DE10239481A1 - New 1-(heterocyclyl-carbonylamino)-cyclopropane-carboxylic acid derivatives, useful as microbicides, especially fungicides or bactericides for protection of plants or materials such as wood - Google Patents

Abstract

1-((Halo-heterocyclyl)-carbonylamino)-cyclopropane-1-carboxylic acid esters and amides (I) are new. Cyclopropane derivatives of formula (I) are new. G = halo-substituted 5- or 6-membered heterocyclyl; R = OR1, NHR2, NR3R4 or optionally substituted N-bonded, nitrogen-containing saturated heterocyclyl; R1 - R4 = alkyl, alkenyl, alkynyl, cycloalkyl, aryl or aralkyl (all optionally substituted). Independent claims are included for: (1) the preparation of (I); (2) new carboxylic acid intermediates of formula (IV); and (3) the preparation of (IV).

Description

The present invention relates to new heterocyclylcarbonylaminocyclopropanecarboxylic acid derivatives, several processes for their manufacture and their use in combating undesirable Microorganisms.

It has already become known that numerous acrylaminocyclopropanecarboxylic acid derivatives have fungicidal properties (cf. DE-A 35 39 307 . DE-A 195 44 674 and WO 01-12 587).

The effectiveness of those described there Fabrics is good, lets but in some cases leaves something to be desired at low application rates.

in welcher
G für halogensubstituiertes fünf- oder sechsgliedriges Heterocyclyl steht und
R für eine Gruppe -O-R¹, -NH-R² oder

steht oder für einen gegebenenfalls substituierten, gesättigten N-Heterocyclyl-Rest steht, der über Stickstoff mit der Carbonylgruppe verbunden ist, wobei
R¹, R², R³ und R⁴ unabhängig voneinander für gegebenenfalls substituiertes Alkyl, gegebenenfalls substituiertes Alkenyl, gegebenenfalls substituiertes Alkinyl, gegebenenfalls substituiertes Cycloalkyl, gegebenenfalls substituiertes Aryl oder für gegebenenfalls substituiertes Aralkyl stehen,
gefunden.There have now been new heterocyclylcarbonylaminopropanecarboxylic acid derivatives of the formula

in which
G represents halogen-substituted five- or six-membered heterocyclyl and
R for a group -OR ¹ , -NH-R ² or

stands for an optionally substituted, saturated N-heterocyclyl radical which is connected to the carbonyl group via nitrogen, where
R ¹ , R ² , R ³ and R ⁴ independently of one another represent optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl or for optionally substituted aralkyl,
found.

• a) Aminocyclopropancarbonsäureester der Formel
  
  in welcher R¹ die oben angegebene Bedeutung hat, bzw. deren Hydrohalogenide oder Hydrogensulfate mit Säurehalogeniden der Formel
  
  in welcher X für Halogen steht und G die oben angegebene Bedeutung hat, gegebenenfalls in Gegenwart eines Verdünnungsmittels und gegebenenfalls in Gegenwart eines Säurebindemittels umsetzt, oder
• b) Acylaminocyclopropancarbonsäuren der Formel
  
  in welcher G die oben angegebene Bedeutung hat, mit Verbindungen der Formel R-H (V) in welcher R die oben angegebene Bedeutung hat, in Gegenwart eines Kondensationsmittels und gegebenenfalls in Gegenwart eines Verdünnungsmittels sowie gegebenenfalls in Gegenwart eines Katalysators umsetzt.

It has furthermore been found that heterocyclylcarbonylaminocyclopropanecarboxylic acid derivatives of the formula (I) are obtained when

• a) Aminocyclopropane carboxylic acid esters of the formula
  
  in which R ^{1 has} the meaning given above, or their hydrohalides or hydrogen sulfates with acid halides of the formula
  
  in which X represents halogen and G has the meaning given above, if appropriate in the presence of a diluent and if appropriate in the presence of an acid binder, or
• b) acylaminocyclopropanecarboxylic acids of the formula
  
  in which G has the meaning given above, with compounds of the formula RH (V) in which R has the meaning given above, in the presence of a condensing agent and, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a catalyst.

Eventually it was found that the new heterocyclylcarbonylaminocyclopropanecarboxylic acid derivatives of the formula (I) have very good microbicidal properties and both in crop protection and in material protection to combat unwanted Microorganisms can be used. The substances according to the invention can not only be used to combat unwanted Use microorganisms, but also practice one on plants resistance-inducing effect.

Surprisingly show the heterocyclylcarbonylaminocyclopropanecarboxylic acid derivatives according to the invention the formula (I) a much better fungicidal activity than the most constitutionally similar, known Active substances with the same direction of action.

steht, worin
R¹ für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkyl mit 1 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkenyl mit 2 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkinyl mit 2 bis 8 Kohlenstoffatomen steht, oder
für gegebenenfalls durch Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Cycloalkyl mit 3 bis 8 Kohlenstoffatomen steht, oder
für Aryl mit 6 oder 10 Kohlenstoffatomen oder für Aralkyl mit 6 oder 10 Kohlenstoffatomen im Arylteil und 1 bis 4 Kohlenstoffatomen im Alkylteil steht, wobei diese Reste jeweils im Arylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Halogen, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl;
jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Haloenalkylsulfinyl oder Halogenalkylsulfonyl mit
jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkylcarbonyloxy, Alkoxycarbonyl, Hydroximinoalkyl oder Alkoximinoalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen oder
Cycloalkyl mit 3 bis 6 Kohlenstoffatomen,
oder die Aryl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Alkylen mit 3 bis 4 Kohlenstoffatomen oder Dioxyalkylen mit 1 oder 2 Kohlenstoffatomen, wobei diese Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein können durch Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 4 Kohlenstoffatomen und 1 bis 9 gleichen oder verschiedenen Halogenatomen,
R² für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkyl mit 1 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkenyl mit 2 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkinyl mit 2 bis 8 Kohlenstoffatomen steht, oder
für gegebenenfalls durch Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Cycloalkyl mit 3 bis 8 Kohlenstoffatomen steht, oder
für Aryl mit 6 oder 10 Kohlenstoffatomen oder für Aralkyl mit 6 oder 10 Kohlenstoffatomen im Arylteil und 1 bis 4 Kohlenstoffatomen im Alkylteil steht, wobei diese Reste jeweils im Arylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Halogen, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl;
jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkylcarbonyloxy, Alkoxycarbonyl, Hydroximinoalkyl oder Alkoximinoalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen oder
Cycloalkyl mit 3 bis 6 Kohlenstoffatomen,
oder die Arylreste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Alkylen mit 3 oder 4 Kohlenstoffatomen oder Dioxyalkylen mit 1 oder 2 Kohlenstoffatomen, wobei diese Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein können durch Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 4 Kohlenstoffstoffaromen und 1 bis 9 gleichen oder verschiedenen Halogenatomen,
und
R³ und R⁴ unabhängig voneinander für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkyl mit 1 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkenyl mit 2 bis 8 Kohlenstoffatomen, für gegebenenfalls durch Alkoxy mit 1 bis 4 Kohlenstoffatomen substituiertes Alkinyl mit 2 bis 8 Kohlenstoffatomen stehen, oder
für gegebenenfalls durch Alkyl mit 1 bis 4 Kohlenstoffatomen substituiertes Cycloalkyl mit 3 bis 8 Kohlenstoffatomen stehen, oder für Aryl mit 6 oder 10 Kohlenstoffatomen oder für Aralkyl mit 6 oder 10 Kohlenstoffatomen im Arylteil und 1 bis 4 Kohlenstoffatomen im Alkylteil stehen, wobei diese Reste jeweils im Arylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Halogen, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl;
jeweils geradkettiges oder verzweigtes Alkyl, Alkoxy, Alkylthio, Alkylsulfinyl oder Alkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Alkenyl oder Alkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen;
jeweils geradkettiges oder verzweigtes Halogenalkyl, Halogenalkoxy, Halogenalkylthio, Halogenalkylsulfinyl oder Halogenalkylsulfonyl mit jeweils 1 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Halogenalkenyl oder Halogenalkenyloxy mit jeweils 2 bis 6 Kohlenstoffatomen und 1 bis 13 gleichen oder verschiedenen Halogenatomen;
jeweils geradkettiges oder verzweigtes Alkylamino, Dialkylamino, Alkylcarbonyl, Alkylcarbonyloxy, Alkoxycarbonyl, Hydroximinoalkyl oder Alkoximinoalkyl mit jeweils 1 bis 6 Kohlenstoffatomen in den einzelnen Alkylteilen oder
Cycloalkyl mit 3 bis 6 Kohlenstoffatomen,
oder die Aryl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Alkylen mit 3 oder 4 Kohlenstoffatomen oder Dioxyalkylen mit 1 oder 2 Kohlenstoffatomen, wobei diese Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein können durch Halogen, Alkyl mit 1 bis 4 Kohlenstoffatomen und/oder Halogenalkyl mit 1 bis 4 Kohlenstoffstoffaromen und 1 bis 9 gleichen oder verschiedenen Halogenatomen.The heterocyclylcarbonylaminocyclopropanecarboxylic acid derivatives according to the invention are generally defined by the formula (I). Preferred substances of the formula (I) are those in which
G represents pyridyl which is monosubstituted to trisubstituted by chlorine and / or bromine,
represents thienyl which is monosubstituted to trisubstituted by chlorine and / or bromine or
represents isothiazolyl substituted once or twice by chlorine and / or bromine, and
R represents a five- to seven-membered, saturated N-heterocyclyl radical which is optionally substituted by alkyl having 1 to 4 carbon atoms and which is linked to the carbonyl group via nitrogen and contains 1 to 3 nitrogen atoms, one nitrogen atom being an oxygen or sulfur atom can be replaced, or
R for a group -OR ¹ , -NH-R ² or

stands in what
R ¹ for alkyl with 1 to 4 carbon atoms optionally substituted by alkoxy with 1 to 4 carbon atoms, for alkenyl with 2 to 8 carbon atoms optionally substituted with alkoxy with 1 to 4 carbon atoms, for alkynyl with 2 to 4 alkoxy optionally substituted with alkoxy with 1 to 4 carbon atoms 8 carbon atoms, or
represents cycloalkyl having 3 to 8 carbon atoms optionally substituted by alkyl having 1 to 4 carbon atoms, or
represents aryl having 6 or 10 carbon atoms or aralkyl having 6 or 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, where these radicals in the aryl part can each be mono- to trisubstituted, identical or different, by halogen, cyano, nitro, amino , Hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;
in each case straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloenalkylsulfinyl or haloalkylsulfonyl
each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyloxy, each with 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts or
Cycloalkyl with 3 to 6 carbon atoms,
or the aryl radicals can be monosubstituted by double-linked alkylene having 3 to 4 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, it being possible for these radicals to be monosubstituted to quadruple, identical or differently substituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
R ² for alkyl with 1 to 8 carbon atoms optionally substituted by alkoxy with 1 to 4 carbon atoms, for alkenyl with 2 to 8 carbon atoms optionally substituted with alkoxy with 1 to 4 carbon atoms, for alkynyl with 2 to 4 atoms optionally substituted by alkoxy with 1 to 4 carbon atoms 8 carbon atoms, or
represents cycloalkyl having 3 to 8 carbon atoms optionally substituted by alkyl having 1 to 4 carbon atoms, or
represents aryl having 6 or 10 carbon atoms or aralkyl having 6 or 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, where these radicals in the aryl part can each be mono- to trisubstituted, identical or different, by halogen, cyano, nitro, amino , Hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts or
Cycloalkyl with 3 to 6 carbon atoms,
or the aryl radicals can be monosubstituted by double-linked alkylene having 3 or 4 carbon atoms or dioxyalkylene having 1 or 2 carbon atoms, where these radicals can be monosubstituted to quadrupled, identical or differently substituted by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl with 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms,
and
R ³ and R ⁴ independently of one another for alkyl with 1 to 8 carbon atoms optionally substituted by alkoxy with 1 to 4 carbon atoms, for alkenyl with 2 to 8 carbon atoms optionally substituted with alkoxy with 1 to 4 carbon atoms, for optionally substituted with alkoxy with 1 to 4 carbon atoms are substituted alkynyl having 2 to 8 carbon atoms, or
stand for cycloalkyl with 3 to 8 carbon atoms optionally substituted by alkyl with 1 to 4 carbon atoms, or for aryl with 6 or 10 carbon atoms or for aralkyl with 6 or 10 carbon atoms in the aryl part and 1 to 4 carbon atoms in the alkyl part, these radicals in each case Aryl part can be monosubstituted to trisubstituted, identical or different, by halogen, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl;
in each case straight-chain or branched alkyl, alkoxy, alkylthio, alkylsulfinyl or alkylsulfonyl each having 1 to 6 carbon atoms;
each straight-chain or branched alkenyl or alkenyloxy each having 2 to 6 carbon atoms;
each straight-chain or branched haloalkyl, haloalkoxy, haloalkylthio, haloalkylsulfinyl or haloalkylsulfonyl each having 1 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched haloalkenyl or haloalkenyloxy each having 2 to 6 carbon atoms and 1 to 13 identical or different halogen atoms;
each straight-chain or branched alkylamino, dialkylamino, alkylcarbonyl, alkylcarbonyloxy, alkoxycarbonyl, hydroximinoalkyl or alkoximinoalkyl each having 1 to 6 carbon atoms in the individual alkyl parts or
Cycloalkyl with 3 to 6 carbon atoms,
or the aryl radicals can be monosubstituted by alkylene linked twice in the ortho position 3 or 4 carbon atoms or dioxyalkylene with 1 or 2 carbon atoms, it being possible for these radicals to be substituted one to four times, in the same way or differently, by halogen, alkyl having 1 to 4 carbon atoms and / or haloalkyl having 1 to 4 carbon atoms and 1 to 9 identical or different halogen atoms.

steht, worin
R¹ für jeweils gegebenenfalls durch Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Buty1, Pentyl, Hexyl, Heptyl oder Octyl, Allyl, Butenyl, Pentenyl, Propargyl, Butinyl oder Pentinyl steht, oder
für jeweils gegebenenfalls durch Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht, oder
für Phenyl, Benzyl oder Phenethyl steht, wobei diese Reste jeweils im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Fluor, Chlor, Brom, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy, Difluorchlormethoxy, Trifluorethoxy, Difluormethylthio, Difluorchlormethylthio, Trifluormethylthio, Trifluormethylsulfinyl oder Trifluormethylsulfonyl , Methylamino, Ethylamino, n- oder i-Propylamino, Dimethylamino, Diethylamino, Acetyl, Propionyl, Acetyloxy, Methoxycarbonyl, Ethoxycarbonyl, Hydroximinomethyl, Hydroximinoethyl, Methoximinomethyl, Ethoximinomethyl, Methoximinoethyl oder Ethoximinoethyl oder
Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl,
oder die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Trimethylen (Propan-1,3-diyl), Tetramethylen (Butan-l,4-diyl) oder Ethylendioxy, wobei jeder dieser Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl, oder
die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Methylendioxy, das einfach oder zweifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl,
R² für jeweils gegebenenfalls durch Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Buty1, Pentyl, Hexyl, Heptyl oder Octyl, Allyl, Butenyl, Pentenyl, Propargyl, Butinyl oder Pentinyl steht, oder
für jeweils gegebenenfalls durch Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl steht, oder
für Phenyl, Benzyl oder Phenethyl steht, wobei diese Reste jeweils im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Fluor, Chlor, Brom, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Buty1, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy, Difluorchlormethoxy, Trifluorethoxy, Difluormethylthio, Difluorchlormethylthio, Trifluormethylthio, Trifluormethylsulfinyl oder Trifluormethylsulfonyl, Methylamino, Ethylamino, n- oder i-Propylamino, Dimethylamino, Diethylamino, Acetyl, Propionyl, Acetyloxy, Methoxycarbonyl, Ethoxycarbonyl, Hydroximinomethyl, Hydroximinoethyl, Methoximinomethyl, Ethoximinomethyl, Methoximinoethyl oder Ethoximinoethyl, oder
Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl,
oder die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Trimethylen (Propan-1,3-diyl), Tetramethylen (Butan-1,4-diyl) oder Ethylendioxy, wobei jeder dieser Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl, oder
die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Methylendioxy, das einfach oder zweifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl,
R³ und R⁴ unabhängig voneinander jeweils für gegebenenfalls durch Methoxy oder Ethoxy substituiertes Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Pentyl, Hexyl, Heptyl oder Octyl, Allyl, Butenyl, Pentenyl, Propargyl, Butinyl oder Pentinyl stehen, oder
für jeweils gegebenenfalls durch Methyl oder Ethyl substituiertes Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl stehen, oder
für Phenyl, Benzyl oder Phenethyl stehen, wobei diese Reste jeweils im Phenylteil einfach bis dreifach, gleichartig oder verschieden substituiert sein können durch Fluor, Chlor, Brom, Cyano, Nitro, Amino, Hydroxy, Formyl, Carboxy, Carbamoyl, Thiocarbamoyl, Methyl, Ethyl, n- oder i-Propyl, n-, i-, s- oder t-Butyl, Methoxy, Ethoxy, n- oder i-Propoxy, Methylthio, Ethylthio, n- oder i-Propylthio, Methylsulfinyl, Ethylsulfinyl, Methylsulfonyl oder Ethylsulfonyl, Trifluormethyl, Trifluorethyl, Difluormethoxy, Trifluormethoxy, Difluorchlormethoxy, Trifluorethoxy, Difluormethylthio, Difluorchlormethylthio, Trifluormethylthio, Trifluormethylsulfinyl oder Trifluormethylsulfonyl, Methylamino, Ethylamino, n- oder i-Propylamino, Dimethylamino, Diethylamino, Acetyl, Propionyl, Acetyloxy, Methoxycarbonyl, Ethoxycarbonyl, Hydroximinomethyl, Hydroximinoethyl, Methoximinomethyl, Ethoximinomethyl, Methoximinoethyl oder Ethoximinoethyl, oder
Cyclopropyl, Cyclobutyl, Cyclopentyl oder Cyclohexyl,
oder die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Trimethylen (Propan-l,3-diyl), Tetramethylen (Butan-l,4-dinyl) oder Ethylendioxy, wobei jeder dieser Reste einfach bis vierfach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl,
oder die Phenyl-Reste einfach substituiert sein können durch zweifach in ortho-Stellung verknüpftes Methylendioxy, das einfach oder zweifach, gleichartig oder verschieden substituiert sein kann durch Fluor, Chlor, – Methyl, Trifluormethyl, Ethyl, n-Propyl oder Isopropyl.Compounds of the formula (I) in which
G represents 2,6-dichloropyrid-4-yl, 3,4-dichloroisothiazol-5-yl, 5-bromo-2-thienyl, 5-chloro-2-thienyl or 4,5-dibromo-2-thienyl, and
R represents pyrrolidinyl, piperidinyl, hexahydroazepinyl, morpholinyl or piperazinyl, which is optionally substituted by methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, or
R for a group -OR ¹ , -NH-R ² or

stands in what
R ¹ for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, optionally substituted by methoxy or ethoxy, pentyl, hexyl, heptyl or octyl, allyl, butenyl, pentenyl, propargyl, Butinyl or pentinyl, or
represents in each case optionally substituted by methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or
represents phenyl, benzyl or phenethyl, these radicals in the phenyl part in each case being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl , n- or i-Propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl , Trifluoromethyl, trifluorethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methylamino, ethylaminoethyl, ethylaminoethyl, ethylaminoethyl Hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl or
Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
or the phenyl radicals can be monosubstituted by trimethylene (propane-1,3-diyl), tetramethylene (butane-1,4-diyl) or ethylenedioxy which are linked in the ortho position, each of these radicals being simple to fourfold, similar or can be differently substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl, or
the phenyl radicals may be monosubstituted by methylenedioxy which is linked in the ortho position and which may be monosubstituted or disubstituted, identical or differently substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl,
R ² for methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, optionally substituted by methoxy or ethoxy, pentyl, hexyl, heptyl or octyl, allyl, butenyl, pentenyl, propargyl, Butinyl or pentinyl, or
represents in each case optionally substituted by methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, or
represents phenyl, benzyl or phenethyl, these radicals in the phenyl part in each case being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl , n- or i-propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl , Trifluoromethyl, trifluorethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methylamino, ethylaminoethyl, ethylaminoethyl, ethylaminoethyl Hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl, or
Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
or the phenyl radicals can be monosubstituted by trimethylene (propane-1,3-diyl), tetramethylene (butane-1,4-diyl) or ethylenedioxy which are linked in the ortho position, each of these radicals being simple to fourfold, similar or can be differently substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl, or
the phenyl radicals may be monosubstituted by methylenedioxy which is linked in the ortho position and which may be monosubstituted or disubstituted, identical or differently substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl,
R ³ and R ⁴ independently of one another each represent methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl or octyl, allyl, butenyl optionally substituted by methoxy or ethoxy , Pentenyl, propargyl, butinyl or pentinyl, or
each represent cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl optionally substituted by methyl or ethyl, or
represent phenyl, benzyl or phenethyl, these radicals in the phenyl part in each case being monosubstituted to triple, identical or differently substituted by fluorine, chlorine, bromine, cyano, nitro, amino, hydroxy, formyl, carboxy, carbamoyl, thiocarbamoyl, methyl, ethyl , n- or i-Propyl, n-, i-, s- or t-butyl, methoxy, ethoxy, n- or i-propoxy, methylthio, ethylthio, n- or i-propylthio, methylsulfinyl, ethylsulfinyl, methylsulfonyl or ethylsulfonyl , Trifluoromethyl, trifluorethyl, difluoromethoxy, trifluoromethoxy, difluorochloromethoxy, trifluoroethoxy, difluoromethylthio, difluorochloromethylthio, trifluoromethylthio, trifluoromethylsulfinyl or trifluoromethylsulfonyl, methylamino, ethylaminoethyl, ethylaminoethyl, ethylaminoethyl Hydroximinoethyl, methoximinomethyl, ethoximinomethyl, methoximinoethyl or ethoximinoethyl, or
Cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl,
or the phenyl radicals can be monosubstituted by trimethylene (propane-l, 3-diyl), tetramethylene (butane-l, 4-dinyl) or ethylenedioxy which are linked in the ortho position, each of these radicals being simple to fourfold, similar or can be differently substituted by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl,
or the phenyl radicals can be monosubstituted by methylenedioxy which is linked in the ortho position and which can be monosubstituted, disubstituted, identical or different by fluorine, chlorine, methyl, trifluoromethyl, ethyl, n-propyl or isopropyl.

A very particularly preferred group of substances according to the invention are those compounds of the formula (I) in which
G represents 2,6-dichloropyrid-4-yl, 3,4-dichloroisothiazol-5-yl, 5-bromo-2-thienyl, 5-chloro-2-thienyl or 4,5-dibromo-2-thienyl, and
R represents a group -OR ¹ or -NH-R ² , wherein
R ¹ represents methyl, ethyl, n- or i-propyl, n-, i-, s- or t-butyl, pentyl, hexyl, heptyl, octyl, allyl, butenyl, pentenyl, propargyl, each optionally substituted by methoxy or ethoxy. Butinyl or pentinyl, or represents in each case optionally substituted by methyl or ethyl cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl, and
R ² for each methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, sec-butyl optionally substituted by methoxy or ethoxy; tert-butyl, pentyl, hexyl, heptyl, octyl, allyl, butenyl, pentenyl, propargyl, butynyl or pentynyl, or represents cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl which is optionally substituted by methyl or ethyl.

If 3,4-dichloro-5-isothiazole carbonyl chloride is used and 1-amino-cyclopropane-1-carboxylic acid n-butyl ester as starting materials, the course of the process (a) according to the invention can be determined by the The following formula diagram can be illustrated.

Using 1 - [(2,6-dichloro-isonicotinoyl) amino] cyclopropane carboxylic acid and Butan-2-ol as starting materials, the course of the process according to the invention (b) are illustrated by the following formula scheme.

Formula (II) provides a general definition of the amino-cyclopropane-carboxylic acid esters required as starting substances when carrying out process (a) according to the invention. In this formula, R ¹ preferably has those meanings which have already been mentioned as preferred for this radical in connection with the description of the substances of the formula (I) according to the invention.

The amino-cyclopropane-carboxylic acid esters of the formula (II) are known or can be prepared by known methods (cf. DE-A 28 24 517 , WO 86-03 378, EP-A 0 199 257 and Plant Growth Regul. 8 (4), 297-307 (1989)). They can be prepared by reacting 1-amino-cyclopropane-carboxylic acid with an alcohol in the presence of thionyl chloride.

The continue to carry out the inventive method (a) required as reaction components halides are generally defined by the formula (III). In this formula G preferably has those meanings that are already related with the description of the substances of formula (I) according to the invention for this Rest were mentioned as preferred. X preferably represents chlorine or bromine.

The acid halides of the formula (III) are known or can be prepared by known methods (cf. DE-A 36 15 293 , WO 99-24 413 and EP-A 0 393 936 ).

As a diluent come in the execution of the method according to the invention (a) all common, inert organic solvents. Preferably used are aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, Benzene, toluene, xylene or decalin; halogenated hydrocarbons, such as chlorobenzene, dichlorobenzene, dichloromethane, chloroform, Carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, diisopropylether, Methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2- Dimethoxyethane, 1,2-diethoxyethane or anisole, or amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or Hexamethylphosphoramide.

The acid binders come from execution of the method according to the invention (a) all usual inorganic and organic bases in question. Preferably used are alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or bicarbonates, such as, for example Sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, Sodium hydroxide, potassium hydroxide, sodium acetate, potassium acetate, calcium acetate, Ammonium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate, Sodium hydrogen carbonate or cesium carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium carbonate or ammonium acetate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethylbenzylamine, pyridine, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

The reaction temperatures can be at the implementation of the method according to the invention (a) in a larger area can be varied. Generally one works at temperatures of 0 ° C to 120 ° C, preferably at temperatures of 0 ° C up to 80 ° C.

When carrying out the method according to the invention (a) is set on 1 mol of amino-cyclopropane-carboxylic acid ester of formula (II) generally 0.2 to 5 moles, preferably 0.5 to 2 moles of acid halide of formula (III). The processing takes place according to usual Methods.

The in the implementation of the inventive method (b) required as starting materials Acylamino-cyclopropane-carboxylic acids are generally defined by the formula (IV). In this formula G preferably has those meanings that are already related with the description of the substances of formula (I) according to the invention for this Rest were mentioned as preferred.

The acylamino-cyclopropane-carboxylic acids of Formula (IV) are not yet known.

Just like the heterocyclylcarbonylamino-cyclopropane-carboxylic acid derivatives of the formula (I) can also the acylamino-cyclopropane-carboxylic acids Formula (IV) very good for combating of unwanted Use microorganisms. In particular, they have fungicidal properties and can be used both for the direct control of phytopathogenic Use fungi as well as to induce resistance in plants. Besides, they can also to combat of unwanted Microorganisms are used in material protection.

• c) Heterocyclylcarbonyl-amino-cyclopropan-carbonsäure-derivate der Formel
  
  in welcher G und R¹ die oben angegebenen Bedeutungen haben, mit Wasser in Gegenwart einer Base und gegebenenfalls in Gegenwart eines organischen Verdünnungsmittels umsetzt.

The acylamino-cyclopropane-carboxylic acids of the formula (IV) can be prepared by

• c) heterocyclylcarbonylamino-cyclopropane-carboxylic acid derivatives of the formula
  
  in which G and R ^{1 have} the meanings given above, with water in the presence of a base and optionally in the presence of an organic diluent.

If 1 - [(2,6-dichloro-isonicotinoyl) amino] -cyclopropane-carboxylic acid methyl ester is used as the starting substance, the course of the method according to the invention (c) are illustrated by the following formula scheme.

Formula (Ia) provides a general definition of the heterocyclylcarbonylamino-cyclopropane-carboxylic acid derivatives required as starting substances when carrying out process (c) according to the invention. In this formula, G and R ¹ preferably have those meanings which have already been mentioned as preferred for these radicals in connection with the description of the substances of the formula (I) according to the invention.

In the case of the heterocyclylcarbonylamino-cyclopropane-carboxylic acid derivatives of the formula (Ia) are substances according to the invention, which are according to the method according to the invention (a) have it made.

As bases come in performing the inventive method (c) all usual inorganic bases. Alkaline earth metal or alkali metal hydroxides, such as lithium hydroxide, Sodium hydroxide, potassium hydroxide or calcium hydroxide.

As a diluent come in the execution of the method according to the invention (c) all common, water-miscible, organic solvents. Preferably Alcohols such as methanol, ethanol, n- or i-propanol, n-, i-, sec- or tert-butanol, ethanediol, propane-1,2-diol, ethoxyethanol, methoxyethanol, Diethylene glycol monomethyl ether or diethylene glycol monoethyl ether.

The reaction temperatures can be at the implementation of the method according to the invention (c) in a larger area can be varied. Generally one works at temperatures of 0 ° C to 80 ° C, preferably at temperatures of 0 ° C up to 50 ° C.

When carrying out the method according to the invention (c) using heterocyclylcarbonylamino-cyclopropane-carboxylic acid derivatives of formula (Ia) in the presence of an equivalent amount or an excess at base with an excess of water around. The processing is again carried out using customary methods.

The in the implementation of the inventive method (b) required as reaction components Compounds are generally defined by the formula (V). In this Formula R preferably has those meanings that are already in Connection with the description of the substances according to the invention of formula (I) for this rest were mentioned as preferred.

The compounds of formula (V) are known or can be prepared by known methods.

As a diluent come in the execution of the method according to the invention (c) all usual inert organic solvents. Preferably used are aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, Benzene, toluene or decalin; halogenated hydrocarbons, such as for example chlorobenzene, dichlorobenzene, dichloromethane, chloroform, Carbon tetrachloride, dichloroethane or trichloroethane; Ethers, such as diethyl ether, Diisopropyl ether, methyl t-butyl ether, Methyl t-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane or anisole; Ketones such as acetone, butanone, methyl isobutyl ketone or cyclohexanone; Nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; Amides, such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide; Esters such as methyl acetate or ethyl acetate; Sulfoxides such as dimethyl sulfoxide or sulfones; like Sulfolan.

Coming as a condensing agent the implementation of the method according to the invention (b) all for Amidation reactions usually applicable aids in question. Acid halide formers can preferably be used such as phosgene, phosphorus tribromide, phosphorus trichloride, phosphorus pentachloride, Phosphorus oxychloride or thionyl chloride; Anhydride formers such as ethyl chloroformate, methyl chloroformate, chloroformate, isobutylchloroformate or methanesulfonyl chloride; Carbodiids such as N, N'-dicyclohexylcarbodiimide (DCC) or other common Condensing agents, such as phosphorus pentoxide, polyphosphoric acid, N, N'-carbonyldumidazole, 2-ethoxy-N-ethoxycarbonyl-1,2-dihydroquinoline (EEDQ, bis- (2-oxo-3-oxazolidinyl) phosphinic acid chloride (BOP-Cl) or triphenylphosphine / carbon tetrachloride.

Acid acceptors, such as conventional inorganic or organic bases, are also suitable as auxiliaries for the condensation when carrying out process (b) according to the invention. Alkaline earth metal or alkali metal hydrides, hydroxides, amides, alcoholates, acetates, carbonates or hydrogen carbonates, such as, for example, sodium hydride, sodium amide, sodium methylate, sodium ethylate, potassium tert-butoxide, sodium hydroxide, potassium hydroxide, are preferably usable , Sodium acetate, potassium acetate, calcium acetate, sodium carbonate, potassium carbonate, potassium hydrogen carbonate or sodium hydrogen carbonate, furthermore ammonium compounds, such as ammonium hydroxide, ammonium acetate or ammonium carbonate, and also tertiary amines, such as trimethylamine, triethylamine, tributylamine, N, N-dimethylaniline, N, N-dimethyl benzylamine, Pyri din, N-methylpiperidine, N-methylmorpholine, N, N-dimethylaminopyridine, diazabicyclooctane (DABCO), diazabicyclonones (DBN) or diazabicycloundecene (DBU).

As catalysts come in the execution of the method according to the invention (b) all for such implementations usual Reaction accelerators in question. 4-Dimethylamino-pyridine can preferably be used, 1-hydroxy-benzotriazole or dimethylformamide.

The reaction temperatures can be at the implementation of the method according to the invention (b) in a larger area can be varied. Generally one works at temperatures between -78 ° C and + 120 ° C, preferably at temperatures between -60 ° C and + 25 ° C.

When carrying out the method according to the invention (b) is set to 1 mol of acylamino-cyclopropane-carboxylic acid Formula (IV) generally between 0.5 and 5 moles, preferably an equimolar amount on compound of formula (V). The processing takes place again according to usual Methods.

When carrying out the method according to the invention (a) to (c) are generally carried out under atmospheric pressure. But it is also possible under reduced or increased Pressure, for example, to work between 0.1 and 10 bar.

The substances according to the invention have a strong microbicidal effect on and can for fighting of unwanted Microorganisms, such as fungi and bacteria, in crop protection and be used in material protection.

Fungicides can be plant protection for fighting from Plasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes, Use Ascomycetes, Basidiomycetes and Deuteromycetes.

Bactericides can be used in crop protection for fighting from Pseudomonadaceae, Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae and use Streptomycetaceae.

Some pathogens of fungal and bacterial diseases that fall under the generic names listed above may be mentioned as examples, but not by way of limitation:
Xanthomonas species, such as, for example, Xanthomonas campestris pv. Oryzae;
Pseudomonas species, such as, for example, Pseudomonas syringae pv. Lachrymans;
Erwinia species, such as, for example, Erwinia amylovora;
Pythium species, such as, for example, Pythium ultimum;
Phytophthora species, such as, for example, Phytophthora infestans;
Pseudoperonospora species, such as, for example, Pseudoperonospora humuli or
Pseudoperonospora cubensis;
Plasmopara species, such as, for example, Plasmopara viticola;
Bremia species, such as, for example, Bremia lactucae;
Peronospora species, such as, for example, Peronospora pisi or P. brassicae;
Erysiphe species, such as, for example, Erysiphe graminis;
Sphaerotheca species, such as, for example, Sphaerotheca fuliginea;
Podosphaera species, such as, for example, Podosphaera leucotricha;
Venturia species, such as, for example, Venturia inaequalis;
Pyrenophora species, such as, for example, Pyrenophora teres or P. graminea (conidial form: Drechslera, Syn: Helminthosporium);
Cochliobolus species, such as, for example, Cochliobolus sativus (conidial form: Drechslera, Syn: Helminthosporium);
Uromyces species, such as, for example, Uromyces appendiculatus;
Puccinia species, such as, for example, Puccinia recondita;
Sclerotinia species, such as, for example, Sclerotinia sclerotiorum;
Tilletia species, such as, for example, Tilletia caries;
Ustilago species, such as, for example, Ustilago nuda or Ustilago avenae;
Pellicularia species, such as, for example, Pellicularia sasakii;
Pyricularia species, such as, for example, Pyricularia oryzae;
Fusarium species, such as, for example, Fusarium culmorum;
Botrytis species, such as, for example, Botrytis cinerea;
Septoria species, such as, for example, Septoria nodorum;
Leptosphaeria species, such as, for example, Leptosphaeria nodorum;
Cercospora species, such as, for example, Cercospora canescens;
Alternaria species, such as, for example, Alternaria brassicae;
Pseudocercosporella species, such as, for example, Pseudocercosporella herpotrichoides.

The active compounds according to the invention also have a strong strengthening Effect in plants. They are therefore suitable for mobilization plant's own defenses against infestation by unwanted Microorganisms.

Plant-strengthening (resistance-inducing) substances are to be understood in the present context as substances which are able to stimulate the immune system of plants in such a way that the treated plants develop extensive resistance to these microorganisms when subsequently inoculated with undesired microorganisms.

Are among unwanted microorganisms in the present case phytopathogenic fungi, bacteria and viruses too understand. The substances according to the invention can So be used to plants within a certain period of time after treatment against infestation by the named pathogens to protect. The period within which protection is brought about extends in the generally from 1 to 10 days, preferably 1 to 7 days after Treatment of plants with the active ingredients.

The good plant tolerance of the active ingredients in the fight necessary concentrations of plant diseases allows a Treatment of above-ground parts of plants, planting and seeds, and the floor.

The active compounds according to the invention can be used here with particularly good success in combating cereal diseases, such as against Erysiphe species. The active compounds according to the invention are suitable also to increase crop yield. They are also less toxic and are well tolerated by plants.

The active compounds according to the invention can, if appropriate in certain concentrations and application rates also as herbicides, to influence plant growth, as well as to combat animal pests be used. If necessary, they can also be used as intermediate and intermediate products for use the synthesis of other active ingredients.

According to the invention, all plants and parts of plants be treated. Plants include all plants and Plant populations understood how desired and undesirable wild plants or Cultivated plants (including Naturally crops). Crop plants can be plants that are caused by conventional breeding and optimization methods or through biotechnological and genetic engineering Methods or combinations of these methods can be obtained, including the transgenic Plants and including of those that can be poured through plant variety rights or non-protectable plant varieties. Under plant parts, all above-ground and underground Parts and organs of plants, such as sprout, leaf, flower and root are understood, examples being leaves, needles, stems, stems, flowers, fruiting bodies, fruits and Seeds as well as roots, tubers and rhizomes are listed. To the plant parts heard also crops and vegetative and generative propagation material, for example cuttings, tubers, rhizomes, cuttings and seeds.

The treatment of the plants according to the invention and parts of plants with the active ingredients are carried out directly or through Impact on their environment, living space or storage space according to the usual Treatment methods, e.g. by dipping, spraying, evaporating, atomizing, Scattering, spreading and propagating material, in particular in the case of seeds, still by single or multi-layer coating.

They can be used in material protection substances according to the invention to protect technical materials against infestation and destruction by undesirable Use microorganisms.

Among technical materials are to understand non-living materials in the present context, the for the use has been prepared in the art. For example can Technical materials that are active against microbial by active ingredients according to the invention change or destruction protected adhesives, glues, paper and cardboard, textiles, Leather, wood, paints and plastic articles, cooling lubricants and other materials infested with microorganisms or can be decomposed. As part of the to be protected Materials are also parts of production plants, such as cooling water circuits, which can be affected by the multiplication of microorganisms. As part of the present invention are preferred as technical materials Adhesives, glues, papers and cartons, leather, wood, paints, coolant and heat transfer fluids called, particularly preferably wood.

As microorganisms that break down or a change of the technical materials can be, for example Bacteria, fungi, yeasts, algae and slime organisms. Preferably act the active compounds according to the invention against fungi, in particular mold, wood-discoloring and wood-destroying fungi (Basidiomycetes) and against mucous organisms and algae.

Microorganisms of the following genera may be mentioned, for example:
Alternaria, such as Alternaria tenuis,
Aspergillus, such as Aspergillus niger,
Chaetomium, like Chaetomium globosum,
Coniophora, such as Coniophora puetana,
Lentinus, such as Lentinus tigrinus,
Penicillium, such as Penicillium glaucum,
Polyporus, such as Polyporus versicolor,
Aureobasidium, such as Aureobasidium pullulans,
Sclerophoma, such as Sclerophoma pityophila,
Trichoderma, like Trichoderma viride,
Escherichia, such as Escherichia coli,
Pseudomonas, such as Pseudomonas aeruginosa,
Staphylococcus, such as Staphylococcus aureus.

The active ingredients can depend on their respective physical and / or chemical properties in the usual Formulations are transferred like solutions, Emulsions, suspensions, powders, foams, pastes, granules, aerosols, Fine encapsulation in polymeric substances and in coating compositions for seeds, as well as ULV cold and warm fog formulations.

These formulations are known in the art Manufactured in such a way, e.g. by mixing the active ingredients with extenders, so liquid solvents pressurized liquefied Gases and / or solid carriers, optionally using surface-active agents, that is to say emulsifiers and / or Dispersing agents and / or foaming agents. In case of Use of water as an extender can e.g. also organic solvents as auxiliary solvent be used. As a liquid solvent essentially come into question: aromatics, such as xylene, toluene or Alkylnaphthalenes, chlorinated aromatics or chlorinated aliphatic Hydrocarbons, such as chlorobenzenes, chlorethylenes or methylene chloride, aliphatic hydrocarbons, such as cyclohexane or paraffins, e.g. Petroleum fractions, Alcohols, such as butanol or glycol, and their ethers and esters, ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polar solvents, such as dimethylformamide and dimethyl sulfoxide, and water. With liquefied gaseous Extenders or carriers are such liquids meant which are gaseous at normal temperature and pressure, e.g. Aerosol propellants, such as halogenated hydrocarbons and butane, propane, nitrogen and Carbon dioxide. As solid carriers come into question: e.g. natural Rock flours, such as kaolins, clays, talc, chalk, quartz, attapulgite, Montmorillonite or diatomaceous earth and synthetic rock powder, like finely divided silica, Alumina and silicates. Possible solid carriers for granules are: e.g. broken and fractionated natural rocks such as calcite, Marble, pumice, sepiolite, dolomite and synthetic granules inorganic and organic flours and granules from organic Material like sawdust, coconut shells, Corn cobs and tobacco stalks. As an emulsifier and / or foam generator Funds are possible: e.g. non-ionic and anionic emulsifiers, such as polyoxyethylene fatty acid esters, Polyoxyethylene fatty alcohol ethers, e.g. alkylaryl, Alkyl sulfonates, alkyl sulfates, aryl sulfonates and protein hydrolyzates. Possible dispersants are: e.g. Lignin liquors and methyl cellulose.

It can be in the formulations Adhesives such as carboxymethyl cellulose, natural and synthetic powdery, grained or latex-shaped Polymers are used, such as gum arabic, polyvinyl alcohol, Polyvinyl acetate, as well as natural Phospholipids such as cephalins and lecithins, and synthetic phospholipids. Further Additives can mineral and vegetable oils his.

Dyes such as inorganic Pigments, e.g. Iron oxide, titanium oxide, ferrocyan blue and organic Dyes such as alizarin, azo and metal phthalocyanine dyes and trace nutrients, such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc be used.

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

The active compounds according to the invention can be used as such or in their formulations also in a mixture with known Fungicides, bactericides, acaricides, nematicides or insecticides can be used e.g. to broaden the spectrum of activity or prevent development of resistance. In many cases you get it synergistic effects, i.e. the effectiveness of the mixture is greater than the effectiveness of the individual components.

For example, come as a mixed partner the following connections in question:

fungicides:

Aldimorph, ampropylfos, ampropylfos potassium, andoprim, anilazine, azaconazole, azoxystrobin,
Benalaxyl, benodanil, benomyl, benzamacril, benzamacrylic isobutyl, bialaphos, binapacrylic, biphenyl, bitertanol, blasticidin-S, bromuconazole, bupirimate, buthiobate,
Calcium polysulfide, carpropamide, capsimycin, captafol, captan, carbendazim, carboxin, carvone, quinomethionate (quinomethionate), chlobenthiazone, chlorfenazole, chloroneb, chloropicrin, chlorothalonil, chlozolinate, clozylacon, cufraneb, cymroconililanil
Debacarb, dichlorophene, diclobutrazole, diclofluanid, diclomezin, dicloran, diethofencarb, difenoconazole, dimethirimol, dimethomorph, diniconazole, diniconazol-M, dinocap, diphenylamine, dipyrithione, ditalimfos, dithorphoxin, dithorphononodine,
Ediphenphos, Epoxiconazole, Etaconazole, Ethirimol, Etridiazole,
Famoxadone, fenapanil, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenitropan, fenpiclonil, fenpropidin, fenpropimorph, fentin acetate, fentin hydroxide, ferbam, ferimzon, fluazinam, flumetover, fluoromid, fluquinconazol, flurprimidololol, flurprimidolanilus, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidololol, flurprimidolutolol Alminium, Fosetyl-Nat rium, fthalide, fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole, furconazole-cis, furmecyclox,
guazatine,
Hexachlorobenzene, hexaconazole, hymexazole,
Imazalil, Imibenconazol, Iminoctadin, Iminoctadinealbesilat, Iminoctadinetriacetat, Iodocarb, Ipconazol, Iprobefos (IBP), Iprodione, Iprovalicarb, Irumamycin, Isoprothiolan, Isovaledione,
Kasugamycin, Kresoxim-methyl, copper preparations, such as: copper hydroxide, copper naphthenate, copper oxychloride, copper sulfate, copper oxide, oxine-copper and Bordeaux mixture,
Mancopper, Mancozeb, Maneb, Meferimzone, Mepanipyrim, Mepronil, Metalaxyl, Metconazol, Methasulfocarb, Methfuroxam, Metiram, Metomeclam, Metsulfovax, Mildiomycin, Myclobutanil, Myclozolin,
Nickel dimethyldithiocarbamate, nitrothal isopropyl, Nuarimol,
Ofurace, Oxadixyl, Oxamocarb, Oxolinicacid, Oxycarboxim, Oxyfenthiin,
Paclobutrazol, pefurazoate, penconazole, pencycuron, phosdiphen, picoxystrobin, PIMARICIN, piperalin, polyoxin, Polyoxorim, probenazole, prochloraz, procymidone, propamocarb, Propanosine sodium, propiconazole, propineb, pyraclostrobin, Pyrazohos, pyrifenox, pyrimethanil, pyroquilon, Pyroxyfur,
Quinconazole, quintozen (PCNB), quinoxyfen,
Sulfur and sulfur preparations, spiroxamines
Tebuconazole, tecloftalam, tecnazene, Tetcyclacis, tetraconazole, thiabendazole, Thicyofen, Thifluzamide, thiophanate-methyl, thiram, Tioxymid, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, Triazbutil, triazoxide, Trichlamid, tricyclazole, tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,
uniconazole
Validamycin A, vinclozolin, viniconazole,
Zarilamid, Zineb, Ziram as well
Dagger G,
OK 8705,
OK 8801,
α- (1,1-dimethylethyl) -β- (2-phenoxyethyl) -1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-fluoro-b-propyl-1H-1,2,4-triazole-1-ethanol,
α- (2,4-dichlorophenyl) -β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,
α- (5-methyl-l, 3-dioxan-5-yl) -β - [[4- (trifluoromethyl) phenyl] methylene] -1H-1,2,4-triazole-l-ethanol,
(SRS, 6RS) -6-hydroxy-2,2,7,7-tetramethyl-5- (1H-1,2,4-triazol-1-yl) -3-octanone,
(E) -a- (methoxyimino) -N-methyl-2-phenoxy-phenylacetamide,
1- (2,4-dichlorophenyl) -2- (1H-1,2,4-triazol-1-yl) -ethanone-O- (phenylmethyl) oxime,
1- (2-methyl-1-naphthalenyl) -1H-pyrrole-2,5-dione,
1- (3,5-dichlorophenyl) -3- (2-propenyl) -2,5-pyrrolidinedione,
1 - [(diiodomethyl) sulphonyl] -4-methylbenzene,
1 - [[2- (2,4-dichlorophenyl) -1,3-dioxolan-2-yl] methyl] -1H-imidazole,
1 - [[2- (4-chlorophenyl) -3-phenyloxiranyl] methyl] -1H-1,2,4-triazole,
1- [1- [2 - [(2,4-dichlorophenyl) methoxy] phenyl] ethenyl] -1H-imidazole,
1-methyl-5-nonyl-2- (phenylmethyl) -3-pyrrolidinol,
2 ', 6'-dibromo-2-methyl-4'-trifluoromethoxy-4'-trifluoro-methyl-1,3-thiazol-5-carboxanilide,
2,6-dichloro-5- (methylthio) -4-pyrimidinyl thiocyanate,
2,6-dichloro-N- (4-trifluoromethylbenzyl) -benzamide,
2,6-dichloro-N - [[4- (trifluoromethyl) phenyl] methyl] benzamide,
2- (2,3,3-triiodo-2-propenyl) -2H-tetrazole,
2 - [(1-methylethyl) sulphonyl] -5- (trichloromethyl) -1,3,4-thiadiazole,
2 - [[6-deoxy-4-O- (4-O-methyl-β-D-glycopyranosyl) -Ad-glucopyranosyl] amino] -4-methoxy-1H-pyrrolo [2,3-d] pyrimidine 5-carbonitrile,
2-aminobutane,
2-bromo-2- (bromomethyl) -pentandinitril,
2-chloro-N- (2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl) -3-pyridine carboxamide,
2-chloro-N- (2,6-dimethylphenyl) -N- (isothiocyanatomethyl) -acetamide,
2-phenylphenol (OPP),
3,4-dichloro-1- [4- (difluoromethoxy) phenyl] -1H-pyrrole-2,5-dione,
3,5-dichloro-N- [cyano [(1-methyl-2-propynyl) -oxy] -methyl] -benzamide,
3- (1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,
3- [2- (4-chlorophenyl) -5-ethoxy-3-isoxazolidinyl] -pyridine,
4-chloro-2-cyano-N, N-dimethyl-5- (4-methylphenyl) -1H-imidazol-1-sulfonamide,
4-methyl-tetrazolo [1,5-a] quinazolin-5 (4H) -one,
8-hydroxyquinoline sulfate,
9H-xanthene-9-carboxylic acid 2 - [(phenylamino) carbonyl] hydrazide,
bis (1-methylethyl) -3-methyl-4 - [(3-methylbenzoyl) oxy] -2,5-thiophene dicarboxylate,
cis-1- (4-chlorophenyl) -2- (1H-1,2,4-triazol-1-yl) cycloheptanol,
cis-4- [3- [4- (1,1-dimethylpropyl) -phenyl-2-methylpropyl] -2,6-dimethyl-morpholine,
Ethyl - [(4-chlorophenyl) azo] cyanoacetate,
potassium bicarbonate,
Methantetrathiol sodium salt,
Methyl-1- (2,3-dihydro-2,2-dimethyl-1H-inden-l-yl) -1H-imidazole-5-carboxylate,
Methyl-N- (2,6-dimethylphenyl) -N- (5-isoxazolylcarbonyl) -DL-alaninate,
Methyl N- (chloroacetyl) -N- (2,6-dimethylphenyl) -DL-alaninate,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-furanyl) acetamide,
N- (2,6-dimethylphenyl) -2-methoxy-N- (tetrahydro-2-oxo-3-thienyl) acetamide,
N- (2-chloro-4-nitrophenyl) -4-methyl-3-nitro-benzenesulfonamide,
N- (4-Cyclohexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (4-hexylphenyl) -1,4,5,6-tetrahydro-2-pyrimidinamine,
N- (5-chloro-2-methylphenyl) -2-methoxy-N- (2-oxo-3-oxazolidinyl) -acetamide,
N- (6-methoxy) -3-pyridinyl) -cyclopropanecarboxamide,
N- [2,2,2-trichloro-1 - [(chloroacetyl) -amino] -ethyl] -benzamide,
N- [3-chloro-4,5-bis- (2-propynyloxy) -phenyl] -N'-methoxy-methanimidamid,
N-formyl-N-hydroxy-DL-alanine-sodium salt,
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat,
O-methyl-S-phenyl-phenylpropylphosphoramidothioate,
S-Methyl-1,2,3-benzothiadiazole-7-carbothioate,
spiro [2H] -1-benzopyran-2,1 '(3'H) -isobenzofuran] -3'-one,
4- [3,4-dimethoxyphenyl) -3- (4-fluorophenyl) acryloyl] morpholine

bactericides:

Bronopol, dichlorophene, nitrapyrin, Nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furan carboxylic acid, oxytetracycline, Probenazole, streptomycin, tecloftalam, copper sulfate and other copper preparations.

Insecticides / acaricides / Nematicides:

Abamectin, Acephate, Acetamiprid, Acrinathrin, Alanycarb, Aldicarb, Aldoxycarb, Alpha-cypermethrin, Alphamethrin, Amitraz, Avermectin, AZ 60541, Azadirachtin, Azamethiphos, Azinphos A, Azinphos M, Azocyclotin,
Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis, Bacillus thuringiensis, Baculoviruses, Beauveria bassiana, Beauveria tenella, Bendiocarb, Benfuracarb, Bensultap, Benzoximate, Betacyfluthrin, Bifenazate, Bifenthrin, Bioethanomifhrin, Bethenomifhrin, Bethenomifhrin, Bethanomifhrin , Butocarboxime, butylpyridaben,
Cadusafos, Carbaryl, Carbofuran, Carbophenothion, Carbosulfan, Cartap, Chloethocarb, Chlorethoxyfos, Chlorfenapyr, Chlorfenvinphos, Chlorfluazuron, Chlormephos, Chlorpyrifos, Chlorpyrifos M, Chlovaporthrin, Chromafenozide, Cis-Resmethrhrhrin, Clofethenethrin, Clofethenethrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Clispethethrin, Cispocetine Thrin, Clispethethrin, Clispethethrin, Clispethethrin, Clispethethrin, Cispocetine Carbin , Cycloprothrin, cyfluthrin, cyhalothrin, cyhexatin, cypermethrin, cyromazine,
Deltamethrin, Demeton M, Demeton S, Demeton-S-methyl, Diafenthiuron, Diazinon, Dichlorvos, Dicofol, Diflubenzuron, Dimethoat, Dimethylvinphos, Diofenolan, Disulfoton, Docusat-sodium, Dofenapyn,
Eflusilanate, Emamectin, Empenthrin, Endosulfan, Entomopfthora spp., Esfenvalerate, Ethiofencarb, Ethion, Ethoprophos, Etofenprox, Etoxazole, Etrimfos,
Fenamiphos, Fenazaquin, Fenbutatin oxide, Fenitrothion, Fenothiocarb, Fenoxacrim, Fenoxycarb, Fenpropathrin, Fenpyrad, Fenpyrithrin, Fenpyroximate, Fenvalerate, Fipronil, Fluazuron, Flubrocythrinate, Flucycloxuron, Flytoxhrhrininate, Fumetoxinhrinate, Foncythrinate, Foncythrinate, Foncythrinate, Foncythrininate, Fonetoxin , Furathiocarb,
granulosis
Halofenozide, HCH, Heptenophos, Hexaflumuron, Hexythiazox, Hydroprene,
Imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion, ivermectin,
nucleopolyhedroviruses
Lambda cyhalothrin, lufenuron
Malathion, Mecarbam, Metaldehyde, Methamidophos, Metharhician anisopliae, Metharhician flavoviride, Methidathione, Methiocarb, Methoprene, Methomyl, Methoxyfenozide, Metolcarb, Metoxadiazone, Mevinphos, Milbemectin, Milbemycin, Monocrotophos,
Naled, Nitenpyram, Nithiazine, Novaluron
Omethoate, oxamyl, oxydemethone M
Paecilomyces fumosoroseus, Parathion A, Parathion M, Permethrin, Phenthoat, Phorat, Phosalone, Phosmet, Phosphamidon, Phoxim, Pirimicarb, Pirimiphos A, Pirimiphos M, Profenofos, Promecarb, Propargite, Propoxur, Prothiofos, Prothrohrine, Pothrohrine, Pothrohrinate, Pothrohrinate, Pothrohrinate , Pyridaben, pyridathione, pyrimidifen, pyriproxyfen,
quinalphos,
ribavirin
Salithion, Sebufos, Silafluofen, Spinosad, Spirodiclofen, Sulfotep, Sulprofos,
Tau-fluvalinate, tebufenozide, tebufenpyrad, Tebupirimiphos, teflubenzuron, tefluthrin, temephos, Temivinphos, terbufos, tetrachlorvinphos, tetradifon Thetacypermethrin, thiacloprid, thiamethoxam, Thiapronil, Thiatriphos, thiocyclam hydrogen oxalate, thiodicarb, thiofanox, thuringiensin, Tralocythrin, tralomethrin, triarathene, Triazamate , Triazophos, triazuron, trichlophenidines, trichlorfon, triflumuron, trimethacarb,
Vamidothion, Vaniliprole, Verticillium lecanii
YI 5302
Zeta-cypermethrin, zolaprofos
(1R-cis) - [5- (phenylmethyl) -3-furanyl] -methyl 3 - [(dihydro-2-oxo-3 (2H) -furanylidene) -methyl] -2,2-dimethylcyclopropanecarboxylate
(3-phenoxyphenyl) methyl-2,2,3,3-tetramethylcyclopropanecarboxylat
1 - [(2-chloro-5-thiazolyl) methyl] tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazin-2 (1H) imine
2- (2-chloro-6-fluorophenyl) -4- [4- (1,1-dimethylethyl) phenyl] -4,5-dihydro-oxazol
2- (Acetlyoxy) -3-dodecyl-l, 4-naphthalenedione
2-chloro-N - [[[4- (1-phenylethoxy) phenyl] amino] carbonyl] -benzamide
2-chloro-N - [[[4- (2,2-dichloro-1,1-difluoroethoxy) phenyl] amino] carbonyl] -benzamide
3-methylphenyl propylcarbamate
4- [4- (4-ethoxyphenyl) -4-methylpentyl] -1-fluoro-2-phenoxy-benzene
4-chloro-2- (1,1-dimethylethyl) -5 - [[2- (2,6-dimethyl-4-phenoxyphenoxy) ethyl] thio] -3 (2H) -pyridazinone
4-chloro-2- (2-chloro-2-methylpropyl) -5 - [(6-iodo-3-pyridinyl) methoxy] -3 (2H) -pyridazinone
4-Chloro-5 - [(6-chloro-3-pyridinyl) methoxy] -2- (3,4-dichlorophenyl) -3 (2H) -pyridazinone Bacillus thuringiensis strain EG-2348
Benzoic acid [2-benzoyl-1- (1,1-dimethylethyl) hydrazide
Butanoic acid 2,2-dimethyl-3- (2,4-dichlorophenyl) -2-oxo-1-oxaspiro [4.5] dec-3-en-4-yl ester
[3 - [(6-chloro-3-pyridinyl) methyl] -2-thiazolidinylidene] -cyanamide
Dihydro-2- (nitromethylene) -2H-1,3-thiazine-3 (4H) -carboxaldehyde
Ethyl [2 - [[1,6-dihydro-6-oxo-1- (phenylmethyl) -4-pyridazinyl] oxy] ethyl] carbamate
N- (3,4,4-trifluoro-1-oxo-3-butenyl) -glycine
N- (4-chlorophenyl) -3- [4- (difluoromethoxy) phenyl] -4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide
N - [(2-chloro-5-thiazolyl) methyl] -N'-methyl-N '' - nitro-guanidine
N-methyl-N '- (1-methyl-2-propenyl) -1,2-hydrazindicarbothioamid
N-methyl-N'-2-propenyl-1,2-hydrazindicarbothioamid
O, O-diethyl [2- (dipropylamino) -2-oxoethyl] -ethylphosphoramidothioat
N-cyanomethyl-4-trifluoromethyl-nicotinamide
3,5-dichloro-1- (3,3-dichloro-2-propenyloxy) -4- [3- (5-trifluoromethylpyridine-2-yloxy) propoxy] benzene

Also a mix with other known ones Active ingredients such as herbicides or with fertilizers and growth regulators is possible.

In addition, the compounds of the invention of the formula (I) also have very good antifungal effects. she have a very broad spectrum of antifungal effects, in particular against dermatophytes and sprout fungi, mold and diphasic fungi (e.g. against Candida species such as Candida albicans, Candida glabrata) as well as Epidermophyton floccosum, Aspergillus species such as Aspergillus niger and Aspergillus fumigatus, Trichophyton species like Trtchophyton mentagrophytes, microsporon species such as microsporon canis and audouinii. The list this fungus does not in any way limit the detectable mycotic Spectrum, but is only explanatory.

The active ingredients as such, in the form of their Formulations or the use forms prepared from them, such as ready-to-use solutions, Suspensions, wettable powders, pastes, soluble powders, dusts and granules are used. The application is done in the usual way Manner, e.g. by pouring, splashing, spraying, Scattering, dusting, foaming, Brushing etc. It is also possible apply the active ingredients using the ultra-low-volume process or the drug preparation or the drug itself into the soil to inject. The seeds of the plants can also be treated.

When the active compounds according to the invention are used as fungicides, the application rates can be varied within a relatively wide range, depending on the type of application. When treating plant parts lie gene application rates of active ingredient in general between 0.1 and 10,000 g / ha, preferably between 10 and 1,000 g / ha.

Lie in the seed treatment the application rates of active ingredient in general between 0.001 and 50 g per kilogram of seed, preferably between 0.01 and 10 g per kilogram of seed. In the treatment of the soil Application rates of active ingredient generally between 0.1 and 10,000 g / ha, preferably between 1 and 5,000 g / ha.

As already mentioned above, according to the invention all plants can and their parts are treated. In a preferred embodiment become wild or by conventional organic breeding methods, plant species obtained such as crossing or protoplast fusion and Plant varieties and their parts treated. In another preferred embodiment are transgenic plants and plant varieties that are caused by genetic engineering Methods if necessary in combination with conventional methods were obtained (Genetic Modified Organisms) and their parts treated. The term "parts" or "parts of plants" or "parts of plants" was explained above.

Plants are particularly preferred according to the invention the commercially available in each case or plant varieties in use. Among plant varieties is understood to mean plants with new properties ("traits") that both through conventional breeding, have been grown by mutagenesis or by recombinant DNA techniques. This can be varieties, Be breeds, bio and genotypes.

Depending on the plant species or plant varieties, their location and growth conditions (soils, climate, growing season, Nutrition) can by the treatment according to the invention also super-additives ("Synergistic") effects occur. For example, they are degraded Application rates and / or exposures of the spectrum of activity and / or a reinforcement the effect of the usable according to the invention Substances and agents, better plant growth, increased tolerance across from high or low temperatures, increased drought tolerance or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of maturity, higher Crop yields, higher quality and / or higher Nutritional value of Crops, higher Shelf life and / or workability of the harvested products is possible, which is beyond what is actually to be expected Effects go beyond.

Among the preferred to be treated according to the invention transgenic (genetically engineered) plants or plant varieties belong all plants that are genetic by genetic modification Received material that these plants particularly advantageous gives valuable properties ("traits"). Examples of such Properties are better plant growth, increased tolerance across from high or low temperatures, increased drought tolerance or against water or soil salt content, increased flowering performance, easier harvesting, Acceleration of maturity, higher Crop yields, higher quality and / or higher nutritional value of crops, higher Shelf life and / or workability of the harvested products. More and special highlighted examples of such properties are an increased defense against the plants animal and microbial pests, like opposite Insects, mites, phytopathogenic fungi, bacteria and / or Viruses as well as an increased Plant tolerance to certain herbicidal active ingredients. As Examples of transgenic plants are the important crops, such as cereals (wheat, rice), corn, soybeans, potatoes, cotton, rapeseed as well as fruit plants (with the fruits apples, pears, citrus fruits and grapes) mentioned corn, soybeans, potatoes, cotton and rapeseed are particularly highlighted become. The properties ("traits") are particularly emphasized the elevated Defense of the plants against insects by arising in the plants Toxins, especially those made by the genetic material Bacillus thuringiensis (e.g. through the genes CryIA (a), CryIA (b), CryIA (c), CryIIA, CryIIIA, CryIIIB2, Cry9c Cry2Ab, Cry3Bb and CryIF and their combinations) are generated in the plants (hereinafter "Bt Plants "). Properties (" traits ") are also particularly emphasized the elevated Defense of plants against fungi, bacteria and viruses by systemic Acquired resistance (SAR), systemin, phytoalexins, elicitors as well as resistance genes and correspondingly expressed proteins and toxins. The properties ("traits") continue to be particularly emphasized the elevated Tolerance of plants certain herbicidal active ingredients, for example imidazolinones, Sulfonylureas, glyphosate or phosphinotricin (e.g. "PAT" gene). The one you want Genes conferring traits can also be used in combinations occur together in the transgenic plants. As examples for "Bt Plants "are maize, cotton, soy and potato under the trade names YIELD GARD © (e.g. maize, Cotton, soy), Knockout © (e.g. Maize), StarLink © (e.g. Corn), Bollgard © (cotton), Nucoton © (cotton) and NewLeaf® (potato) to be expelled. As examples of herbicide-tolerant plants Maize, cotton and soybeans are mentioned below the trade names Roundup Ready® (tolerance against glyphosate e.g. Corn, cotton, soy), Liberty Link © (tolerance to phosphinotricin, e.g. Rape), IMI © (tolerance against imidazolinones) and STS® (tolerance against sulfonylureas e.g. Maize). As a herbicide resistant (conventionally grown to herbicide tolerance) plants also the varieties sold under the name Clearfield © (e.g. Corn) mentioned. Of course these statements also apply to developed in the future or coming onto the market in the future Plant varieties with these or future developed genetic Properties ("traits").

The plants listed can be special advantageous according to the invention with the Compounds of the general formula (I) or the active compound mixtures according to the invention be treated. The above for the active ingredients or mixtures Preferred areas also apply to the treatment of these plants. The is particularly emphasized Plant treatment with the compounds specifically listed in this text or mixtures.

The manufacture and use of the substances according to the invention is illustrated by the following examples.

Preparation Examples

example 1

Procedure (a)

A solution of 17 g (78.5 mmol) of 3,4-dichloro-5- is added to a mixture of 11.9 g (78.5 mmol) of methyl 1-aminocyclopropane-1-carboxylic acid and 19.9 g of triethylamine in 120 ml of tetrahydrofuran. isothiazole carbonyl chloride in 160 ml tetrahydrofuran and stirred for 16 hours at room temperature. The reaction mixture is poured into 1.5 l of water and extracted three times with 300 ml of ethyl acetate each time. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. 17.6 g (72% of theory) of 1 - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester are obtained.
HPLC: logP = 2.03

Example 2

Method (b)

0.1 g (1.45 mmol) of n-butylamine, 0 is added to a mixture of 0.2 g (0.73 mmol) of 1 - [(2,6-dichloroisonicotinoyl) amino] cyclopropanecarboxylic acid in 5 ml of dichloromethane under argon , 19 g of diisopropylethylamine and 0.204 g of bis- (2-oxo-3-oxazolidinyl) phosphinic acid chloride and stirred for 16 hours at room temperature. The reaction mixture is poured into 50 ml of water and extracted three times with 50 ml of ethyl acetate each time. The combined organic phases are dried over sodium sulfate and concentrated under reduced pressure. The residue is chromatographed on silica gel using cyclohexane / ethyl acetate (3: 1). 0.05 g (21% of theory) of 1 - [(2,6-dichloroisonicotinoyl) amino] cyclopropanecarboxylic acid butylamide is obtained.
¹ H NMR (DMSO): δ = 0.87 (t, 3H), 1.32 (m, 8H), 7.05 (t, 1H), 7.92 (s, 2H), 9.22 ( s, 1H) ppm.

Tabelle 1

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

Tabelle 1 (Fortsetzung)

The compounds of the formula (I) mentioned in Table 1 below are also obtained by the methods given above.

Table 1

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

Table 1 (continued)

The logP values were determined according to the EEC directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1 % aqueous phosphoric acid)

# stands for the connecting point

Manufacture of intermediate products of the formula (IV)

Example 35

Procedure (c)

150 ml of 1N sodium hydroxide solution are added to a solution of 11.5 g (39.0 mmol) of 1 - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid methyl ester in 250 ml of isopropanol and the mixture is stirred for 1 hour at room temperature , The reaction mixture is poured into 1.5 l of water and acidified with 1N hydrochloric acid until a pH between 3 and 4 is reached. The precipitate is filtered off, washed with 300 ml of water and dried. 7.23 g (59% of theory) of 1 - {[(3,4-dichloro-5-isothiazolyl) carbonyl] amino} cyclopropanecarboxylic acid are obtained.
HPLC: logP = 1.57

According to the methods given above will also be the compounds listed in Table 2 below of formula (IV) obtained.

Table 2

The logP values were determined according to the EEC directive 79/831 Annex V. A8 by HPLC (gradient method, acetonitrile / 0.1 % aqueous phosphoric acid)

# stands for the connecting point

Production of an intermediate product of the formula (II)

Example 39

In 50 ml of isopropanol cooled to -10 ° C., 21.2 ml of thionyl chloride with stirring slowly dropped. Subsequently 5 g of 1-aminocyclopropane-1-carboxylic acid are added in portions at -10 ° C. After that the reaction mixture is heated to 40 ° C. for 40 hours. Then you cool down to room temperature, again add 10.6 ml of thionyl chloride and stir at 40 ° C. for 7 days. It will turn cooled to room temperature, again with 10.6 ml of thionyl chloride and again for 7 days long at 40 ° C touched. A portion of the volatile is distilled under reduced pressure Components off and on cool to room temperature. The crystalline product is filtered off, washed with diisopropyl ether and dried. You get 9.48 g (98% of theory) of 1-aminocyclopropane-1-carboxylic acid isopropyl ester in the form of the hydrochloride.

¹ H-NMR (DMSO): δ = 1.41 (d, 6H), 1.90 (m, 1H), 7.05 (t, 1H), 3.92 (d, 2H), 8.78 ( s, 2H) ppm.

use Examples

Example A

Erysiphe test (barley) / induction of resistance

Solvent: 50 parts by weight of N, N-dimethylformamide
Emulsifier: 1 part by weight of alkylaryl polyglycol ether

For the preparation of a suitable active ingredient preparation 1 part by weight of active ingredient is mixed with the stated amounts solvent and emulsifier and diluted the concentrate with water to the desired concentration.

For testing for resistance-inducing Effectiveness sprayed to young plants with the active ingredient preparation in the specified Application rate. 5 days after the treatment, the plants are with Spores of Erysiphe graminis f. sp. hordei pollinated. Then be the plants in a greenhouse at a temperature of approx. 20 ° C and a relative humidity of approx. 80% to promote the development of mildew pustules.

7 days after the inoculation the evaluation. 0% means an efficiency that the one corresponds to the control while an efficiency of 100% means that no infection is observed.

In this test, those in the Examples 4, 10, 13, 14, 16, 18, 19, 20, 21, 23, 24, 25, 26, 29, 35 and 37 listed substances according to the invention with an application rate of 375 g / ha an efficiency of at least 90%.

Claims (8)

Heterocyclylcarbonyl-aminocyclopropanecarboxylic acid derivatives of the formula

in which G represents halogen-substituted five- or six-membered heterocyclyl and R represents a group -OR ¹ , -NH-R ² or or

stands or represents an optionally substituted, saturated N-heterocyclyl radical which is connected to the carbonyl group via nitrogen; R ¹ , R ² , R ³ and R ⁴ independently of one another represent optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl or for optionally substituted aralkyl, Process for the preparation of heterocyclylcarbonyl-aminocyclopropanecarboxylic acid derivatives of the formula (I) according to Claim 1, characterized in that a) aminocyclopropanecarboxylic acid esters of the formula

in which R ^{1 has} the meaning given above, or their hydrohalides or hydrogen sulfates with acid halides of the formula

in which X represents halogen and G has the meaning given above, if appropriate in the presence of an diluent and if appropriate in the presence of a sawing binder, or b) acylaminocyclopropanecarboxylic acids of the formula

in which G has the meaning given above, with compounds of the formula RH (V) in which R has the meaning given above, in the presence of a condensing agent and, if appropriate, in the presence of a diluent and, if appropriate, in the presence of a catalyst. Microbicidal agents, characterized by a content of at least a heterocyclylcarbonyl aminocyclopropanecarboxylic acid derivative of formula (I) according to claim 1 in addition to extenders and / or surface-active substances. Use of heterocylylcarbonyl aminocyclopropanecarboxylic acid derivatives of formula (I) according to claim 1 to combat of unwanted Microorganisms. Control procedures of unwanted Microorganisms, characterized in that heterocyclylcarbonyl-aminocyclopropanecarboxylic acid derivatives of formula (I) according to claim 1 spreads on the microorganisms and / or their habitat. Process for the preparation of microbicidal agents, thereby characterized in that heterocyclylcarbonyl aminocyclopropanecarboxylic acid derivatives of formula (I) according to claim 1 mixed with extenders and / or surfactants. Acylaminocyclopropane carboxylic acids of the formula

in which G represents halogen-substituted, five- or six-membered heterocyclyl. A process for the preparation of acylaminocyclopropanecarboxylic acids of the formula (IV) according to claim 7, characterized in that c) heterocyclylcarbonyl-aminocyclopropane-carboxylic acid derivatives of the formula

in which G represents halogen-substituted, five- or six-membered heterocyclyl and R ^{1 represents} optionally substituted alkyl, optionally substituted alkenyl, optionally substituted alkynyl, optionally substituted cycloalkyl, optionally substituted aryl or for optionally substituted arakyl, with water in the presence of a base and optionally in the presence of an organic diluent.