DE4438807A1 - Heterocyclyl-amino and heterocyclyl-oxy-cycloalkenyl derivatives, their use as pesticides and fungicides - Google Patents

Abstract

The invention concerns heterocyclylamino and heterocyclyloxy-cycloalkenyl derivatives of the formula (a) in which Ar is optionally substituted 4-pyridyl or 4-pyrimidyl; X is NH, O, S, SO or SO2; E is a bond or alkanediyl; a and b may each be 0 to 3, but not 0 at the same time; R<4> is halogen, alkyl, cycloalkyl, haloalkyl, alkoxy, haloalkoxy or optionally substituted phenyl; v may be 0 to 2; U is a bond, O, S, SO, SO2 or optionally substituted imino; V is a bond, CO, -CQ-T- or -CT'=N- where Q, T and T' are as defined in the description and R<5> is alkyl, alkenyl, alkinyl, optionally substituted aryl or heteroaryl, cyano, NO2, alkyloximino or a silyl group. The invention also concerns methods for the preparation of such compounds and their use as pest-control agents and fungicides.

Description

The invention relates to heterocyclyl-amino and heterocyclyl-oxy-cycloalkenyl Derivatives, processes for their preparation and their use as Pesticides and fungicides.

It is already known that certain 4-cycloalkoxy-substituted nitrogen Heterocyclic insecticidal, acaricidal, ixodicidal and fungicidal activity (see WO 9300536).

There were new 4-amino and 4-alkoxy-substituted nitrogen heterocycles general formula I found

in which
R¹ is hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₅) cycloalkyl or (C₃-C₅) halocycloalkyl;
R² and R³ are the same or different and are each independently hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₈) cycloalkyl, (C₃-C₈) halocycloalkyl, (C₁- C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) haloalkoxy- (C₁-C₄) alkyl, (C₁-C₄) -Alkoxy- (C₁-C₄) haloalkyl, (C₁-C₄) - haloalkoxy- (C₁-C₄) haloalkyl, (C₁-C₄) alkylamino, (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl , (C₁-C₄) alkylsulfonyl, (C₁-C₄) haloalkylthio, (C₁-C₄) haloalkylsulfinyl, (C₁-C₄) haloalkylsulfonyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, ( C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₁-C₄) alkoxycarbonyl, cyano, (C₁-C₄) cyanoalkyl or thiocyano; or
R² and R³ together with the carbon atoms to which they are attached form an unsaturated 5- or 6-membered isocyclic ring which, if it is a 5-ring, may contain an oxygen or sulfur atom instead of CH₂, or the , if it is a 6-ring, may contain one or two nitrogen atoms instead of one or two CH units and which is optionally substituted by 1, 2 or 3 identical or different radicals and these radicals (C₁-C₄) - Alkyl, (C₁-C₄) haloalkyl, preferably trifluoromethyl, halogen, (C₁-C₄) alkoxy or (C₁-C₄) haloalkoxy, or R² and R³ together with the carbon atoms to which they are attached are saturated 5 - Form, 6- or 7-membered isocyclic ring which may contain oxygen and / or sulfur instead of one or two CH₂ groups and which is optionally substituted by 1, 2 or 3 (C₁-C₄) - alkyl groups;
A represents CH or N;
X represents NH, oxygen or S (O) _q , with q = 0, 1 or 2;
E represents a direct bond or a straight-chain or branched (C₁-C₄) alkanediyl group, preferably a direct bond;
a and b are the same or different and independently of one another represent the numbers 0, 1, 2 or 3, where a and b do not simultaneously mean 0;
R⁴ is halogen, (C₁-C₄) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, (C₁ - C₄) alkoxy, (C₁-C₄) haloalkoxy or optionally substituted phenyl;
v represents 0, 1 or 2;
U is a direct single bond, oxygen, a group S (O) y, with y = 0, 1 or 2 or a group NR⁶, where R⁶ is hydrogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy;
V for a direct single bond, carbonyl or a grouping of the formula

is where Q is oxygen, sulfur or (C₁-C₄) alkylimino, T oxygen, sulfur or a group NR ^{6 '} , and T' (C₁-C₄) alkoxy, (C₁-C₄) alkylthio or NR ^{6 '} R ^{6 ''} means and where R⁶, and R⁶ '' are the same or different and have the meanings given above for R⁶;
R⁵ is a radical from the series alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, nitro, alkyloximino or a group SiR⁷R⁸R⁹, where R⁷ and R⁸ (C₁-C₄) alkyl and R⁹ alkyl, cycloalkyl, Mean aryl and arylalkyl;
and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R⁵, R⁷, R⁸ and R⁹ may have at least one of the following features:

• i. one or more, preferably up to three non-adjacent CH₂ groups are through CO and / or heteroatom units, such as O, S (O) y with y = 0, 1 or 2, NR ^{6 '''} or SiR ^7' R ^{8 '} , replaced, where R ^{6''' has} the meanings given above for R⁶ and where R⁷ 'and R ^{8' have} the meanings given above for R⁷ and R⁸;
• ii. 3 to 12 atoms of these radicals form an up to 12-membered group Cycle;
• iii. the radicals are optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, haloalkyl, arylalkyl , Cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, cycloalkoxy, alkanoyloxy, haloalkanoyloxy, cycloalkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, substituted or unsubstituted by hydroxy, cyano, nitro, cyclo, cyano, nitro, cyclo, cyclo, cyclo, benzo Substituents can be unsubstituted or can be provided with up to three, in the case of halogen, preferably fluorine, up to the maximum number of identical or different substituents;
  and their salts, preferably acid addition salts.

Compounds of the formula I in which
R⁴ is halogen, preferably fluorine, chlorine and bromine, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy or (C₁-C₄) - alkylthio ; and
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, hydroxy, carboxy, nitro, (C₁-C₂₀) alkyloximino or can mean a group SiR⁷R⁸R⁹, where R⁷ and R⁸ (C₁-C₄) alkyl and
R⁹ is (C₁-C₂₀) alkyl or optionally substituted aryl;
and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R⁵, R⁷, R⁸ and R⁹, optionally have at least one of the following features:

• i. one or more, preferably up to three non-adjacent CH₂ groups are through CO and / or heteroatom units, such as O, S (O) _y with y = 0, 1 or 2, NR ^{6 '''} or SiR ^7' R ^{8 '} , replaced, wherein R ^{6''' has} the meanings given above for R⁶ and where R⁷, and R⁸, have the meanings given above for R⁷ and R⁸;
• ii. 3 to 8 atoms of these radicals form an up to 8-membered cycle;
• iii. the radicals are optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, (C₁-C₁₂) alkyl, (C₃-C₈) cycloalkyl, aryl, aryloxy , Arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (C₁-C₁ ₂) haloalkyl, aryl- (C₁-C₄) - alkyl, (C₃-C₈) -cycloalkyl- (C₁-C₄) -alkyl, (C₁-C₁ ₂) -Alkoxy, (C₁-C₁ 2) - haloalkoxy, (C₁-C₁₂) alkylthio, (C₃-C₈) -cycloalkoxy, (C₁-C₁ 2) - alkanoyloxy, (C₁-C₁₂) -haloalkanoyloxy, (C₃-C₈) -Cycloalkanoyloxy, (C₃-C₈) -cycloalkyl- (C₁-C₁₂) -alkanoyloxy, aroyloxy, aryl- (C₁-C₄) alkanoyloxy, (C₁-C₁₂) alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy or nitro, hydroxy, substituted, hydroxyl the cycloaliphatic, aromatic or heterocyclic ring systems under the just mentioned substituents are unsubstituted or with up to three, in the case of halogen, preferably flu or can also be provided with the same or different substituents up to the maximum number and the remaining radicals and variables are as defined above;
  and their salts, preferably acid addition salts.

Compounds of the formula I in which are more preferred
R1 is hydrogen or fluorine;
R² is (C₁-C₄) alkyl, cyclopropyl, halocyclopropyl, halogen (C₁-C₂) alkyl, methoxymethyl or cyano;
R³ is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C₁-C₄) alkoxycarbonyl; or
R² and R³ together with the carbon atoms to which they are attached form an optionally substituted unsaturated 5- or 6-membered ring which, in the case of the 5-ring, may contain a sulfur atom instead of a CH₂ unit, or
R² and R³, together with the carbon atoms to which they are attached, form a saturated 5- or 6-membered ring which may contain a sulfur or an oxygen atom instead of a CH₂ unit;
A represents CH or N;
X represents NH or oxygen;
E stands for a direct bond;
a is 1 and b is 2;
R⁴ represents hydrogen, (C₁-C₄) alkyl, trifluoromethyl or (C₁-C₄) alkoxy;
and the remaining residues and variables are as defined above;
and their salts;
in particular those compounds in which
R1 is hydrogen;
R² is methyl, ethyl, propyl, isopropyl, 1-fluoroethyl, trifluoromethyl, cyclopropyl or methoxymethyl;
R³ is halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C₁-C₄) alkoxycarbonyl, or
R² and R³ together with the ring system to which they are attached form the quinazoline or quinoline system which may be substituted by fluorine in the carbocyclic part, or
R² and R³ together with the carbon atoms to which they are attached form a saturated 6-membered ring which may contain an oxygen or sulfur atom instead of a CH₂ group;
r = O;
U represents a direct bond or oxygen;
V represents a direct bond;
as well as their salts.

Those compounds of the formula I in which
R1 is hydrogen;
R² denotes ethyl, propyl, isopropyl, 1-fluoroethyl, trifluoromethyl or methoxymethyl,
R³ is fluorine, chlorine, bromine or methoxy;
or if A is nitrogen,
R² and R³ together with the ring system to which they are attached form the quinazoline system, which may be substituted with a fluorine atom, or
R² and R³ together with the ring system to which they are attached form the 5,6,7,8-tetrahydroquinazoline system;
A represents CH or N;
X represents NH or oxygen;
E stands for a direct bond;
a the number 1 and
b represents the number 2;
v = 0;
U means a direct bond or oxygen,
V represents a direct bond;
as well as their salts.

Most preferred are those compounds of the formula I in which
R1 is hydrogen;
R² is ethyl or methoxymethyl;
R³ is fluorine, chlorine, bromine or methoxy, or
R² and R³ for A = N together with the ring system to which they are attached form the quinazoline or the 5,6,7,8-tetrahydroquinazoline system;
R⁵ is (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl or (C₂-C₂₀) alkynyl, where 3-6 carbon atoms of these carbon radicals can form a cycle and / or these hydrocarbon radicals optionally with a phenyl radical may be substituted, which may be unsubstituted or provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents;
A represents CH or N;
X represents NH or oxygen;
R⁵ means (C₁-C₂₀) alkyl or (C₂-C₂₀) alkenyl, where 3-6 carbon atoms of this radical can form a cycle and / or this can optionally be substituted with a phenyl radical which is unsubstituted or with up to three, im In the case of fluorine, the same or different substituents can also be provided up to the maximum number;
E stands for a direct bond;
U and V together stand for a direct bond;
v = 0
the remaining radicals and variants are as defined above;
and their salts;
especially those in which
R² is methoxymethyl and R³ is methoxy, or
R² is ethyl and R³ is chlorine or bromine,
X represents NH;
the remaining radicals and variants are as defined above;
as well as their salts.

In the above formula I, "halogen" means a fluorine, chlorine, bromine or iodine atom, preferably a fluorine, chlorine or bromine atom;
under the expression "(C₁-C₄) alkyl" an unbranched or branched hydrocarbon radical having 1-4 carbon atoms, such as. B. the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical;
under the expression "(C₁-C₂₀) alkyl" the aforementioned alkyl radicals, such as. B. the pentyl, 2-methylbutyl or 1,1-dimethylpropyl, the hexyl, heptyl, octyl, 1,1,3,3-tetramethylbutyl, nonyl, 1-decyl, 2-decyl , Undecyl, dodecyl, pentadecyl or eicosyl radical;
under the expression "(C₁-C₄) -haloalkyl" an alkyl group called under the expression "(C₁-C₄) - alkyl", in which one or more hydrogen atoms are replaced by the above-mentioned halogen atoms, preferably chlorine or fluorine, such as, for example Trifluoromethyl group, the 1-fluoroethyl group, the 2,2,2-trifluoroethyl group, the chloromethyl, fluoromethyl group, the difluoromethyl group or the 1,1,2,2-tetrafluoroethyl group;
under the expression "(C₃-C₅) cycloalkyl" preferably the cyclopropyl, cyclobutyl or cyclopentyl group;
under the expression "(C₃-C₈) cycloalkyl" preferably the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl group, but also bicyclic systems, such as. B. the norbornyl group;
under the expression "(C₃-C₈) -halo-cycloalkyl" a group mentioned under the expression "(C₃-C₈) -cycloalkyl" in which one or more hydrogen atoms are replaced by the above-mentioned halogen atoms, preferably chlorine or fluorine;
under the term "(C₁-C₄) alkoxy" an alkoxy group whose hydrocarbon radical has the meanings given under the term "(C₁-C₄) alkyl";
under the expression "(C₁-C₄) -haloalkoxy" a haloalkoxy group whose halogenated hydrocarbon radical has the meanings given under the expression "(C₁-C₄) -haloalkyl"; under the expression "(C₁-C₄) alkoxy- (C₁-C₄) alkyl", for example a 1-methoxyethyl group, a 2-methoxyethyl group, a 2-ethoxyethyl group, a methoxymethyl or ethoxymethyl group, a 3-methoxypropyl group or a 4- Butoxybutyl group;
under the expression "(C₁-C₄) alkylthio" an alkylthio group whose hydrocarbon radical has the meanings given under the expression "(C₁-C₄) alkyl";
under the expression "(C₁-C₄) alkylthio- (C₁-C₄) alkyl" for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl or 3-methylthiopropyl; under the expression "(C₂-C₄) alkenyl" z. B. the vinyl, allyl, 2-methyl-2-propenyl or 2-butenyl group;
under the expression "(C₂-C₂₀) alkenyl" the above radicals and z. B. the 2-pentenyl, 2-decenyl or the 2-eicosenyl group;
under the expression "(C₂-C₄) alkynyl" z. B. the ethynyl, proparyl, 2-methyl-2-propyne or 2-butynyl group;
under the expression "(C₂-C₂₀) alkynyl" the above radicals and z. B. the 2-pentynyl or the 2-decynyl group;
under the expression "(C₁-C₄) alkoxycarbonyl" z. B. the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl or tert-butoxycarbonyl group;
under the expression "(C₁-C₁₂) alkoxycarbonyl" the above radicals and z. B. the hexyloxycarbonyl, 2-methylhexyloxycarbonyl, decyloxycarbonyl or dodecyloxycarbonyl group;
under the term "cyan (C₁-C₄) alkyl" a cyanoalkyl group whose hydrocarbon radical has the meanings given under the term "(C₁-C₄) alkyl";
under the expression "(C₁-C₂₀) alkylidene" z. B. the exo-methylene, ethylidene, propylidene, 1-methyl-propylidene, butylidene, octylidene or dodecylidene group under the expression "(C₁-C₂₀) alkyloximino" is an oximino group which is on the oxygen with one of the is etherified under the expression "(C₁-C₂₀) alkyl";
the term "aryl" means an isocyclic aromatic radical having preferably 6 to 14, in particular 6 to 12, carbon atoms, such as, for example, phenyl, naphthyl or biphenylyl, preferably phenyl;
the term "heterocyclyl" means a heteroaromatic or heteroaliphatic ring system, where "heteroaromatic ring system" means an aryl radical in which at least one CH group has been replaced by N and / or at least two adjacent CH groups have been replaced by S, NH or O. is, e.g. B. a residue of thiophene, furan, pyrrole, thiazole, oxazole, imidazole, isothiazole, isoxazole, pyrazole, 1,3,4-oxadiazole, 1,3,4-thiadiazole, 1,3,4-triazole, 1,2 , 4-oxadiazole, 1,2,4-thiadiazole, 1,2,4-triazole, 1,2,3-triazole, 1,2,3,4-tetrazole, benzo [b] thiophene, benzo [b] furan , Indole, benzo [c] thiophene, benzo [c] furan, isoindole, benzoxazole, benzothiazole, benzimidazole, benzisoxazole, benzisothiazole, benzopyrazole, benzothiadiazole, benzotriazole, dibenzofuran, dibenzothiophene, carbazole, pyridine, 1,3-pyridine, pyrazine, pyridine, pyridine, pyridine, pyridine, pyridine, , 5-triazine, 1,2,4-triazine, 1,2,4,5-triazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine , 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine or 4H-quinolizine;
and under the expression "heteroaliphatic ring system" a (C₃-C₈) cycloalkyl radical in which at least one carbon unit, preferably up to three carbon units, has been replaced by O, S or a group NR¹¹ and R¹¹ is hydrogen, (C₁-C₄) -Alkyl, (C₁-C₄) alkoxy or aryl;
under the expression "substituted aryl" an aryl radical which is substituted by one or more, preferably up to three, in the case of fluorine, up to the maximum number of identical or different radicals from the series halogen, (C₁-C₄) alkyl, (C₁-C₄ ) Haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio, (C₁-C₄) - Alkoxyalkyl, phenyl, phenoxy, halophenoxy, (C₁-C₄) alkylphenoxy, (C₁-C₄) haloalkoxyphenoxy, (C₁-C₄) haloalkylphenoxy, phenylthio, heterocyclyl, heterocylylthio or heterocyclyloxy may be provided;
the term "substituted heterocyclyl" is to be understood as a heteroaromatic or heteroaliphatic ring system which, with one or more, preferably up to three, in the case of fluorine also up to the maximum number of identical or different radicals from the above under the term "substituted aryl" listed substituents may be provided;
under optionally provided with substituents "cycloaliphatic, aromatic and heterocyclic radicals", radicals are to be understood, such as. B. aryloxy, arylthio, heterocyclyloxy, heterocyclylthio, aroyl, aroyloxy, cycloalkyl or cycloalkanoyl, with one or more, preferably up to three, in the case of fluorine also up to the maximum number of the same or different of the substituents listed under "substituted aryl" can be provided;
the term "aryl- (C₁-C₄) -alkyl" is an alkyl group called "(C₁-C₄) -alkyl" which is substituted by an aryl radical;
under the term "aryloxy" z. B. the phenoxy or 1- or 2-naphthyloxy group;
under the expression "arylthio" z. B. the phenylthio or the 1- or 2-naphthylthio group;
under the expression "heterocyclyoxy" or "heterocycloylthio" one of the heterocyclic radicals mentioned above which are linked via an oxygen or sulfur atom.

The substituents with which the various aliphatic, aromatic and heterocyclic ring systems can include z. B. halogen,  (C₁-C₄) alkyl, trimethylsilyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) - Haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) alkylthio, alkylsulfinyl, Alkylsulfonyl, phenyl, phenoxy, halophenoxy, (C₁-C₄) alkylphenoxy, (C₁-C₄) alkoxyphenoxy, (C₁-C₄) haloalkoxyphenoxy, (C₁-C₄) - Haloalkylphenoxy, phenylthio, heterocyclyl, heterocyclylthio or Heterocyclyloxy, being in the alkyl radicals and the radicals derived therefrom one or more hydrogen atoms, in the case of fluorine also up to Maximum number can be replaced by halogen, preferably chlorine or fluorine.

Furthermore, under the definition that "those mentioned in R⁵, R⁷, R⁸ and R⁹ Alkyl, alkenyl, alkynyl or alkyloximino radicals, if appropriate at least have one of the following characteristics:

• i. one or more, preferably up to three non-adjacent CH₂ groups are through CO and / or heteroatom units, such as O, S (O) y with y = 0, 1 or 2, NR ^{6 '''} or SiR ^7' R ^{8 '} , replaced, wherein R ^{6''' has} the meanings given above for R⁶ and where R ^{7 '} and R ^{8' have} the meanings given above for R⁷ and R⁸;
• ii. 3 to 12 atoms of these radicals form an up to 12-membered group Cycle;
• iii. the radicals are optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, haloalkyl, arylalkyl , Cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, cycloalkoxy, alkanoyloxy, haloalkanoyloxy, cycloalkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, substituted or unsubstituted by hydroxy, cyano, nitro, cyclo, cyano, nitro, cyclo, cyclo, cyclo, benzo Substituents can be unsubstituted or can be provided with up to three, in the case of halogen, preferably fluorine, up to the maximum number of identical or different substituents;
  for example alkoxyalkyl radicals such as. B. the methoxymethyl, methoxyethyl or ethoxyethyl group are detected; or alkoxy-alkoxy-alkyl radicals such as. B. the methoxy or ethoxyethoxyethyl group; or alkylthioalkyl radicals such as. B. the methyl or ethylthioethyl group; or alkylsulfinyl-alkyl radicals such as. B. the methyl or ethylsulfinylethyl group; or alkylsulfonyl-alkyl radicals such as. B. the methyl or ethylsulfonylethyl group; or alkyl dialkylsilyl-alkyl radicals, such as. B. the trimethylsilylmethyl or the ethyltrimethylsilylethyl group; or alkyl-cycloalkyl radicals such as. B. the 4-methyl-cyclohexyl, 3-ethyl-cyclopentyl or the 4-tert-butyl-cyclohexyl group; or cycloalkyl-alkyl radicals such as. B. cyclohexylmethyl, cyclohexylethyl, cyclohexylpropyl, cyclohexylbutyl or 1-cyclohexyl-1-methylethyl group or aryl-alkyl radicals such as. B. the benzyl, the 2-phenylethyl, the 1-phenylethyl, the 1-methyl-1-phenylethyl group, the 3-phenylpropyl, the 4-phenylbutyl group, the 2-methyl-2-phenylethyl group or the 1-methyl or 2-methyl naphthyl group; or heterocyclylalkyl radicals such as, for. B. the thienyl methyl, pyridylmethyl, furfuryl, tetrahydrofurfuryl, tetrahydropyranylmethyl or the 1,3-dioxolan-2-ylethyl group; or aryloxyalkyl radicals such as. B. the phenoxymethyl or naphthoxymethyl group; or cycloalkyl radicals, the monocyclic as listed above under the expression "(C₃-C₈) cycloalkyl", bicyclic such. B. the norbornyl radical or the bicyclo [2,2,2] octane radical or condensed as the decahydronaphthyl radical; or also haloalkyl derivatives of the corresponding groups such as, for example, haloalkyl, haloalkoxyalkyl, alkoxyhaloalkyl, haloalkylcycloalkyl or halocycloalkyl radicals.

The explanation given above applies accordingly to homologues or their derived residues.

The explanation given above applies accordingly to residues without a specific one Indication of the number of carbon atoms, as well as for homologues or their derived ones Leftovers.  

The present invention relates to the compounds of formula I in the form of free base or an acid addition salt. Acids leading to salt formation can be used are inorganic acids, such as hydrochloric acid, Hydrobromic acid, nitric acid, sulfuric acid, phosphoric acid or organic acids such as formic acid, acetic acid, propionic acid, oxalic acid, Fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid, Benzenesulfonic acid or toluenesulfonic acid.

Some of the compounds of the formula I have one or more Chirality elements. Racemates or diastereomers can therefore be used occur. The invention encompasses both the pure isomers and theirs Mixtures. The mixtures of diasteromers can be customary Methods, e.g. B. by selective crystallization from suitable solvents or separated into the components by chromatography. Racemate can be separated into the enantiomers by conventional methods, for. B. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers by means of a Base.

The invention further relates to a method for producing compounds of formula I, which is characterized in that a compound of Formula II

wherein A, R¹, R² and R³ have the meanings given under formula I. and L is a leaving group such as halogen, alkylthio, Means alkanesulfonyloxy or arylsulfonyloxy, alkylsulfonyl or arylsulfonyl, with a nucleophile of formula III  

wherein X, E, a, b, v, U, V, R⁴ and R⁵ the specified under formula I. Have meanings, implemented and received in one way or another Compounds of formula I, if R³ is hydrogen, optionally in the Position 5 of the heterocycle halogenated, preferably chlorinated or brominated, or further derivatized in the side chain R⁵.

The substitution reaction described above is known in principle. The Leaving group L can be varied within wide limits and can, for example, be a Halogen atom, such as fluorine, chlorine, bromine or iodine or alkylthio such as Methyl or ethyl thio; or alkanesulfonyloxy, such as methane, trifluoromethane or Ethanesulfonyloxy, or arylsulfonyloxy, such as benzenesulfonyloxy or Toluenesulfonyloxy or alkylsulfonyl, such as methyl or ethylsulfonyl or Arylsulfonyl such as phenyl or toluenesulfonyl.

The above reaction is carried out in a temperature range of 20-150 ° C, expediently in the presence of a base and optionally in an inert organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, Dimethyl sulfoxide, N-methylpyrrolidin-2-one, dioxane, tetrahydrofuran, 4-methyl-2- pentanone, methanol, ethanol, butanol, ethylene glycol, Ethylene glycol dimethyl ether, toluene, chlorobenzene or xylene. It mixtures of the solvents mentioned can also be used. Suitable bases are, for example, alkali metal or alkaline earth metal carbonates, -hy drug carbonates, amides or hydrides such as sodium carbonate, Sodium hydrogen carbonate, potassium carbonate, sodium amide or sodium hydride, organolithium compounds such as n-butyllithium.  

Suitable bases for the case where X is oxygen are, for example Alkali or alkaline earth metal carbonates, bicarbonates, amides or hydrides such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium amide or sodium hydride, in the case where X is NH, for example Alkali or alkaline earth metal carbonates, hydrogen carbonates, hydroxides, amides or hydrides such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, Sodium hydroxide, sodium amide or sodium hydride or organic bases, such as Triethylamine or pyridine. Also a second equivalent of an amine of the formula III can be used as an auxiliary base.

The starting compounds of the formula II are either known or they can be prepared analogously to known processes; see e.g. B .:
Quinolines: Org. Synth., Coll. Vol. 3, 272 (1955)
1,5-naphthyridines: J. Amer. Chem. Soc. 68, 1317 (1946) and British Patent Office 1147760
1,6-naphthyridines: J. Chem. Soc. 1960, 1790
1,7-Naphthyridine: J. Org. Chem. 19, 2008 (1954)
1,8-naphthyridines: Synthesis 1974, 809
Pyridopyrimidines: EP-A-414 386
Pteridine: J. Chem. Soc. 1951, 474.

In the case where A is a nitrogen atom, Acetoacetic ester derivatives, which via the corresponding hydroxypyrimidines in the Halogenpyrimidines are transferred:  

The starting compounds of the formula II can also be analogous to known processes can be obtained from malonic ester derivatives:

The compounds of formula II, wherein R³ is halogen, can according to known methods are halogenated.

The nucleophiles of the formula III required as starting products can be used for the  If X is oxygen, can be prepared by known processes, for example by reducing a carbonyl group with a suitable one Reducing agents, for example a complex metal hydride or in the case an aldehyde or ketone also with hydrogen and a hydrogenation catalyst. To represent the cis-cyclohexanols, the starting materials for the particularly preferred Cis-cyclohexyloxy derivatives are particularly suitable for catalytic hydrogenation appropriately substituted phenols or the reduction of appropriately substituted Cyclohexanone derivatives with complex hydrides, the substituents with large Wear space, such as B. L-Selectride®.

The nucleophiles of the formula III required as starting products can be used for the If III is NH, can be prepared by known processes, for example by reducing an oxime or a nitrile with a suitable reducing agents, for example a complex metal hydride or Hydrogen in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction an alkyl halide or tosylate. To represent the cyclohexylamine, the Educts for the particularly the reductive amination of appropriately substituted Cyclohexanones with ammonium salts and sodium cyanoborohydride or with Ammonia and hydrogen in the presence of metal catalysts such as nickel, Ruthenium, rhodium or palladium with which the proportion of desired cis amine is particularly high. Another method is the Hydrogenation of amines in the presence of hydrogenation catalysts.

For the preparation of the starting materials for the particularly preferred cyclohexanyl derivatives The following implementations are particularly suitable:

1.) Alkyl, alkenyl, aryl derivatives (a = 1, b = 2, U, V = direct bond)

2.) Alkyl, alkenyl, aryl derivatives (a = 1, 2, 3, b = 1, 2, 3, U, V = direct bond)

3.) Cyclohex-3-enylamino and alkoxy derivatives

Preparation of 1-methoxy-1,4-cyclohexadienes, cyclohex-3-enones:
J. Chem. Soc. Perkin Trans 1, 7 (1983); J. Org. Chem. 29, 2351 (1964); J. Org. Chem. 41, 531 (1976).

With good plant tolerance and favorable warm-blood toxicity, the active substances are suitable for combating animal pests, in particular insects, arachnids, helminths and molluscs, very particularly preferably for combating insects and arachnids which are used in agriculture, in animal husbandry, in forests, in stock and material protection as well as in the hygiene sector. They are effective against normally sensitive and resistant species as well as all or individual stages of development. The pests mentioned above include:
From the order of Acarina z. B. Acarus siro, Argas spp., Ornithodoros spp., Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora, Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma spp., Ixodes spp., Psoroptes spp.,. Sarcoptes spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp., Tetranychus spp., Eotetranychus spp., Oligonychus spp., Eutetranychus spp.

From the order of the Isopoda z. B. Oniscus asselus, Armadium vulgar, Porcellio scaber.

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

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

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

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

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

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

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

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

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

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

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

From the order of Homoptera z. B. Aleurodes brassicae, Bemisia tabaci,  Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata Iugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

From the order of the Coleoptera z. B. Anobium punctatum, Rhizopertha dominica, Bruchidius obtectus, Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni, Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp., Psylloides chrysocephala, Epilachna varivestis, Atomaria spp., Oryzaephilus surinamensis, Anthonumus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma, Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

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

From the order of the Diptera z. B. Aedes spp., Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp., Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia spp., Cuterebra spp., Gastrophilus spp., Hypobosca spp., Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp., Tannia  spp., Bibio hortulanus, Oscinella frit, Phorbia spp., Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula paludosa.

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

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

From the class of the Helminth z. B. Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis as well as Fasciola and plant-damaging Nematodes e.g. B. those of the genera Meloidogyne, Heterodera, Ditylenchus, Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus and Xiphinema.

From the class of the Gastropoda z. B. Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp.

From the class of the Bivalva z. B. Dreissena spp.

The plant-parasitic nematodes that can be controlled according to the invention include, for example, the root-parasitic soil nematodes, such as, for. For example, those of the genera Meloidogyne (root-knot nematodes such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and of the genera Radopholus, such as Radopholus similis, Pratylenchus such as Pratyglenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus;
Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Halicotylenchus such as Haliocotylenchus multicinctus, Belonoaimus such as Belonoaimus longicausususus longusususus, such as longitude.

Furthermore, with the compounds according to the invention  Nematode genera Ditylenchus (stem parasites such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (leaf nematodes, such as Aphelenchoides ritzemabosi) and Anguina (flower nematodes, such as Anguina fight tritici).

The invention also relates to agents, in particular insecticidal and acaricidal agents, which the compounds of formula I in addition to suitable formulation auxiliaries contain.

The agents according to the invention contain the active ingredients of the formulas I in generally 1 to 95% by weight.

They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulations are therefore:
Wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil or water-based dispersions (SC), suspoemulsions (SE), dusts (DP), mordants, granules in the form of , Spray, elevator and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.

These individual types of formulation are known in principle and are described, for example, in:
Winnacker-Küchler, "Chemical Technology", Volume 7, C. Hauser Verlag Munich, 4th ed. 1986; van Falkenberg, "Pesticides Formulations", Marcel Dekker NY, 2nd Ed. 1972-73; K. Martens, "Spray Drying Handbook", 3rd Ed. 1979, G. Goodwin Ltd. London.

The necessary formulation aids such as inert materials, surfactants, solvents and other additives are also known and are described, for example, in:
Watkins, "Handbook of Insecticide Dust Diluents and Garriers," 2nd Ed., Darland Books, Caldwell NJ; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, NY; Marschen, MSolvents Guide ", 2nd Ed., Interscience, NY 1950; McCutcheon's," Detergents and Emulsifiers Annual ", MC Publ. Corp., Ridgewood NJ; Sisley and Wood," Encyclopedia of Surface Active Agents ", Chem. Publ Co. Inc., NY 1964; Schönfeldt, "interfacial ethylene oxide adducts", Wiss. Verlagsgesellschaft., Stuttgart 1967; Winnacker-Küchler, "Chemische Technologie", volume 7, C. Hauser Verlag Munich, 4th ed. 1986.

Based on these formulations, combinations can also be made with other pesticidal substances, fertilizers and / or Produce growth regulators, e.g. B. in the form of a finished formulation or as Tank mix. Spray powders are preparations that are evenly dispersible in water in addition to the active substance, in addition to a diluent or inert substance, wetting agents e.g. B. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or Alkylphenol sulfonates and dispersants, e.g. B. sodium lignosulfonic acid, Contain 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.

Emulsifiable concentrates are made by dissolving the active ingredient in one organic solvents, e.g. B. butanol, cyclohexanone, dimethylformamide, Xylene or even higher-boiling aromatics or hydrocarbons Addition of one or more emulsifiers produced. As emulsifiers can be used for example: alkylarylsulfonic acid calcium salts such as cadodecylbenzene sulfonate or nonionic emulsifiers such as Fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, Propylene oxide-ethylene oxide condensation products, alkyl polyethers, Sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or Polyoxethylene sorbitol ester.

Dusts are obtained by grinding the active ingredient with finely divided solids, e.g. B. talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth. Granules can be obtained either by spraying the Active ingredient can be produced on adsorbable, granulated inert material  or by applying active ingredient concentrates using adhesives, e.g. B. Polyvinyl alcohol, polyacrylic acid sodium or mineral oils on which Surface of carriers such as sand, kaolinite or granulated Inert material. Suitable active ingredients can also be used in the production of Fertilizer granules in the usual way - if desired in a mixture with Fertilizers - be granulated.

In wettable powders, the active ingredient concentration is e.g. B. about 10 to 90% by weight the rest of 100% by weight consists of customary formulation components. At emulsifiable concentrates, the active ingredient concentration can be about 5 to Amount to 80% by weight. Dust-like formulations usually contain 5 to 20 wt .-% of active ingredient, sprayable solutions about 2 to 20 wt .-%. At Granules, the active ingredient content depends in part on whether the effective Connection is liquid or solid and what granulation aids, fillers etc. can be used.

In addition, the active ingredient formulations mentioned optionally contain the usual adhesive, wetting, dispersing, emulsifying, penetrating, Solvents, fillers or carriers.

The concentrates available in commercial form are used optionally diluted in a conventional manner, e.g. B. with wettable powders, emulsifiable concentrates, dispersions and sometimes also Microgranules using water. Dusty and granular preparations as well as sprayable solutions are usually not used before use more diluted with other inert substances.

With the external conditions such as temperature, humidity and. a. varies the required application rate. It can fluctuate within wide limits, e.g. B. between 0.0005 and 10.0 kg / ha or more of active substance, preferably however, it is between 0.001 and 5 kg / ha.  

The active compounds according to the invention can be in their commercially available Formulations as well as those prepared from these formulations Application forms in mixtures with other active ingredients, such as insecticides, Attractants, sterilants, acaricides, nematicides, fungicides, growth regulating substances or herbicides.

Pesticides include, for example Phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, Tin compounds, substances produced by microorganisms u. a. Preferred Are mix partners

• 1. from the group of phosphorus compounds
  Acephate, Azamethiphos, Azinphos-ethyl-, Azinphosmethyl, Bromophos, Bromophos-ethyl, Chlorfenvinphos, Chlormephos, Chlorpyrifos, Chlorpyrifos methyl, Demeton, Demeton-S-methyl, Demeton-S-methyl sulfphone, Dialifos, Diazinon, Dichlorvos, O. Dicrotoph , O-1,2,2,2-Tetrachlorethylphosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos, Formothion, Heptenophos, Isozophos, Isothio Isoxathion, Malathion, Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoximosiphiphiphos -methyl, Profenofos, Propaphos, Proetamphos, Prothiofos, Pyraclofos, Pyridapenthion, Quinalphos, Sulprofos, Temephos, Terbufos, Tetrachlorvinphos, Thiometon, Triazophos, Trichlorphon, Vamidothion;
• 2. from the group of carbamates
  Aldicarb, 2-sec.-Butyphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, Isoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl (methyl) carbamate, Oxamyl, Pirimicarb, Pirimicarb Thiofanox, ethyl-4,6,9-triaza-4-benzyl-6, 10-dimethyl-8-oxa-7-oxo-5,11-dithia-9-dodecenoare (OK 135), 1-methylthio (ethylideneamino) - N-methyl-N- (morpholinothio) carbamate (UC 51717);
• 3. from the group of carboxylic acid esters
  Allethrin, alphametrin, 5-benzyl-3-furylmethyl- (E) - (1R) -cis, 2,2-di-methyl-3- (2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, bioallethrin, bioallethrip ((S) -cyclopentyl isomer), bioresmethrin, biphenates, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1RS) -trans-3- (4-tert.butylphenyl) -2,2-dimethylcyclopropane decarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, Esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D-isomer), perm -Pralethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, tralomethrin;
• 4. from the group of amidines
  Amitraz, chlorodime form;
• 5. from the group of tin compounds
  Cyhexatin, fenbutatin oxides;
• 6. Other
  Abamectin, Bacillus thuringiensis, Bensultap, Binapacryl, Bromopropylate, Buprofezin, Camphechlor, Cartap, Chlorobenzilate, Chlorfluazuron, 2- (4-Chlorphenyl) -4,5-diphenylthiophene (UBI-T 930), Chlorfentezine, Cyclopropanecarboxylic acid- (2-naphthyl) -methyl ester (Ro 12-0470), cyromazine, N- (3,5-dichloro-4- (1,1,2,3,3,3-hexafluoro-1-propyloxy) phenyl) carbamoyl -) - 2-chlorobenzcarboximidic acid ethyl ester, DDT, Dicofol, N- (N- (3,5-Di-chloro-4- (1,1,2,2-tetrafluoroethoxy) phenylamino) carbonyl) -2,6-difluorobenzamide (XRD 473), diflubenzuron, N- (2,3-dihydro-3-methyl-1,3-thiazol-2-ylidenes) -2,4-xylidines, dinobutone, dinocap, endosulfan, ethofenprox, (4-ethoxyphenyl) (dimethyl) (3- (3- phenoxyphenyl) propyl) silane, (4-ethoxyphenyl) (3- (4-fluoro-3-phenoxyphenyl) propyl) dimethylsilane, fenoxycarb, 2-fluoro-5- (4- (4-ethoxyphenyl) -4-methyl-1- pentyl) diphenyl ether (MTI 800), granulosic and nuclear polyhedron viruses, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, gamma-HCH, hexythiazox, hydramethylnon (AC 217300), ivermectin, 2 -Nitromethyl-4,5-dihydro-6H-thiazine (DS 52618), 2-nitromethyl-3,4-dihydrothiazole (SD 35651), 2-nitromethylene-1,2-thiazinan-3-ylcarbamaldehydes (WL 108477), propargite , Teflubenzuron, tetradifon, tetrasul, thiocyclam, trifumuron, imidacloprid.

The active substance content of those prepared from the commercially available formulations Forms of use can range from 0.00000001 to 95% by weight of active ingredient, preferably between 0.00001 and 1% by weight.

The application takes place in a customary manner adapted to the application forms Wise.

The active compounds according to the invention are also suitable for combating endo- and Ectoparasites in the veterinary field or in the field animal husbandry.

The active compounds according to the invention are used here in a known manner Way like by oral use in the form of e.g. tablets, Capsules, drinkers, granules, in the form of dermal application for example diving (dipping), spraying (spraying), pouring (pour-on and spot-on) and powdering as well as by parenteral application in the form for example the injection.

The new compounds of formula I according to the invention can accordingly also particularly advantageous in livestock farming (e.g. cattle, sheep, pigs and poultry such as chickens, geese, etc.). In a preferred one Embodiment of the invention, the animals the new compounds, if necessary in suitable formulations (see above) and if necessary with administered orally to drinking water or feed. Because an excretion in the feces in  done effectively, development can be done very easily in this way prevent insects in the animal droppings. The appropriate dosages and formulations are particularly of the type and Stage of development of farm animals and also dependent on the infestation pressure and can be easily determined and determined using the usual methods. The new compounds in cattle z. B. in doses of 0.01 to 1 mg / kg body weight can be used.

The compounds of the formula I according to the invention are also notable for an excellent fungicidal effect. Already in the plant tissue Invaded fungal pathogens can be successfully curated fight. This is particularly important and advantageous for such Fungal diseases that occur after infection with the usual ones Fungicides can no longer be effectively combated. The Spectrum of action of the claimed compounds covers various economically important, phytopathogenic fungi, such as. B. Plasmopara viticola, Erysiphe graminis, Phytophtora infestaus, Piriculavia oryzal, Pyrenophora teres, Leptosphaera noctorum, Pelliskulavia sasakii and Puccinia recondita.

The compounds of the invention are also suitable for use in technical areas, for example as wood preservatives, as Preservatives in paints, in cooling lubricants for the Metalworking or as a preservative in drilling and cutting oils.

The active compounds according to the invention can be in their commercially available Formulations either alone or in combination with other Fungicides known from the literature are used.

As fungicides known in the literature which, according to the invention, with the compounds of Formula I can be combined, for. B. to name the following products: Aldimorph, Andoprim, Anilazine, BAS 480F, BAS 450F, Benalaxyl, Benodanil, Benomyl, Binapacryl, Bitertanol, Bromuconazol, Buthiobate, Captafol, Captan,  Carbendazim, carboxin, CGA 173506, cyprofuram, dichlofluanid, dichlomezin, Diclobutrazole, diethofencarb, difenconazole (CGA 169374), difluconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Dithianon, Dodemorph, Dodine, Edifenfos, Ethirimol, Etridiazol, Fenarimol, Fenfuram, Fenpiclonil, Fenpropidin, fenpropimorph, fentin acetates, fentihydroxide, Ferimzone (TF164), Fluazinam, fluobenzimine, fluquinconazole, fluorimide, flusilazole, flutolanil, Flutriafol, Folpet, Fosetylaluminium, Fuberidazole, Fulsulfamide (MT-F 651), Furalaxyl, furconazole, furmecyclox, guazatine, hexaconazole, ICI A5504, Imazalil, Imibenconazole, Iprobefos, Iprodione, Isoprothiolane, KNF 317, Copper compounds such as Cu-oxychloride, Oxine-Cu, Cu-oxide, Mancozeb, Maneb, Mepanipyrim (KIF 3535), metconazole, mepronil, metalaxyl, methasulfocarb, Methfuroxam, MON 24000, myclobutanil, nabam, nitrothalidopropyl, nuarimol, Ofurace, oxadixyl, oxycarboxin, penconazole, pencycuron, PP 969, probenazole, Propineb, Prochloraz, Procymidon, Propamocarb, Propiconazol, Prothiocarb, Pyracarbolid, Pyrazophos, Pyrifenox, Pyroquilon, Rabenzazole, RH7592, Sulfur, tebuconazole, TF 167, thiabendazole, thicyofen, thiofanatemethyl, Thiram, Tolclofos-methyl, Tolylfluanid, Triadimefon, Triadimenol, Tricyclazole, Tridemorph, triflumizole, triforine, validamycin, vinchlozolin, XRD 563, Zineb, Sodium dodecyl sulfonate, sodium dodecyl sulfate, sodium C13 / C15 alcohol ether sulfonate, sodium cetostearyl phosphate ester, dioctyl sodium sulfosuccinate, Sodium isopropyl naphthalenesulfonate, sodium methylenebisnaphthalenes sulfonate, cetyl-trimethyl-ammonium chloride, salts of long-chain primary secondary or tertiary amines, alkyl propylene amines, lauryl pyrimidinium bromide, ethoxylated quaternized fatty amines, alkyl-dimethyl-benzyl ammonium chloride and 1-hydroxyethyl-2-alkyl-imidazoline.

The combination partners mentioned above are known active ingredients that for the most part in Ch.R. Worthing, S.B. Walker, The Pesticide Manual, 7th edition (1983), British Crop Protection Council. The active substance content of those prepared from the commercially available formulations Application forms can vary widely Drug concentration of use forms can range from 0.0001 to  95% by weight of active ingredient, preferably between 0.0001 and 1% by weight. The application takes place in a customary manner adapted to the application forms Wise.

The following examples serve to illustrate the invention without this would be limited to this.

A. Examples of formulation

• a) A dust is obtained by adding 10 parts by weight of active ingredient and Mixes 90 parts by weight of talc as an inert substance and in a hammer mill crushed.
• b) a wettable powder which is readily dispersible in water is obtained, by adding 25 parts by weight of active ingredient, 65 parts by weight of kaolin-containing quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight oleoylmethyltauric acid sodium as a wetting and dispersing agent and grind in a pin mill.
• c) A dispersion concentrate which is easily dispersible in water is prepared by mixing 40 parts by weight of active ingredient with 7 parts by weight of one Sulfosuccinic acid half ester, 2 parts by weight of a lignosulfonic acid Sodium salt and 51 parts by weight of water and mixed in one Grinding ball mill ground to a fineness of less than 5 microns.
• d) An emulsifiable concentrate can be prepared from 15 parts by weight Active ingredient, 75 parts by weight of cyclohexane as a solvent and 10 parts by weight Share oxyethylated nonylphenol (10 AEO) as an emulsifier.
• e) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granulate carrier material such as attapulgite, pumice granulate and / or quartz sand. It is advisable to use one  Suspension of the wettable powder from Example b) with a solids content of 30% and sprayed this onto the surface of an attapulgite granulate, dries and mixes intimately. The weight percentage is Spray powder about 5% and that of the inert carrier material about 95% of the finished granules.

B. Biological examples Insecticidal and acaricidal effects Example 1 Effect on the brown-backed rice leafhopper

Young rice plants (Oryza sativa) were diluted in an aqueous solution Spray powder concentrate with a concentration of 250 ppm (based on Active ingredient) and dipped after draining with L4 larval stages of the brown-backed rice leafhopper Nilaparvata lugens.

After being placed in a test cage, they were at 28 ° C and higher Humidity observed for 3 days and the mortality of the test animals certainly.

At 250 ppm the compounds according to Examples B and C produced a 100% Mortality in the experimental animals.

Example 2 Effect on Diabrotica undecimpunctata

Larvae (L3) of the Southern Corn Rootworm (Diabrotica undecimpunctata) were put on filter paper discs, each with 1 ml of an acetone dilution of a wettable powder in a concentration of 250 ppm based on active ingredient were soaked. After the acetone had evaporated, the shells sealed, these 3 days at 28 ° C and then the mortality of the Larvae determined.

The compounds according to Examples B and C showed 100% mortality.  

Example 3 Effect on the eggs of the American cotton bug

Filter paper discs with eggs on top (egg age: 2 days) of the American Cotton bugs (Oncopeltus fasciatus) were each with 1 ml of an aqueous Preparation, which contained 250 ppm of the respective active ingredient, treated. To The filter paper discs were dried on the surface at room temperature and maximum humidity in Petri dishes. After 7 days the ovicidal effect is determined. 100% ovicidal activity (egg mortality) was observed found in Examples B and C.

Example 4 Effect on the black bean aphid

Heavily populated with black bean aphids (Aphis fabae, full population) Field bean plants (Vicia faba) were treated with an aqueous preparation that Contained 250 ppm of the respective active ingredient until it started to drain sprayed. After 3 days of cultivation of the plants in the greenhouse, the Mortality of the aphids (full population) checked. 100% mortality was found in Examples A, B, C and D found.

Example 5 Effect on the common spider mite

Severely infested with common spider mites (Tetranychus urticae, full population) Bean plants (Phaseolus vulgaris ssp. Vulgaris var. Nanus) were grown with a aqueous preparation, which contained 250 ppm of the respective active ingredient, up to sprayed starting dripping. After 7 days of cultivating the plants in the The greenhouse mortality of the spider mites (full population) was checked. 100% mortality was found in Examples A, B, C and D.

Example 6 Effect on the fruit tree spider mite

Heavily infested with fruit tree spider mites (Panonychus ulmi, full population) Apple plants (Malus domestica) were treated with an aqueous preparation that  Contained 250 ppm of the respective active ingredient until it started to drain sprayed. After cultivating the plants in the greenhouse for 9 days, the Mortality of fruit tree spider mites (full population) checked. 100% Mortality was found in Examples A, B, C and D.

Example 7 Citrus Mealybug

With citrus smear lice (Planococcus citri, 2nd stage larvae) heavily infested bean plants (Phaseolus vulgaris ssp. vulgaris var. nanus) were with an aqueous preparation containing 250 ppm of each active ingredient contained, sprayed until drip begins. After 7 days of cultivation of the plants in the greenhouse became the mortality of the citrus oil lice (Full population) checked. 100% mortality was found in Examples B and C detected.

Example 8 Effect on the housefly

The bottom and lid of a Petri dish are filled with 3 ml on the inside an aqueous dilution of a wettable powder concentrate containing 250 ppm of Contained respective active ingredient, coated. After the surface has dried 24-hour-old houseflies (Musca domestica) were placed in the petri dishes set and closed with the treated lid. After 3 hours the mortality of the flies was checked at room temperature 20 ° C. 100% Killing was achieved with compounds B and C.

Example 9 Ovicidal effects (Manduca sexta)

Petri dishes were covered with Jaan filter paper on the inside and each Put 20 pieces of 1 day old manduca sexta eggs on the paper. Then about 1 ml of an artificial was placed in the middle of the Petri dish Insect food diet and the inside of the floor with eggs and feed diet with an aqueous wettable powder suspension of the test products accordingly  Sprayed 600 l / ha. After closing the petri dish and storage The mortality of the eggs was determined over 5 days at room temperature. Compound B was 100% effective.

Example 10

Cockroach larvae (L4), Blaberus craniifer, were dissolved in methanol Active ingredients injected.

After application of the compounds according to Example B and C (2 × 10 ^-4 g ai / animal), 100% mortality was found after 48 hours.

Example 11

Larvae (L4) of the tobacco owl, Manduca sexta, were dissolved in acetone Active ingredients injected.

After application of the compound according to Example B and C (2 × 10 ^-4 g ai / animal), 100% mortality was found after 48 hours.

Use as anti parasite Example 12 In vitro test on tropical cattle ticks (Boophilus microplus)

The effectiveness of the compounds according to the invention against ticks was demonstrated in the following experimental setup:
To prepare a suitable preparation of active compound, the active compounds were dissolved in 10% (w / v) in a mixture consisting of dimethylformamide (85 g), nonylphenol polyglycol ether (3 g) and oxyethylated castor oil (7 g), and the emulsion concentrates thus obtained were dissolved in water diluted a test concentration of 500 ppm.

Ten fully-sucked females were added to each of these active ingredient dilutions the tropical tick, Boophilus microplus, dipped for five minutes. The Ticks were then dried on filter paper and then for the purpose the egg laying with the back attached to an adhesive film. The storage the ticks took place in an oven at 28 ° C and a humidity of 90%.

As a control, female ticks were only immersed in water. For Efficacy was assessed two weeks after treatment Inhibition of egg laying used.

In this test, the compounds according to Example C act in one Active ingredient concentration of 500 ppm each a 100% inhibition of Oviposition.

C. Manufacturing Examples Example A 4- [4- (1,1,3,3-Tetramethylbutyl) cyclohex-3-enoxy] -5,6,7,8-tetrahydro-quinazoline

A solution of 2.3 g (11.2 mmol) of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3- enol in 20 ml of tetrahydrofuran was treated with 0.46 g (15.3 mmol) of sodium hydride (80% dispersion in mineral oil) and heated under reflux for 3 h. To Cooling to room temperature gave 1.7 g (10.2 mmol) of 4-chloro-5,6,7,8- tetrahydroquinazoline, dissolved in 5 ml of tetrahydrofuran, and heated a further 2 h under reflux. After cooling to room temperature, isopropanol became Added reaction solution, stirred for 15 minutes and then with Extracted methylene chloride. The organic phase was dried and constricted. For cleaning was carried out on silica gel with petroleum ether / ethyl acetate 1: 1 chromatographed. 2.3 g (66% of theory) of yellow oil were obtained, which gradually solidified.  

Preparation examples for 4- (4-alkylcyclohex-3-enylamino) pyrimidines Example B 4- [4- (1,1,3,3-tetramethylbutyl) cyclohex-3-enylamino] -5-chloro-6-eth-ylpyrimidine

1.2 g (13.5 mmol) of K₂CO₃ were placed in 10 ml of dimethylformamide and 1.6 g (9 mmol) of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3-enylamine were added and stirred at 80 ° C for 4 h. The cooled down was worked up Reaction solution taken up in water. It was extracted with ether, the combined organic phases washed with water, dried and constricted. For cleaning was carried out on silica gel with petroleum ether / ethyl acetate 5: 1 chromatographed. 1.3 g (43.3% of theory) of colorless oil were obtained.

Preparation of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3-enylamine

7 g (33 mmol) of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3-enone were dissolved in 100 g Isopropanol with 2.1 g (33 mmol) sodium cyanoborohydride and 25.9 g (0.33 mol) Ammonium acetate in the presence of 7 g molecular sieve (3A) for 72 h Room temperature stirred. The reaction solution was filtered and the filtrate constricted. The residue was taken up in 15% NaOH and with CH₂Cl₂ extracted. The combined methylene chloride phases were twice with diluted hydrochloric acid and the combined hydrochloric acid phases with 30% sodium hydroxide solution made basic. It was extracted with methylene chloride, dried the organic phase and concentrated. There remained 4.6 g (70% of theory) yellow oil.

Preparation of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3-enol

10.0 g (48 mmol) of 4 - [(1,1,3,3-tetramethyl) buty] cyclohex-3-enone were added in 60 ml of ethanol were introduced, 2.7 g (0.07 mol) of sodium borohydride, dissolved in 20 ml Water were added dropwise and the mixture was stirred at room temperature for 3 hours. The  Reaction solution was evaporated to dryness, the residue with water taken up and made weakly acidic at 0 ° C with 2nHCl. It was with Extracted ether, the combined ether phases with saturated NaCl solution washed and dried. After concentration, 7.1 g (70% of theory) were obtained Product as a colorless solid that was reacted without further purification.

Preparation of 4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-3-enone

40 g (0.17 mol) of 1-methoxy-4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-1,4-diene were placed in 500 ml of methanol and 600 ml of 10% at room temperature H₂SO₄ added dropwise and stirred for 2 hours. The reaction solution was on Water and extracted with ether. The combined ether phases were with H₂O and sat. NaCl solution washed and dried. After constriction 37 g (99% of theory) of colorless liquid were obtained without further purification was implemented.

Preparation of 1-methoxy-4 - [(1,1,3,3-tetramethyl) butyl] cyclohex-1,4-diene

105 g were added to a mixture of 180 ml of tert-butanol and 120 ml of THF (0.48 mol) of 4 - [(1,1,3,3-tetramethyl) butyl] anisole and at -78 ° C. 1600 ml of ammonia condensed. 13.3 g (1.9 mol) of lithium were added in portions and then refluxed for 1 h. It was getting slow Methanol and water were added to the reaction solution. After evaporating the Ammonia is extracted with ether. The organic phase was washed with water washed, dried over MgSO₄ and concentrated. 95.8 g (90% d. Th.) A colorless liquid that was reacted without further purification.

Preparation of 4 - [(1,1,3,3-tetramethyl) butyl] anisole

100 g (0.48 mol) of 4 - [(1,1,3,3-tetramethyl) butyl] were added to 260 ml of acetone. phenol and 93.8 g (0.68 mol) of K₂CO₃ submitted. Was added to the reaction solution 67 g (0.53 mol) of dimethyl sulfate were added dropwise. When the heat tone subsides  was heated to reflux with stirring for 4 h. There were 130 ml of acetone distilled off, 40 ml NH₄OH added and stirred for 10 min. Subsequently water was added to the reaction solution, extracted with ether and the combined organic phases with water, 2N NaOH and then with sat. Washed NaCl solution and dried over MgSO₄. After constriction 105 g (98% of theory) of solid product were obtained without further purification was implemented.

Preparation examples for 4- (1-aryl-1-cyclohexen-4-ylamino) pyrimidines Example C 5-chloro-6-ethyl-4- [1- (3-fluoro-4-methoxyphenyl) cyclohexen-4-ylamino -] - pyrimidine

1.6 g (7 mmol) 4-amino-1- (3-fluoro-4-methoxyphenyl) cyclohexene, 1.2 g (7 mmol) 4,5-dichloro-6-ethyl-pyrimidine and 1.4 g (14 mmol) triethylamine heated in 5 ml of toluene under reflux for 10 h. The mixture was worked up with toluene diluted and stirred with water. The organic phase was dried and constricted. For cleaning was carried out on silica gel with petroleum ether / ethyl acetate 7: 3 chromatographed. 0.6 g (27.6% of theory) of colorless oil were obtained, the gradually crystallized. Mp 86-87 ° C.

Production of the educt amine 4-amino-1- (3-fluoro-4-methoxyphenyl) cyclohexene

10.1 g (46 mmol) 1- (3-fluoro-4-methoxyphenyl) cyclohexen-4-one, 35.5 g (0.46 mol) ammonium acetate and 17 g 3 Å molecular sieve were in 250 ml Isopropanol submitted and with stirring 2.9 g (46 mmol) Sodium cyanoborohydride added in portions at 0 ° C. The mixture was stirred at room temperature for 72 h, the solvent was stripped off and the Residue was stirred out several times with methylene chloride / 2N sodium hydroxide solution. The  Combined methylene chloride phases were washed twice with dilute hydrochloric acid stirred and the combined hydrochloric acid phases strong with 30% sodium hydroxide solution made basic. The mixture was extracted with methylene chloride and the organic was dried Phase and constricted. 3.3 g (32.4% of theory) of product remained as a yellow oil, that gradually froze.

Preparation of 1- (3-fluoro-4-methoxyphenyl) cyclohexen-4-one

101.0 g (0.36 mol) of 4-hydroxy-4- (3-fluoro-4-methoxyphenyl) cyclohexanone ethylene ketal was mixed in a mixture of 500 ml of formic acid and 30 ml Water stirred for 24 h at room temperature. After removing the formic acid the residue was taken up with methylene chloride with Sodium bicarbonate solution and water washed, dried and constricted. This gave 71 g (89.5% of theory) of a colorless solid which was without further cleaning was implemented. Mp 68-70 ° C.

Preparation of 4-hydroxy-4- (3-fluoro-4-methoxyphenyl) cyclohexanone ethylene ketal

From 100 g (0.49 mol) of 4-bromo-2-fluoroanisole and 13 g (0.53 mol) of magnesium A Grignard solution was prepared in 350 ml of tetrahydrofuran. To a solution of 64.0 g (0.41 mol) was added dropwise at 20-30 ° C. Cyclohexane-1,4-dione-monoethylene ketal in 150 ml of tetrahydrofuran. You stirred 2 h at room temperature and 2 h at reflux. The approach was on hold poured, solid ammonium chloride added, diluted with 500 ml of toluene, the separated organic phase, dried and concentrated. 101 g were obtained (88% of theory) solid product which was reacted without further purification. Mp 126-128 ° C.  

Example D

A solution of 2.5 g (11 mmol) of 1- (3-fluoro-4-methoxy-phenyl) -4-hydroxy cyclohexene in 30 ml of tetrahydrofuran was treated with 0.36 g (12 mmol) Sodium hydride (80% dispersion in mineral oil) added and 2 h to the end the hydrogen evolution heated under reflux. After cooling down At room temperature, 2.0 g (11 mmol) of 4,5-dichloro-6-ethyl-pyrimidine were added and heated under reflux for a further 6 h. After removing the solvent taken up with water / methylene chloride, the organic phase dried and constricted. For cleaning was carried out on silica gel with petroleum ether / ethyl acetate 4: 1 chromatographed. 3.0 g (75.3% of theory) of a yellow solid were obtained. Mp 63-64 ° C.

Preparation of the starting material 1- (3-fluoro-4-methoxy-phenyl) -4-hydroxy-cyclohexene

10.0 g (45 mmol) of 1- (3-fluoro-4-methoxy-phenyl) -cyclohexen-4-one were in 100 ml of methanol dissolved and at 0 ° C in portions with 0.9 g (23 mmol) Sodium borohydride added. After stirring at room temperature for 1 h, 5 ml Acetone added, the solvent removed and with 2N sodium hydroxide solution and Methylene chloride added. The organic phase was dried and constricted. 7.4 g (74.0% of theory) of a yellow solid remained, the without further cleaning was implemented.

The following was obtained analogously:

Example E

4- (cis-4-tert-butylcyclohex-3-enyloxy) quinazoline; Mp 56-57 ° C.  

Example F

5-chloro-6-ethyl-4- (cis-4-tert-butylcyclohex-3-enylamino) pyrimidine; colorless Oil.

Example G

5-bromo-6-ethyl-4- (cis-4-tert-bu-l-cyclohex-3-enylamino) pyrimidine; - colorless Oil.

Example H

5-chloro-6-ethyl-4- [4- (3,4-dimethylphenyl) cyclohex-3-enylamino] pyrimidine; colorless oil.

Example I

4- [4- (3-fluoro-4-methoxy) phenylcyclohex-3-enyloxy] quinazoline; Mp 82-83 ° C.

Claims (21)

1. Compounds of the general formula I, in which
R¹ is hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₅) cycloalkyl or (C₃-C₅) halocycloalkyl;
R² and R³ are the same or different and are each independently hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₃-C₈) cycloalkyl, (C₃-C₈) halocycloalkyl, (C₁- C₄) alkoxy, (C₁-C₄) haloalkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₄) haloalkoxy- (C₁-C₄) alkyl, (C₁-C₄) -Alkoxy- (C₁-C₄) haloalkyl, (C₁-C₄) - haloalkoxy- (C₁-C₄) haloalkyl, (C₁-C₄) alkylamino, (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl , (C₁-C₄) alkylsulfonyl, (C₁-C₄) haloalkylthio, (C₁-C₄) haloalkylsulfinyl, (C₁-C₄) haloalkylsulfonyl, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, ( C₂-C₄) alkenyl, (C₂-C₄) alkynyl, (C₁-C₄) alkoxycarbonyl, cyano, (C₁-C₄) cyanoalkyl or thiocyano; or
R² and R³ together with the carbon atoms to which they are attached form an unsaturated 5- or 6-membered isocyclic ring which, if it is a 5-ring, may contain an oxygen or sulfur atom instead of CH₂, or the , if it is a 6-ring, may contain one or two nitrogen atoms instead of one or two CH units and which is optionally substituted by 1, 2 or 3 identical or different radicals and these radicals (C₁-C₄) - Alkyl, (C₁-C₄) haloalkyl is preferably trifluoromethyl, halogen, (C₁-C₄) alkoxy or (C₁-C₄) haloalkoxy, or
R² and R³ together with the carbon atoms to which they are attached form a saturated 5-, 6- or 7-membered isocyclic ring which may contain oxygen and / or sulfur instead of one or two CH₂ groups and which may be replaced by 1, 2 or 3 (C₁-C₄) alkyl groups is substituted;
A represents CH or N;
X represents NH, oxygen or S (O) _q , with q = 0, 1 or 2;
E represents a direct bond or a straight-chain or branched (C₁-C₄) alkanediyl group, preferably a direct bond;
a and b are the same or different and independently of one another represent the numbers 0, 1, 2 or 3, where a and b do not simultaneously mean 0;
R⁴ is halogen, (C₁-C₄) alkyl, (C₃-C₇) cycloalkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy or optionally substituted phenyl;
v represents 0, 1 or 2;
U is a direct single bond, oxygen, a group S (O) _y , with y = 0, 1 or 2 or a group NR⁶, where R⁶ is hydrogen, (C₁-C₄) alkyl or (C₁-C₄) alkoxy;
V for a direct single bond, carbonyl or a grouping of the formula is where Q is oxygen, sulfur or (C₁-C₄) alkylimino, T oxygen, sulfur or a group NR ^{6 '} , and T' (C₁-C₄) alkoxy, (C₁-C₄) alkylthio or NR ^{6 '} R ^{6 ''} means and where R ^{6 '} and R ^{6''are the} same or different and have the meanings given above for R⁶;
R⁵ is a radical from the series alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, nitro, alkyloximino or a group SiR⁷R⁸R⁹, where R⁷ and R⁸ (C₁-C₄) alkyl and R⁹ alkyl, cycloalkyl, Mean aryl and arylalkyl;
and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R⁵, R⁷, R⁸ and R⁹, optionally have at least one of the following features:

• i. one or more, preferably up to three non-adjacent CH₂ groups are through CO and / or heteroatom units, such as O, S (O) _y with y = 0, 1 or 2, NR ^{6 '''} or SiR ^7' R ^{8 '} replaced, where R ^{6''' has} the meanings given above for R⁶ and where R ^{7 '} , and R ^8' , have the meanings given above for R⁷ and R⁸;
• ii. 3 to 12 atoms of these radicals form an up to 12-membered cycle;
• iii. the radicals are optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, alkyl, cycloalkyl, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, haloalkyl, arylalkyl , Cycloalkylalkyl, alkoxy, haloalkoxy, alkylthio, cycloalkoxy, alkanoyloxy, haloalkanoyloxy, cycloalkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxy or cyano, hetero-cyclo-denatured with hydroxy, cyano-benzo, hydroxy-cyano-benzo-nitro or can be provided with up to three, in the case of halogen, preferably fluorine, up to the maximum number of identical or different substituents;
  and their salts.

2. Compounds of formula I according to claim 1, in which
R⁴ is halogen, preferably fluorine, chlorine and bromine, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy, (C₁-C₄) haloalkoxy or (C₁-C₄) - alkylthio ; and
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, optionally substituted aryl, optionally substituted heterocyclyl, cyano, halogen, hydroxy, carboxy, nitro, (C₁-C₂₀) alkyloximino or may represent a group SiR⁷R⁸R⁹, where R⁷ and R⁸ represent (C₁-C₄) alkyl and R⁹ (C₁-C₂₀) alkyl or optionally substituted aryl; and the alkyl, alkenyl, alkynyl or alkyloximino radicals mentioned for R⁵, R⁷, R⁸ and R⁹, optionally have at least one of the following features:

• i. one or more, preferably up to three non-adjacent CH₂ groups are through CO and / or heteroatom units, such as O, S (O) _y with y = 0, 1 or 2, NR ^{6 '''} or SiR ^7' R ^{8 '} , replaced, wherein R ^{6''' has} the meanings given above for R⁶ and where R ^{7 '} and R ^{8' have} the meanings given above for R⁷ and R⁸;
• ii. 3 to 8 atoms of these radicals form an up to 8-membered cycle;
• iii. the radicals are optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, (C₁-C₁₂) alkyl, (C₃-C₈) cycloalkyl, aryl, aryloxy , Arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (C₁-C₁₂) haloalkyl, aryl- (C₁-C₄) alkyl, (C₃-C₈) -cycloalkyl- (C₁-C₄) alkyl, (C₁-C₁ ₂) alkoxy , (C₁-C₁₂) haloalkoxy, (C₁-C₁₂) alkylthio, (C₃-C₈) cycloalkoxy, (C₁-C₁₂) alkanoyloxy, (C₁-C₁₂) haloalkanoyloxy, (C₃-C₈) cycloalkanoyloxy, ( C₃-C₈) -cycloalkyl- (C₁-C₁₂) alkanoyloxy, aroyloxy, aryl- (C₁-C₄) alkanoyloxy, (C₁-C₁₂) alkylsulfonyloxy, arylsulfonyloxy, heterocyclylcarbonyloxy, hydroxy, cyano or nitroaliphatic, wherein the cyclo substituted, cyclo substituted or heterocyclic ring systems under the just mentioned substituents unsubstituted or with up to three, in the case of halogen, preferably flu or can also be provided with the same or different substituents up to the maximum number and the remaining radicals and variables are as defined above; as well as their salts.

3. Compounds of formula I according to claim 1 or 2, in which
R1 is hydrogen or fluorine;
R² is (C₁-C₄) alkyl, cyclopropyl, halocyclopropyl, halogen (C₁-C₂) alkyl, methoxymethyl or cyano;
R³ is hydrogen, halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C₁-C₄) alkoxycarbonyl; or
R² and R³ together with the carbon atoms to which they are attached form an optionally substituted unsaturated 5- or 6-membered ring which, in the case of the 5-ring, may contain a sulfur atom instead of a CH₂ unit, or
R² and R³, together with the carbon atoms to which they are attached, form a saturated 5- or 6-membered ring which may contain a sulfur or an oxygen atom instead of a CH₂ unit;
A represents CH or N;
X represents NH or oxygen;
E stands for a direct bond;
a is the number 1 and b is the number 2,
R⁴ is hydrogen, (C₁-C₄) alkyl, trifluoromethyl or (C₁-C₄) alkoxy;
and the remaining residues and variables are as defined above;
as well as their salts. 4. Compounds of formula I according to any one of claims 1 to 3, in which
R1 is hydrogen;
R² is methyl, ethyl, propyl, isopropyl, 1-fluoroethyl, trifluoromethyl, cyclopropyl or methoxymethyl;
R³ is halogen, methyl, ethyl, methoxy, ethoxy, cyano or (C₁-C₄) alkoxycarbonyl, or
R² and R³ together with the ring system to which they are attached form the quinazoline or quinoline system which may be substituted by fluorine in the carbocyclic part, or
R² and R³ together with the carbon atoms to which they are attached form a saturated 6-membered ring which may contain an oxygen or sulfur atom instead of a CH₂ group;
r = 0;
U represents a direct bond or oxygen;
V represents a direct bond;
as well as their salts. 5. Compounds of formula I according to any one of claims 1 to 4, in which
R1 is hydrogen;
R² denotes ethyl, propyl, isopropyl, 1-fluoroethyl, trifluoromethyl or methoxymethyl,
R³ is fluorine, chlorine, bromine or methoxy;
or if A is nitrogen,
R² and R³ together with the ring system to which they are attached form the quinazoline system, which may be substituted with a fluorine atom, or
R² and R³ together with the ring system to which they are attached form the 5,6,7,8-tetrahydroquinazoline system;
A represents CH or N;
X represents NH or oxygen;
E stands for a direct bond;
a the number 1 and
b represents the number 2;
v = 0;
U means a direct bond or oxygen,
V represents a direct bond; as well as their salts. 6. Compounds of formula I according to any one of claims 1 to 5, in which
R1 is hydrogen;
R² is ethyl or methoxymethyl;
R³ is fluorine, chlorine, bromine or methoxy, or
R² and R³ for A = N together with the ring system to which they are attached form the quinazoline or the 5,6,7,8-tetrahydroquinazoline system;
R⁵ is (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl or (C₂-C₂₀) alkynyl, where 3-6 carbon atoms of these carbon radicals can form a cycle and / or these hydrocarbon radicals optionally with a phenyl radical may be substituted, which may be unsubstituted or provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents;
A represents CH or N;
X represents NH or oxygen;
E stands for a direct bond;
U and V together stand for a direct bond;
v = 0
the remaining radicals and variants are as defined above;
as well as their salts. 7. Compounds of formula I according to any one of claims 1 to 6, in which
R² is methoxymethyl and R³ is methoxy, or
R² is ethyl and R³ is chlorine or bromine,
R⁵ means (C₁-C₂₀) alkyl or (C₂-C₂₀) alkenyl, where 3-6 carbon atoms of this radical can form a cycle and / or this can optionally be substituted with a phenyl radical which is unsubstituted or with up to three, im In the case of fluorine, the same or different substituents can also be provided up to the maximum number;
X represents NH;
the remaining radicals and variants are as defined above;
as well as their salts. 8. A process for the preparation of compounds of formula I according to any one of claims 1 to 7, characterized in that a compound of formula II wherein A, R¹, R² and R³ have the meanings given under formula I and L represents a leaving group, with a compound of formula III wherein X, E, a, b, v, U, V, R⁴ and R⁵ have the meanings given in claim 1 under formula I, and the compounds of the formula I obtained in this way or otherwise, if R³ is hydrogen, optionally in halogenated at position 5 of the heterocycle or further derivatized in the side chain R⁵, and the compounds thus obtained are optionally converted into their salt. 9. Compositions containing at least one compound according to one of the Claims 1 to 7 and at least one formulation agent.   10. Fungicidal composition according to claim 9, containing a fungicidally active Amount of at least one compound according to one of Claims 1 to 7 together with the usual additives for this application. 11. Insecticidal, acaricidal, ixodicidal or nematicidal agent according to Claim 9, containing an effective amount of at least one compound according to one of claims 1 to 7 together with those for this application usual additives. 12. Plant protection products containing a fungicidal, insecticidal, acaricidal, ixodicidal or nematicidal amount of at least one compound according to one of the Claims 1 to 7 and at least one further active ingredient, preferably from the range of fungicides, insecticides, attractants, sterilants, acaricides, Nematicides and herbicides together with those customary for this application Auxiliaries and additives. 13. Agents for use in wood protection or as a preservative in Sealants, in paints, in cooling lubricants for metalworking or in drilling and cutting oils containing at least an effective amount a compound according to any one of claims 1 to 7 together with those for these applications usual auxiliaries and additives. 14. A compound according to any one of claims 1 to 7 or means according to Claim 9, for use as a veterinary medicinal product, preferably in the Control of endo- or ectoparasites. 15. A method for producing an agent according to any one of claims 9 to 14, characterized in that the active ingredient and the other additives together and brings it into a suitable form of application. 16. Use of a compound according to any one of claims 1 to 7 or  Agent according to one of claims 9, 10, 12 and 13 as a fungicide. 17. Use of a compound according to any one of claims 1 to 7 or an agent according to any one of claims 9, 10 and 13 as a wood preservative or as a preservative in sealants, in paints, in Cooling lubricants for metalworking or in drilling and cutting oils. 18. Process for combating phytopathogenic fungi, thereby characterized in that one looks at this or the plants infested by them, Surfaces or substrates or on seed a fungicidally effective amount of A compound according to any one of claims 1 to 7 or an agent according to applied one of claims 9, 10 and 11. 19. Procedures for controlling insect pests, acarina, mollusks and Nematodes, in which one looks at these or the plants infected by them, Surfaces or substrates an effective amount of a compound according to a of claims 1 to 7 or an agent according to any one of claims 9, 10 and 12 applied. 20. Use of compounds according to one of claims 1 to 7 or an agent according to any one of claims 9, 10 and 12 for combating Insect pests, acarina, mollusks and nematodes. 21. Seeds treated or coated with an effective amount of one A compound according to any one of claims 1 to 7 or an agent according to one of claims 9, 10 and 12.