-carbon acid anilide, 2,5-dimethyl-furan-3-carboxylic acid anilide, 2,4, 5-tri methyl-furan-3-carboxylic acid anilide, 2,5-dimethyl-furan-3-carbon Acid cyclohexylamide, N-cyclohexyl-N-methoxy-2,5-dimethyl-furan-3-carboxamide, 2-methyl-benzoic acid anilide, 2-iodo-benzoic acid anilide, N-formyl-N-morpholine-2,2 , 2-trichloroethyl acetal, piperazin-1,4-diylbis- (1- (2,2,2-trichloro-ethyl) -formamide, 1- (3,4-dichloroanilino) -1-formylamino-2,2,2- trichloroethane, 2,6-dimethyl-N-tridecyl-morpholine or its salts, 2,6-dimethyl-N-cycl ododecyl morpholine or its salts, N- [3- (p-tert-butylphenyl) -2-methylpropyl] cis-2,6-dimethyl morpholine, N- [3- (p-tert-butylphenyl) - 2-methylpropyl] piperidine, 1- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-yl-ethyl] -1H- 1,2,4-triazole, 1- [ 2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan- 2-yl-ethyl] -1H-1,2,4-triazole, N- (n-propyl) -N- ( 2,4,6-trichlorophenoxyethyl) -N'-imidazol-yl urea, 1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) - 3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanol, α- (2-chlorophenyl) - α- (4-chlorophenyl) -5-pyrimidine-methanol, 5-butyl-2-dimethylamino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol, 1,2-bis- (3-ethoxycarbonyl-2-thioureido) benzene, 1,2-bis (3-methoxycarbonyl-2-thioureido) benzene,
as well as various fungicides, such as dodecylguanidine acetate, 3- [3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene, DL-methyl-N- (2,6-dimethyl-phenyl) -N -furoyl (2) - alaninate, DL-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) -alanine methyl ester, N- (2,6-dimethylphenyl) -N-chloroacetyl- D, L-2-amino butyrolactone, DL-N- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine methyl ester, 5-methyl-5-vinyl-3- (3,5-dichlorophenyl) -2, 4-dioxo-1,3-oxazolidine, 3- [3,5-dichlorophenyl (-5-methyl-5-methoxymethyl] - 1,3-oxazolidine-2,4-dione, 3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin, N- (3,5-dichlorophenyl) -1,2-dimethylcyclopropane-1,2-dicarboximide, 2-cyano- [N- (ethylaminocarbonyl) -2-methoximino] acetamide, 1- [ 2- (2,4-dichlorophenyl) pentyl] -1H-1,2,4-tri azole, 2,4-difluoro-α- (1H-1,2,4-triazolyl-1-methyl) benzhydric alcohol , N- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5- trifluoromethyl-3-chloro-2-aminopyridine, 1 - ((bis- (4-fluorophenyl) methylsilyl) methyl) -1H-1,2,4-triazole.

The compounds of formula 1 are also suitable for pests effective from the class of insects, arachnids and nematodes to fight. You can in crop protection as well as on the Hygiene, storage protection and veterinary sector as a pest pesticides are used.

The harmful insects belong to the order of the Shmet terlings (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta  malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris brassicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparga nothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusiani, Zeiraphera canadensis.

From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.

From the order of the two-winged birds (Diptera), for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthro pophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata,  Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, tipula paludosa.

From the order of the thrips (Thysanoptera) for example Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

From the order of the hymenoptera, for example Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.

From the order of the bugs (Heteroptera), for example, Acroster num hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euschistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.

From the order of the plant suckers (Homoptera), for example Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nord mannianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.

From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.

From the order of the straight wing aircraft (Orthoptera) for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migrato ria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.  

Arachnoid, for example, arachnids (Acarina) such as Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobius megnini, Paratetranychus pilosus, Dermanyssus gallinae, Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetra nychus urticae.

From the class of nematodes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cyst-forming nematodes, e.g. B. Globodera rostochiensis, heterodera avenae, heterodera glycines, heterodera schachtii, Heterodera trifolii, stick and leaf whale, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.

The active ingredients as such, in the form of their formulations or the application forms prepared from it, e.g. B. in the form of directly sprayable solutions, powders, suspensions or Dispersions, emulsions, oil dispersions, pastes, dusts, Scattering agents, granules by spraying, atomizing, dusting, Scatter or pour. The application forms depend entirely on the purposes; they should be in in any case, the finest possible distribution of the invention Ensure active ingredients.

The drug concentrations in the ready-to-use Preparations can be varied in larger areas.

Generally they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume process (ULV) can be used, it is possible to use form with more than 95% by weight of active ingredient or even the active ingredient without applying additives.  

The amount of active ingredient used to control pests is 0.1 to 2.0, preferably in the field 0.2 to 1.0 kg / ha.

For the production of directly sprayable solutions, emulsions, Pastes or oil dispersions come from mineral oil fractions medium to high boiling point such as kerosene or diesel oil Coal tar oils as well as oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, ethanol, Propanol, butanol, chloroform, carbon tetrachloride, cyclo hexanol, cyclohexanone, chlorobenzene, tsophorone, strongly polar Solvents, e.g. B. dimethylformamide, dimethyl sulfoxide, N-methyl pyrrolidone, water.

Aqueous application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) Water can be added. For the production of emulsions NEN, pastes or oil dispersions can the substances as such or dissolved in an oil or solvent, using wetting, adhesive, Dispersants or emulsifiers are homogenized in water. However, wetting, adhesive, Dispersing or emulsifying agent and possibly solvent or Oil existing concentrates are made for dilution are suitable with water.

Alkali, alkaline earth, Ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, Phenolsulfonic acid, dibutylnaphthalenesulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and Fatty acids and their alkali and alkaline earth salts, salts of sulfated fatty alcohol glycol ether, condensation products from sulfonated naphthalene and naphthalene derivatives with formaldehyde, Condensation products of naphthalene or naphthalene sulfone acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkyl phenol polyglycol ether, tributylphenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide Condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite liquor and methyl cellulose into consideration.  

Powders, materials for spreading and dusts can be mixed or joint grinding of the active substances with a solid Carrier are manufactured.

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are:

• I. 5 parts by weight of a compound according to the invention 95 parts by weight of finely divided kaolin intimately mixed. Man receives a dusting agent that contains 5% by weight of the Contains active ingredient.
• II. 30 parts by weight of a compound according to the invention are with a mixture of 92 parts by weight of powdered pebble acid gel and 8 parts by weight of paraffin oil, which on the upper surface of this silica gel was sprayed intimately mixes. In this way, a preparation of the Active ingredient with good adhesiveness (active ingredient content 23% by weight).
• III. 10 parts by weight of a compound according to the invention are in dissolved a mixture consisting of 90 parts by weight of xylene, 6 parts by weight of the adduct of 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of Addition product of 40 moles of ethylene oxide with 1 mole Castor oil consists (active ingredient content 9% by weight).
• IV. 20 parts by weight of a compound according to the invention are in dissolved a mixture consisting of 60 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 5 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil (active ingredient content 16% by weight).
• V. 80 parts by weight of a compound of the invention 3 parts by weight of the sodium salt of diisobutylnaphthalene alpha-sulfonic acid, 10 parts by weight of the sodium salt Lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight powdered silica gel well mixed and in one Hammer mill ground (active ingredient content 80% by weight).  
• VI. 90 parts by weight of a Ver according to the invention are mixed bond with 10 parts by weight of N-methyl-α-pyrrolidone and receives a solution for use in the form of tiny drops is suitable (active ingredient content 90% by weight).
• VII. 20 parts by weight of a compound according to the invention are described in dissolved a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the addition product of 7 moles of ethylene oxide with 1 mole of isooctylphenol and 10 parts by weight of the adduct of 40 moles of ethylene oxide on 1 mole of castor oil. By pouring and fine Distribute the solution in 100,000 parts by weight of water an aqueous dispersion containing 0.02% by weight of the active ingredient contains.
• VIII. 20 parts by weight of a compound according to the invention are with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α- sulfonic acid, 17 parts by weight of the sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 60 parts by weight powdered silica gel well mixed and in one Grind hammer mill. By finely distributing the mixture a spray mixture is obtained in 20,000 parts by weight of water, which contains 0.1% by weight of the active ingredient.

Granules, e.g. B. wrapping, impregnation and homogeneous granules, by binding the active ingredients to solid carriers fabrics are made. Solid carriers are e.g. B. Mineral earth, such as silica gel, silicas, silica gels, silicates, talc, Kaolin, Attaclay, limestone, lime, chalk, bolus, loess, clay, Dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide, ground plastics, fertilizers, such as. B. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas and plant Liche products such as flour, tree bark, wood and nut shell flour, cellulose powder and other solid carriers.

Various types of oils, herbicides, Fungicides, other pesticides, bactericides, if necessary, only immediately before use (tank mix), be added. These agents can be added to those of the invention Agents are mixed in a weight ratio of 1:10 to 10: 1.  

Examples of the action against harmful fungi

The fungicidal activity of the compounds of the general formula 1 was shown by the following experiments:

The active ingredients were made up as a 20% emulsion in a mixture 70% by weight cyclohexanone, 20% by weight Nekanil® LN (Lutensol® AP6, Wetting agent with an emulsifying and dispersing effect on the base ethoxylated alkylphenols) and 10% by weight Emulphor®EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols) processed and in accordance with the desired concentration Diluted water.

1. Erysiphe graminis var. Tritici

Leaves of wheat seedlings (variety "Chancellor") were first with the aqueous preparation of the active ingredients (containing 250 ppm) treated. After about 24 hours, the plants were covered with spores of the Wheat powdery mildew (Erysiphe graminis var. Tritici) pollinated. The so Treated plants were then at 20-22 ° C for 7 days and a relative humidity of 75-80%. The extent of fungal development was then determined.

In this test, those with the compounds according to the invention were shown treated plants an infestation of 15% and less that with a known active ingredient (Compound No. 195, Table 3, EP-A 463 488) treated plants 40% infestation and the unbe plants traded 70% infestation.

In a corresponding test (wheat seedlings of the variety "Chancellor", application rate 63 ppm), at which the plants first were infected and incubated and then with the drug substances treated with those according to the invention showed Compounds treated plants with an infestation of 5% and less with a known active ingredient (Compound No. 195, Table 3, EP-A 463 488) treated plants 25% and the untreated plants 60% infestation.

Examples of action against animal pests

The insecticidal activity of the compounds of the general formula 1 was shown by the following experiments:  

The active ingredients were

• a) as a 0.1% solution in acetone or
• b) as a 10% emulsion in a mixture of 70% by weight cyclo hexanol, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with Emulsifying and dispersing action based on ethoxylated Alkylphenols) and 10% by weight Emulphor®EL, emulsifier on the Based on ethoxylated fatty alcohols)

processed and in accordance with the desired concentration Dilute acetone in the case of a) or with water in the case of b).

After the end of the tests, the lowest concentration was obtained tration determined in which the connections compared to unbe control attempts were still 80-100% inhibition or Cause mortality (threshold of action or minimum concentration).

Claims (22)

1. Phenylacetic acid derivatives of the general formula 1 in which the substituents and the index have the following meanings: R² cyano, nitro, trifluoromethyl, halogen, C₁-C₄ alkyl or C₁-C₄ alkoxy;
m is 0, 1 or 2, it being possible for the radicals R 2 to be different if m is 2;
R³ is hydrogen, hydroxy, cyclopropyl, halogen, C₁-C₄ alkyl, cyano, C₁-C₄ alkoxy or C₁-C₄ alkylthio;
R⁴ C₁-C₈-alkyl, C₂-C₈-alkenyl, C₂-C₈-alkynyl, C₃-C₈-cyclo alkyl, aryl or hetaryl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: cyano , Nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino thiocarbonyl, halogen, C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁ -C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxy carbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl, di-C₁-C₆- alkylaminocarbonyl- C₁-C₆-alkylaminothiocarbonyl- di-C₁-C₆-alkylaminothiocarbonyl- C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, and hetaryloxy
or the group R⁵-YN = C (R⁶) -, in which
R⁵ is hydrogen or C₁-C₁₀-alkyl, C₃-C₆-cycloalkyl, C₂-C₁₀-alkenyl, C₃-C₁₀-alkynyl, C₁-C₁₀-alkyl carbonyl, C₂-C₁₀-alkenylcarbonyl, C₃-C₁₀-alkynyl carbonyl or C₁ -C₁₀-alkylsulfonyl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, amino-thiocarbonyl, halogen, C₁-C₆- Alkyl, C₁-C₆-haloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxy, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkylthio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylamino carbonyl, C₁-C₆-alkylaminothiocarbonyl, di-C₁-C₆-alkylaminothiocarbonyl- C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, arylthio, hetaryl, hetaryloxy and hetarylthio, the aromatic and he teroaromatic radicals can be partially or completely halogenated and / or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, halogen, aminothiocarbonyl, C₁-C₆-alkyl, C₁- C₆-haloalkyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkyloxycarbonyl, C₁-C₆-alkylthio, C₁-C₆- Alkylamino, di-C₁-C₆-alkyl amino, C₁-C₆-alkylaminocarbonyl, di-C₁-C₆-alkylamino carbonyl, C₁-C₆-alkylaminothiocarbonyl, di-C₁ C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy , Benzyl, Benzyloxy, Aryl, Aryloxy, Arylthio, Hetaryl, Hetaryloxy, Hetarylthio or C (= NOR⁷) -A _n -R⁸ or
Aryl, hetaryl, arylcarbonyl, hetarylcarbonyl, aryl sulfonyl or hetarylsulfonyl, where these groups can be partially or completely halogenated or can carry one to three of the following groups: cyano, nitro, hydroxy, mercapto, amino, carboxyl, aminocarbonyl, aminothiocarbonyl, halogen , C₁-C₆-alkyl, C₁-C₆-halogeno alkyl, C₁-C₆-alkylcarbonyl, C₁-C₆-alkylsulfonyl, C₁-C₆-alkylsulfoxyl, C₃-C₆-cycloalkyl, C₁-C₆-alkoxy, C₁-C₆-haloalkoxy, C₁-C₆-alkoxycarbonyl, C₁-C₆-alkyl thio, C₁-C₆-alkylamino, di-C₁-C₆-alkylamino, C₁-C₆-alkyl aminocarbonyl, di-C₁-C₆-alkylaminocarbonyl, C₁-C₆-alkyl aminothiocarbonyl, di -C₁-C₆-alkylaminothiocarbonyl, C₂-C₆-alkenyl, C₂-C₆-alkenyloxy, benzyl, benzyloxy, aryl, aryloxy, hetaryl, hetaryloxy or C (= NOR⁷) -A _n -R⁸,
in which
A represents oxygen, sulfur or nitrogen and the nitrogen carries hydrogen or C₁-C₆-alkyl;
n 0 or 1;
R⁷ is hydrogen or C₁-C₆ alkyl and
R⁸ is hydrogen or C₁-C₆-alkyl,
and in which
R⁶ has hydrogen, hydroxy, halogen or one of the meanings given for R³
and
Y represents O or NR⁹, where R⁹ is hydrogen or C₁-C₆-alkyl,
as well as their salts. 2. Compounds of formula 1 according to claim 1, in which m is 0 stands. 3. Compounds of formula 1 according to claim 1, in which the Pharmacophore R1 for those given as 1a, 1b, 1c and 1d Groups stands. 4. Compounds of formula 1 according to claim 1, in which the Pharmacophore R1 represents the group indicated as 1b. 5. Compounds of formula 1 according to claim 1, in which R¹ is the group given as 1d stands. 6. Compounds of formula 1 according to claim 1, in which R³ C₁-C₄ alkyl means. 7. Compounds of formula 1 according to claim 1, in which R³ Methyl means. 8. Compounds of formula 1 according to claim 1, in which R⁴ gege optionally substituted C₁-C₄ alkyl means. 9. Compounds of formula 1 according to claim 1, in which R⁴ gege also means substituted aryl. 10. Compounds of formula 1 according to claim 9, in which the ge optionally substituted aryl is 3-substituted phenyl. 11. Compounds of formula 1 according to one of claims 8 to 10, in which R³ means methyl. 12. Compounds of formula 1 according to claim 1, in which R⁴- the Group R⁵-Y-N = C (R⁶) - means with R⁵, R⁶ and Y as in the Be spelling defined. 13. Compounds of formula 1 according to claim 12, in which Y is Oxygen and R⁵ for methyl, ethyl, allyl or propargyl stands. 14. Compounds of formula 1 according to claim 13, in which R³ Methyl means. 15. Containing agents against animal pests or harmful fungi usual additives and an effective amount of a compound of formula 1 according to claim 1.   16. Composition according to claim 1 for controlling animal pests from the class of insects, arachnids or nematodes. 17. Procedures for controlling animal pests or Harmful fungi, characterized in that the pests or harmful fungi, their habitat or that of them freely plants, surfaces, materials or rooms with a effective amount of a compound of formula 1 according to An spell 1 treated. 18. Use of the compounds 1 according to claim 1 for the manufacture treatment of agents against animal pests or harmful fungi. 19. Use of the compounds 1 according to claim 1 for combating of animal pests or harmful fungi. 20. Intermediates of formula 4 for the preparation of compounds of formula 1 wherein in formula 4 R³¹ is C₁-C₈-alkyl and R², R³, R⁴ and m have the meanings given above. 21. Intermediates of Formula 2A in which X represents fluorine or another nucleofugic leaving group and R², R³¹ and m have the meanings given above. 22. Intermediates of formula 2A according to claim 21, in which X Fluorine, R³¹ is methyl or ethyl and R² is hydrogen.