DE19523906A1 - Substituted 1,3-dioxan-5-ylamino heterocycles, process for their preparation and their use as pesticides - Google Patents

Abstract

The invention pertains to new substituted 1,3-dioxan-5-ylamino heterocyclic compounds of formula (I), wherein A is CH or N; X is NH, O or S(O)q, with q = 0-2; Y is O or S(O)m, with m = 0-2, and R<1>, R<2>, R<3>, R<4>, R<4'>, and R<5> are as indicated in the description. The invention also pertains to methods for preparing said compounds and to their use as pesticides and fungicides.

Description

The invention relates to new substituted 1,3-dioxan-5-ylamino heterocycles, Process for their preparation and their use as Pesticides and fungicides.

It is already known that certain cycloalkylamino and alkoxy Show heterocyclic fungicidal, acaricidal and insecticidal activity (DE-A-42 08 254). The biological action of these compounds, however, is especially at low application rates and concentrations, not in all Satisfactory application examples.

There were new 1,3-dioxan-5-ylamino heterocycles of the general formula I found,

where the radicals and groups are as defined below, which is very good with good plant tolerance and favorable warm-blood toxicity good for controlling animal pests, such as insects, arachnids, Nematodes, helminths and mollusks, to combat endo- and Ectoparasites in the veterinary field and for the control of Harmful fungi are suitable.  

The invention therefore relates to compounds of the formula I in which
R¹ is hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or (C₃-C₅) cycloalkyl;
R² and R³ are the same or different and are each hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) haloalkenyl, (C₂-C₄) alkynyl , (C₂-C₄) -haloalkynyl, (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, halogen, hydroxy, (C₁-C₄) hydroxyalkyl , (C₁-C₄) alkanoyl, (C₁-C₄) alkanoyl- (C₁-C₄) alkyl, (C₁-C₄) haloalkanoyl, (C₃-C₅) cycloalkyl, (C₃-C₅) halocycloalkyl, cyano , (C₁-C₄) cyanoalkyl, nitro, (C₁-C₄) nitroalkyl, thiocyano, (C₁-C₄) thiocyanoalkyl, (C₁-C₄) alkoxycarbonyl, (C₁-C₄) alkoxycarbonyl- (C₁-C₄) -alkyl, (C₁-C₄) - haloalkoxycarbonyl, (C₁-C₄) -alkylthio, (C₁-C₄) -alkylthio- (C₁-Calkyl) -alkyl, (C₁-C₄) -haloalkylthio, (C₁-C₄) -alkylsulfinyl , (C₁-C₄) - haloalkylsulfinyl, (C -C₄) alkylsulfonyl, or (C₁-C₄) - haloalkylsulfonyl group; 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 which 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 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;
Y and Z are oxygen or a group S (O) _m with m = 0.1 or 2,
R⁴, R⁴, and R⁵ are substituents of the heteroaliphatic ring system;
R⁴ and R⁴ are hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkylthio;
R⁵ denotes alkyl, alkenyl, alkynyl, aryl or heterocyclyl, where the aryl or heterocyclyl radicals listed can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different radicals and in the alkyl mentioned, Alkenyl or alkynyl radicals one or more, preferably up to three, non-adjacent saturated carbon units through a carbonyl group or through heteroatom units, such as oxygen, S (O) _x , with x = 0, 1 or 2, NR⁶ or SiR⁷R⁸ can be replaced, where R⁶ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkanoyl and R⁷ and R⁸ are (C₁-C₄) alkyl, preferably methyl ;
and in which, in addition, 3 to 12 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle, and these hydrocarbon radicals with or without the stated variations, optionally with one or more, preferably up to three, in the case of fluorine, up to the maximum number on identical or different radicals from the series halogen, aryl, aryloxy, arylthio, cycloalkoxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, alkanoyl, cycloalkanoyl, haloalkanoyl, aroyl, arylalkanoyl, cycloalkylalkanoyloxycarbonyl, cycloalkoxyalkoxy, carbonyl, alkoxyloxyyloxycarbonyl heterocyclylalkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, alkanoyloxy, Halogenalkanoyloxy, cycloalkanoyloxy, Cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, Heterocycloylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, hydroxyl, cyano, thiocyano or nitro, w the cycloaliphatic, aromatic or heterocyclic ring systems may be unsubstituted under the just mentioned substituents or may be provided with up to three, in the case of fluorine also up to the maximum number of identical or different substituents, or
R⁴ and R⁵ together form a three- to eight-membered ring system which is spirocyclically linked to the ring system containing the heteroatoms Y and Z and in which one or two CH₂ groups, preferably a CH₂ group, are formed by heteroatom units such as oxygen, S ( O) _{n can be replaced} with n = 0, 1 or 2 or NR⁹, where R⁹ is hydrogen, alkyl, alkoxy, alkanoyl, benzoyl, aryl or heteroaryl, the benzoyl, aryl or heteroaryl radicals being unsubstituted or with up to three, in the case of fluorine also up to the maximum number of the same or
can be provided with different substituents, and the ring system formed from R⁴ and R⁵ can be unsubstituted or can be provided with up to three, but preferably one, substituent and these substituents are identical or different and are each alkyl, haloalkyl, alkoxy, alkylthio, aryl, aryloxy, Arylthio, arylalkyl, arylalkoxy, arylalkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, trialkylsilyl or alkoxycarbonyl, where the cycloaliphatic, aromatic or heterocyclic ring systems from the above-mentioned fluorine to unsubstituted or unsubstituted or unsubstituted or unsubstituted or unsubstituted or unsubstituted or unsubstituted or unsubstituted or unsubstituted by the above-mentioned substituents may have the same or different substituents for the maximum number,
or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring forms a condensed ring system, preferably the indane, 1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptane system and the benzene ring in these condensed systems unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents,
and their salts, preferably acid addition salts;
especially those compounds for which
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, aryl or heterocyclyl means, the aryl or heterocyclyl radicals listed unsubstituted or with up to three, in the case of fluorine can also be provided up to the maximum number of identical or different radicals and in the alkyl, alkenyl or alkynyl radicals mentioned one or more, preferably up to three non-adjacent saturated carbon units by a carbonyl group or by heteroatom units, such as oxygen, S (O) _x , with x = 0, 1 or 2, NR⁶ or SiR⁷R⁸ can be replaced, where R⁶ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) -Alkanoyl and R⁷ and R⁸ are (C₁-C₄) alkyl, preferably methyl,
and in which in addition 3 to 12 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle and these hydrocarbon radicals with or without the stated variations, optionally with one or more, preferably up to three, in the case of halogen up to the maximum number on identical or different radicals from the series halogen, aryl, aryloxy, arylthio, (C₃-C₈) -cycloalkoxy, (C₃-C₈) -cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (C₁-C₁₂) alkanoyl, (C₃-C₈ ) - Cycloalkanoyl, (C₂-C₁₂) -haloalkanoyl, aroyl, aryl- (C₁-C₄) -alkanoyl, (C₃-C -C) -cycloalkyl- (C₁-C₄) -alkanoyl, heterocyclyl- (C₁-C₄) -alkanoyl, (C₁-C₁₂) alkoxycarbonyl, (C₁-C₁₂) haloalkoxycarbonyl, (C₃-C₈) - cycloalkoxycarbonyl, (C₃-C₈) cycloalkyl- (C₁-C₄) alkoxycarbonyl-, aryl- (C₁-C₄) alkoxycarbonyl , Heterocyclyl- (C₁-C₄) alkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, (C₁-C₁ ) -Alkanoyloxy, (C₂-C₁₂) -haloalkanoylalkoxy, (C₃-C₈) -cycloalkanoyloxy, (C₃-C₈) -cycloalkyl- (C₁-C₄) -alkanoyloxy, aroyloxy, aryl- (C₁-C₄) -alkanoyloxy, heterocyclyl (C₁-C₄) alkanoyloxy, (C₁-C₁₂) alkylsulfonyloxy, arylsulfonyloxy, hydroxy, cyano, thiocyano or nitro may be substituted, the cycloaliphatic, aromatic or heterocyclic ring systems being unsubstituted or with up to three, im under the substituents just mentioned In the case of fluorine, the same or different substituents can also be provided up to the maximum number,
or R⁴ and R⁵ together form a three- to eight-membered ring system which is spirocyclically linked to the ring system containing the heteroatoms Y and Z and in which one or two CH₂ groups, preferably a CH₂ group, are formed by heteroatom units such as oxygen, S ( O) _{n can be replaced} with n = 0, 1 or 2 or NR⁹, where R⁹ is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) alkoxy, (C₁ C₈) alkanoyl, benzoyl, aryl or heteroaryl , where the benzoyl, aryl or heteroaryl radicals can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents and the ring system formed from R⁴ and R⁵ can be unsubstituted or with up to three, but preferably one, may be provided and these substituents are the same or different and each (C₁-C₈) alkyl, (C₁-C₈) haloalkyl, (C₁-C₈) alkoxy, (C₁-C₈) alkylthio, ( C₃-C₈) -cycloalkyl, (C₃-C₈) -cycloalkoxy, ( C₃-C₈) -cycloalkylthio, aryl, aryloxy, arylthio, aryl- (C₁-C₄) -alkyl, aryl- (C₁-C₄) -alkoxy, aryl- (C₁-C₄) -alkylthio, heterocycyl, heterocyclyloxy, heterocyclylthio, ( C₁-C₈) - trialkylsilyl, preferably (C₁-C₈) alkyl-dimethylsilyl- or (C₁-C₈) - alkoxycarbonyl, the cycloaliphatic, aromatic or heterocyclic ring systems being substituted by the just mentioned substituents or by up to three, im In the case of fluorine, the same or different substituents can also be provided up to the maximum number,
or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring forms a condensed ring system, preferably the indane, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene or benzocycloheptane system and the benzene ring in these condensed systems unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents, preference being given to the compounds X and R⁵ among the compounds for which the carbon atom between the heteroatoms Y and Z bears only the substituent R⁵ are cis-constant with each other.

Compounds of the formula I in which
R1 is hydrogen or fluorine;
R² is (C₁-C₄) alkyl, (C₁-C₄ alkenyl, (C₁-C₄) alkynyl, (C₁-C₄) haloalkyl, cyclopropyl, halocyclopropyl, methoxymethyl or cyano;
R³ is hydrogen, halogen, methyl, ethyl, ethynyl, methoxy, ethoxy, cyano, trifluoromethyl, fluoromethylthio or methoxycarbonyl; 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 can contain a sulfur or an oxygen atom instead of a CH₂ unit;
A represents CH or N;
X represents NH or oxygen;
Y and Z each represent oxygen or sulfur;
R⁴ represents hydrogen, (C₁-C₄) alkyl, trifluoromethyl or (C₁-C₄) alkoxy;
R⁴ represents hydrogen;
in particular those compounds in which
R¹ is hydrogen,
R² is methyl, ethyl, propyl, isopropyl, (C₁-C₂) fluoroalkyl, cyclopropyl or methoxymethyl;
R³ is halogen, methyl, ethyl, ethynyl, methoxy, ethoxy, trifluoromethyl, fluoromethylthio, methoxycarbonyl or cyano; or
R² and R³ together with the ring system to which they are attached form the quinazoline or quinoline system which can 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;
R⁴ is hydrogen or methyl.

Compounds of the formula I in which
R1 is hydrogen;
R² is ethyl, propyl, isopropyl, 1-fluoroethyl or methoxymethyl;
R³ represents fluorine, chlorine, bromine, cyano 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;
A represents CH or N;
X represents NH;
Y and Z represent oxygen or sulfur;
R⁴ represents hydrogen or methyl;
R⁴ means hydrogen.

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
A represents CH or N;
X represents NH;
Y and Z are oxygen;
R⁴ and R⁴ represent hydrogen;
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, aryl or heterocyclyl means, the aryl or heterocyclyl radicals listed unsubstituted or with up to three, in the case of fluorine can also be provided up to the maximum number of identical or different radicals and in the alkyl, alkenyl or alkynyl radicals mentioned one or more, preferably up to three non-adjacent saturated carbon units can be replaced by heteroatom units, such as oxygen or SiR⁷R⁸ where R wobei and R⁸ are (C₁-C₄) alkyl, preferably methyl,
and in which in addition 3 to 6 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle and these hydrocarbon radicals with or without the stated variations, optionally with one or more, preferably up to three, in the case of halogen up to the maximum number may be substituted on identical or different radicals from the halogen series, preferably fluorine, aryl, aryloxy, arylthio, (C₃-C₈) cycloalkoxy, (C₃-C₈) cycloalkylthio, heterocyclyl, heterocyclyloxy or (C₁-C₂) alkoxycarbonyl, where the cycloaliphatic, aromatic or heterocyclic ring systems can be unsubstituted under the just mentioned substituents or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents,
or R⁴ and R⁵ together form a five- or six-membered ring system which is preferably spirocyclically linked to the ring system containing the heteroatoms Y and Z and in which a CH₂ group is formed by heteroatom units such as oxygen, S (O) _n with n = 0 , 1 or 2 or NR⁹ can be replaced,
where R⁹ is hydrogen (C₁-C₈) alkyl, (C₁-C₈) alkanoyl, benzoyl, aryl or heteroaryl, the benzoyl, aryl or heteroaryl radicals unsubstituted or with up to three, in the case of fluorine also up may be provided to the maximum number of identical or different substituents, and the ring system formed from R⁴ and R⁵ may be unsubstituted or may be provided with up to three, but preferably one, substituent and these substituents are the same or different and are each (C₁-C₈) alkyl , (C₃-C₈) -cycloalkyl, aryl or aryl- (C₁-C₄) -alkyl mean, the cycloaliphatic, aromatic or heterocyclic ring systems under the just mentioned substituents unsubstituted or with up to three in the case of fluorine also up to the maximum number same or different substituents can be provided, or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring together a condensed ring system bil det, preferably the indane, 1,2,3,4-tetrahydronaphthalene, decalin or benzocycloheptane system, and the benzene ring in these condensed systems unsubstituted or with up to three, in the case of fluorine also up to the maximum number of the same or different Substituents can be provided, wherein among the compounds for which the carbon atom between the heteroatoms Y and Z carries only the substituent R⁵, the substituents X and R⁵ on the heteroaliphatic six-membered ring are preferably cis to one another; especially such connections for the
R⁵ (C₁-C₁₅) alkyl, aryl or heterocyclyl in the sense of heteroaromatic ring system, where the aryl or heterocyclyl radical can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different radicals and in said alkyl radical one or more, preferably up to three, non-adjacent saturated carbon units can be replaced by oxygen,
and in which, in addition, 3 to 8 atoms of this optionally modified alkyl radical can form a cycle and this alkyl radical with or without the specified variations, optionally with one or more halogen atoms, in the case of fluorine also up to a maximum number or with an aryl -Rest may be substituted and this aryl residue may be unsubstituted or may be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents, and the substituents X and R heter on the heteroaliphatic six-membered ring are preferably cis to one another.

In the above formula, "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 to 4 carbon atoms, such as. B. to understand the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical;
under the expression "(C₁-C₈) alkyl" the aforementioned alkyl radicals, such as. B. the pentyl, 2-methylbutyl, 1,1-dimethylpropyl, hexyl, heptyl, octyl, or the 1,1,3,3-tetramethylbutyl radical;
under the expression "(C₁-C₂₀) alkyl" the aforementioned alkyl radicals, and z. B. 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 "(C₁-C₂) fluoroalkyl" z. B. to understand the 1-fluoroethyl, 2-fluoroethyl, 1,1-difluoroethyl or the 2,2,2-trifluoroethyl group;
under the term "cycloalkyl" preferably (C₃-C₈) cycloalkyl;
under the term "cycloalkoxy" preferably (C₃-C₈) cycloalkoxy;
under the term "cycloalkylthio" preferably (C₃-C₈) cycloalkylthio;
under the expression "(C₃-C₅) cycloalkyl" the cyclopropyl, cyclobutyl or cyclopentyl group;
under the expression "(C₃-C₈) -cycloalkyl", the radicals mentioned above under "(C₃-C₅) -cycloalkyl" and the cyclohexyl, cycloheptyl or cyclooctyl radical;
under the expression "(C₃-C₅) -halogenocycloalkyl" one of the (C₃-C₅) -cycloalkyl radicals listed above in which one or more, in the case of fluorine, if appropriate also all hydrogen atoms, have been replaced by halogen, preferably fluorine or chlorine, such as the 2,2-difluoro or 2,2-dichlorocyclopropane group or the fluorocyclopentane radical;
under the expression "(C₂-C₄) alkenyl" z. B. the vinyl, allyl, 2-methyl-2-propene 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) haloalkenyl" a (C₂-C₄) alkenyl group in which the hydrogen atoms are partially or in the case of fluorine also completely replaced by halogen, preferably fluorine or chlorine;
under the expression "(C₂-C₄) alkynyl" z. B. the ethynyl, propargyl, 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 "(C₂-C₄) haloalkynyl" a (C₂-C₄) alkynyl group in which the hydrogen atoms are partially, in the case of fluorine also completely, replaced by halogen atoms, preferably fluorine or chlorine;
under the expression "(C₁-C₄) hydroxyalkyl" z. B. the hydroxymethyl, 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-1-methyl-ethyl or the 1-hydroxypropyl group;
under the expression "(C₁-C₄) alkanoyl" z. B. the formyl, acetyl, propionyl, 2-methylpropionyl or butyryl group;
under the expression "(C₁-C₁₂) alkanoyl" z. B. the aforementioned radicals and, for example, the valeroyl, pivaloyl, hexanoyl, decanoyl or the dodecanoyl group;
under the expression "(C₂-C₄) haloalkanoyl" a (C₁-C₄) alkanoyl group in which the hydrogen atoms are partially, in the case of fluorine also completely, replaced by halogen atoms, preferably fluorine or chlorine;
under the expression "(C₂-C₁₂) haloalkanoyl" a (C₁-C₂₀) alkanoyl group in which the hydrogen atoms are partially, in the case of fluorine also completely, replaced by halogen atoms, preferably fluorine or chlorine;
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-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 expression "(C₁-C₄) haloalkoxycarbonyl" a (C₁-C₄) alkoxycarbonyl group in which one or more, in the case of fluorine, if appropriate also all hydrogen atoms, are replaced by halogen, preferably fluorine or chlorine;
under the expression "(C₁-C₄) alkylthio" an alkylthio group whose hydrocarbon radical has the meaning given under the expression "(C₁-C₄) alkyl";
under the expression "(C₁-C₄) haloalkylthio" a (C₁-C₄) alkylthio group in which one or more, in the case of fluorine, if appropriate, all the hydrogen atoms in the hydrocarbon part are replaced by halogen, in particular chlorine or fluorine ;
under the term "fluoromethylthio" the mono-, di- and trifluoromethylthio group;
under the expression "(C₁-C₄) alkylsulfinyl" z. B. the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butylsulfinyl group;
under the expression "(C₁-C₄) alkylsulfonyl" z. B. the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butylsulfonyl group;
under the terms "(C₁ C₄) haloalkylsulfinyl" and "(C₁-C₄) haloalkylsulfonyl" (C₁-C₄) alkylsulfinyl and sulfonyl radicals with the meanings given above, in which one or more, in the case of fluorine optionally also all hydrogen atoms of the hydrocarbon part are replaced by halogen, in particular chlorine or fluorine;
under the terms "fluoromethylsulfinyl" and "fluoromethylsulfonyl" the mono-, di- and trifluoromethyl-sulfinyl and -sulfonyl group;
under the term "(C₁-C₄) alkoxy" an alkoxy group whose hydrocarbon radical has the meaning given under the term "(C₁-C₄) alkyl";
under the expression "(C₁-C₄) -haloalkoxy" a haloalkoxy group whose halogenated hydrocarbon radical has the meaning given under the expression "(C₁-C₄) -haloalkyl";
under the expression "(C₁-C₄) alkoxy- (C₁-C₄) alkyl", for example a 1-methoxyethylene 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 terms "(C₁-C₄) haloalkoxy- (C₁-C₄) alkyl," (C₁-C₄) alkoxy- (C₁-C₄) haloalkyl "and" (C₁-C₄) haloalkoxy- (C₁- C₄) haloalkyl "(C₁-C₄) alkoxy- (C₁-C₄) alkyl radicals with the meanings given above, in which one or more, in the case of fluorine, optionally also all hydrogen atoms of the corresponding hydrocarbon moieties by halogen, chlorine or fluorine are preferably replaced;
under the expression "(C₁-C₄) alkylthio- (C₁-C₄) alkyl" for example methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl, 2-ethylthioethyl or 3-methylthiopropyl;
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;
under the expression "heterocyclyl" a heteroaromatic or heteroaliphatic ring system, under "heteroaromatic ring system" an aryl radical in which at least one CH group is replaced by N and / or at least two adjacent CH groups are replaced by S, NH or O. understand 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 is replaced by O, S or a group NR¹¹ and R¹¹ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) -Alkoxy or aryl;
under the expression "arylthio" z. B. the phenylthio or the 1- or 2-naphthylthio group;
under the term "aryloxy" z. B. the phenoxy or 1- or 2-naphthyloxy group;
under the expression "heterocyclyloxy" or "heterocyclylthio" one of the abovementioned heterocyclic radicals which are linked via an oxygen or sulfur atom;
under the expression "(C₃-C₈) -cycloalkoxy" or "(C₃-C₈) -cycloalkylthio" one of the above-mentioned (C₃-C₈) -cycloalkyl radicals which are linked via an oxygen or sulfur atom;
under the expression "aroyl" z. B. the benzoyl, naphthoyl or the biphenylcarbonyl group;
under the expression "aryl (C₁-C₄) alkanoyl" z. B. the phenylacetyl, 3-phenylpropionyl, 2-phenylpropionyl, 2-methyl-2-phenyl-propionyl, 4-phenylbutyryl or the naphthylacetyl group;
under the expression "(C₃-C₈) cycloalkyl (C₁-C₄) alkanoyl" z. B. the cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, cyclohexylacetyl or the cyclohexylbutyryl group;
under the expression "heterocyclyl- (C₁-C₄) alkanoyl" z. B. the Thenoyl, Furoyl, Nicotinoyl, Thienylacetyl or the pyridine-propionyl group;
under the expression "(C₃-C₈) cycloalkoxycarbonyl" z. B. the cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl or the cycloheptyloxycarbonyl group;
under the expression "(C₃-C₈) cycloalkyl- (C₁-C₄) alkoxycarbonyl" z. B. the cyclopropylmethoxycarbonyl, cyclobutylmethoxycarbonyl, cyclopentyloxymethoxycarbonyl, cyclohexyloxymethoxycarbonyl, 1- (cyclohexyl) ethoxycarbonyl or the 2- (cyclohexyl) ethoxycarbonyl group;
under the expression "aryl (C₁-C₄) alkoxycarbonyl" z. B. the benzyloxycarbonyl, 1-naphthylmethoxycarbonyl, 2-naphthylmethoxycarbonyl, 1-phenyl-ethoxycarbonyl or the 2-phenyl-ethoxycarbonyl group; under the expression "heterocyclyl- (C₁-C₄) alkoxycarbonyl", e.g. B. the thienylmethoxycarbonyl, furylmethoxycarbonyl, tetrahydrofurylmethoxycarbonyl or the pyridylethoxycarbonyl group;
under the term "aryloxycarbonyl" z. B. the phenoxycarbonyl, naphthoxycarbonyl or the biphenyloxycarbonyl group;
under the term "hetercyclyloxycarbonyl" z. B. the tetrahydropyran-4-oxycarbonyl group;
under the expression "(C₁-C₂₀) alkanoyloxy" z. B. the formyloxy, acetoxy, propionyloxy, butyryloxy, pivaloyloxy, valeroyloxy or the hexanoyloxy group;
under the expression "(C₂-C₂₀) haloalkanoyloxy" a (C₂-C₂₀) alkanoyloxy group in which one or more, in the case of fluorine, if appropriate, all the hydrogen atoms in the hydrocarbon part are replaced by halogen, in particular fluorine or chlorine;
under the expression "(C₃-C₈) cycloalkanoyloxy" z. B. the cyclopropanoyloxy, cyclobutenoyloxy, cyclopentanoyloxy, cyclohexanoyloxy or the cycloheptanoyloxy group;
under the expression "(C₃-C₈) cycloalkyl- (C₁-C₄) alkanoyloxy" z. B. the cyclopropylcarbonyloxy, cyclopropylacetoxy, cyclobutylcarbonyloxy, cyclopentylcarbonyloxy, cyclohexylcarbonyloxy, cyclohexylacetoxy or the 4-cyclohexyl-butyryloxy group;
under the term "aroyloxy" e.g. B. the benzoyloxy or the naphthoyloxy group;
under the expression "aryl (C₁-C₄) alkanoyloxy" z. B. the benzoyloxy, naphthoyloxy, biphenylcarbonyloxy, phenylacetoxy or the phenylbutyryloxy group;
under the expression "heterocyclyl- (C₁-C₄) alkanoyloxy" z. B. the thienylcarbonyloxy, thienylacetoxy, pyridylcarbonyloxy or the pyrimidinylcarbonyloxy group;
under the expression "(C₁-C₂₀) alkylsulfonyloxy" z. B. the methane, ethane, butane or hexanesulfonyloxy group;
under the term "arylsulfonyloxy" e.g. B. the phenylsulfonyloxy or the toluenesulfonyloxy group.

The substituents with which the various aliphatic, aromatic and heterocyclic ring systems can be provided include, for. B. halogen, nitro, cyano, di- (C₁-C₄) alkylaminio, (C₁-C₄) alkyl, (C₃-Cd₈) cycloalkyl, (C₁-C₄) -trialkylsilyl, (C₁-C₄) alkoxy, (C₁-C₄) alkoxy- (C₁-C₄) alkyl, (C₁-C₂) alkoxy- [CH₂CH₂O] _1,2- ethoxy, (C₁-C₄) alkylthio, (C₁-C₄) alkylsulfinyl, ( C₁-C₄) - alkylsulfonyl, phenyl, benzyl, phenoxy, halophenoxy, (C₁-C₄) alkylphenoxy, (C₁-C₄) alkoxyphenoxy, phenylthio, heterocyclyl, heterocylylthio or heterocyclyloxy, one of the alkyl radicals and the radicals derived therefrom or one of them several hydrogen atoms, in the case of fluorine also up to the maximum number can be replaced by halogen, preferably chlorine or fluorine, where in the event that these substituents are (C₁-C₄) alkyl, these can also be cyclically linked and condensed therein Ring systems such as B. indan, di, tetra or decahydronaphthyl or benzocycloheptane system one or two aliphatic carbon units can be replaced by heteroatom units such as oxygen or sulfur and one or more hydrogen atoms on the aliphatic carbon atom units, in the case of Fluorine can also be replaced up to the maximum number by halogen or (C₁-C₄) alkyl.

Furthermore, under the definition that "in said alkyl, alkenyl or alkynyl radicals one or more, preferably up to three non-adjacent saturated carbon units by a carbonyl group or by heteroatom units, such as oxygen, S (O ) _x , can be replaced with x = 0, 1 or 2, NR⁶ or SiR⁷R,, where R⁶ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkanoyl and R⁷ and R⁸ (C₁-C₄) alkyl, preferably methyl
and in which, in addition, 3 to 12 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle, and these hydrocarbon radicals with or without the stated variations, optionally with one or more, preferably up to three, in the case of fluorine, up to the maximum number on identical or different radicals from the series halogen, aryl, aryloxy, arylthio, cycloalkoxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, alkanoyl, cycloalkanoyl, haloalkanoyl, aroyl, arylalkanoyl, cycloalkylalkanoyloxycarbonyl, cycloalkoxyalkoxy, carbonyl, alkoxyloxyyloxycarbonyl heterocyclylalkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, alkanoyloxy, Halogenalkanoyloxy, cycloalkanoyloxy, Cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, Heterocycloylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, hydroxyl, cyano, thiocyano or nitro, w The cycloaliphatic, aromatic or heterocyclic ring systems may be unsubstituted under the just mentioned substituents or may be provided with up to three, in the case of fluorine also up to the maximum number of identical or different substituents, the cycloaliphatic, aromatic or heterocyclic ring systems being among the just mentioned substituents may be unsubstituted or may have up to three, in the case of fluorine, up to the maximum number of identical or different substituents ",
e.g. B. to understand:
Alkoxyalkyl radicals, such as. B. the methoxymethyl, methoxyethyl or ethoxyethyl group; or
Alkoxy-alkoxy-alkyl radicals, such as. B. the methoxy or the ethoxy-ethoxyethyl 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, preferably alkyl-dimethylsilyl-alkyl radicals, such as, for. B. the trimethylsilylmethyl or the trimethylsilylethyl group; or
Trialkylsilyl, preferably alkyldimethylsilyl radicals, such as. B. the trimethylsilyl, ethyldimethylsilyl, tert-butyldimethylsilyl or the octyldimethylsilyl group; or
Cycloalkyldialkylsilyl-, preferably Cycloalkyldimethylsilyl residues, such as. B. the cyclohexyldimethylsilyl group; or
Aryldialkylsilyl-, preferably aryldimethylsilyl radicals such as. B. phenyldimethylsilyl group; or
Arylalkyldialkylsilyl, preferably aryldimethylsilyl radicals such as. B. the benzyldimethylsilyl or the phenylethyldimethylsilyl group; or
Alkanoylalkyl radicals such as. B. the acetylmethyl or the pivaloylmethyl group; or
Cycloalkanoylalkyl radicals such as. B. the cyclopropylcarbonylmethyl or the cyclohexylcarbonylmethyl group; or
Halogenalkanoylalkyl residues such as. B. the trifluoro or trichloroacetylmethyl group; or
Aroylalkyl radicals such as. B. the benzoyl or naphthoylalkyl radicals such as. B. the phenylacetylmethyl group; or
Heterocyclylcarbonylalkyl residues such as. B. the thienyl or pyridylacetylmethyl 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 residues, such as. B. the thienylmethyl, pyridylmethyl, furfuryl, tetrahydrofurfuryl, tetrahydropyranylmethyl or the 1,3-dioxalane-2-methyl group; or
Aryloxyalkyl radicals, such as. B. the phenoxymethyl or naphthoxymethyl group; or
Cycloalkyl residues, monocyclic such as. B. the cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical, bicyclic such as. B. the norbornyl radical or the bicyclo [2,2,2] octane radical or condensed like the decahydronaphthyl radical;
Alkyl cycloalkyl radicals such as. B. the 4-methyl or 4-tert-butylcyclohexyl group or the 1-methyl-cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl group;
Cycloalkyl-alkyl radicals such as. B. the cyclohexylmethyl or ethyl group;
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 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, malonic acid, Oxalic acid, fumaric acid, adipic acid, stearic acid, oleic acid, methanesulfonic acid, Benzenesulfonic acid or toluenesulfonic acid.

In addition to the cis / trans isomerism mentioned on the cycloalkyl group, the Compounds of formula I partially one or more asymmetrical Carbon atoms or stereoisomers on double bonds. It can therefore Enantiomers or diastereomers occur. The invention includes both pure isomers as well as their mixtures. The mixtures of diasteromers can according to common methods, for. B. by selective crystallization suitable solvents or by chromatography in the components be separated. Racemates can be added to the Enantiomers are separated, e.g. B. by salt formation with an optical  active acid, separation of the diastereomeric salts and release of the pure Enantiomers using 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, for example halogen, alkylthio, alkanesulfonyloxy or Arylsulfonyloxy, alkylsulfonyl or arylsulfonyl means with a nucleophile of formula III

wherein X, Y, Z, R⁴, R⁴, and R⁵ have the meanings given above under formula I, implemented and obtained in the same or another way Compounds of formula I, optionally the nitrogen heterocycle or Side chain R⁵ further derivatized.

The substitution reaction described above is known in principle. The Leaving group Z can be varied within wide limits and can, for example, be a Halogen atom such as fluorine, chlorine, bromine or iodine mean or alkylthio such 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 to 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 performed. It mixtures of the solvents mentioned can also be used.

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 compounds of the formula II required as starting products are mostly known from the literature or can be analogous to known methods be produced (cf. EP 370 391, EP 470 600, DOS 43 31179, DOS 44 04 702.

Suitable is used to prepare the nucleophiles of the formula III substituted 1,3-dioxan-5-ones or 1,3-dithian-5-ones from (A.A. Marei, R.A. Raphael, J. Chem. Soc. 1960, 886; H. Vorbrüggen, Acta Chem. Scand., 1982, 420; B. Bockstiegel, Synthesis 1989, 493; A. Lüttringhaus, M. Mohr, N. Engelhard, Liebigs Ann. Chem. 661 (1963) 84.) and converts them reductive amination (H₂, NH₃, metal catalyst or Ammonium acetate / sodium cyanoborohydride or Leuckart-Wallach reduction in the corresponding amines or by reduction with a complex Metal hydride in the corresponding alcohols. To make the particularly  preferred cis derivatives are particularly suitable for reductive amination a rhodium or a rhodium / palladium mixed catalyst, as a complex Metal hydride are particularly suitable, in addition to the hydrogen Wear alkyl substituents with a large amount of space, such as. B. ®L-Selectride.

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

in which R¹, R², R³, R⁴ ,, A, X, Y and Z are those given above for formula I. Have meanings, reacted with a compound of the formula V,

wherein R⁴ and R⁵ have the meanings given for formula I and in the compounds of the formula I obtained in this way or in another way Nitrogen heterocycle or the side chain R⁵ further varied.

The implementation is conveniently such that the compounds of Formula IV and formula V in the presence of an acid catalyst in one Temperature range of 20-200 ° C, preferably between 600 and 150 ° C in Substance or can react in an inert organic solvent.

The ketalization reaction described above is known in principle. She will be in a temperature range of 20-200 ° C, preferably between 600 and 150 ° C in the presence of an acidic dehydration catalyst, in bulk  or carried out in an inert solvent. Suitable catalysts are e.g. B. hydrochloric acid, sulfuric acid, phosphoric acid, sodium hydrogen sulfate, Sulfonic acid, such as methane or toluenesulfonic acid, phosphorus V-oxide, iron (III) - chloride, zinc chloride, anhydrous copper sulfate, iodine or acid Ion exchangers such as B. ®Amberlite IR-120. The one formed in the reaction Water is expedient by distilling off, if necessary, under reduced pressure or by azeotropic distillation using a Entrainer removed from the reaction mixture. Suitable entrainer are z. As benzene, toluene, xylene or petroleum ether.

The compounds of formula IV required as starting products can be as can be synthesized as follows:

The reaction conditions of the reactions described under a) and b) correspond to that of the preparation of the compounds III from the Compounds of the formula II. The starting materials of the formula VIa are commercially available, known in the literature or can be synthesized analogously to known processes (see M. Kujima, Yakugaku Zasshi 90, (1970), 670).  

Compounds of the formula VIb are used in a protected form. A suitable protective group is e.g. B. the benzyl group after the implementation is removed hydrogenolytically. The starting materials of the formula VIb are commercially available, known in the literature or can be synthesized analogously to known processes.

The active ingredients are suitable for good plant tolerance and cheaper Warmblood toxicity to control animal pests, in particular Insects, arachnids, helminths and molluscs, especially preferred to control insects and arachnids used in agriculture animal breeding, in forests, in the protection of stocks and materials and on the Hygiene sector occur. They are against normally sensitive and resistant species as well as all or individual stages of development. To the above Pests 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., Chorioptes 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 lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.

From the order of the Lepidoptera z. B. Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padella, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., 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.

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, Heliocotylenchus such as Haliocotylenchus multicinctus, Belonoaimus such as Belonoaimus Trachusususus longusus x longus.

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 put through the biological and / or chemical-physical parameters is specified. 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), pickling agents, granules in the form of micro, 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; Marsden, Solvents 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, "Interface-active ethylene oxide adducts", Wiss. Publishing company, Stuttgart 1967; Winnacker-Küchler, "Chemical Technology", 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 with microgranules Water. Dust-like and granulated preparations as well as sprayable Solutions are usually no longer combined with other solutions before use inert substances diluted.  

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 mixing partners are

• 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.-Butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, Usoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl (methyl) carbamate, Oxamyl, Piruricarb Thiofanox, ethyl-4,6,9-triaza-4-benzyl-6,10-dimethyl-8-oxa-7-oxo-5, 11-dithia-9-dodecenoate (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, bioallethrin ((S) -cyclopentyl isomer), bioresmethrin, biphenates, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1RS) -trans-3- (4-tert.butylphenyl) -2,2-dimethylcyclopropane decarboxylate (NCl 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, Cyclopropancarbonsäurem (2-naphthyl) -methyl ester (Ro12-0470), 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 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, Phytophthora infestans, Erysiphe graminis, Piricularia oryzae, Pyrenophora teres, Leptosphaerea nodorum and Pellikularia 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, ICl 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 EO) 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. Production examples

Example A

5-chloro-6-ethyl-4- [2- (4-methylphenyl) -1,3-dioxan-5-ylamino] pyrimidi-n
4.6 g (0.02 mol) of 5-chloro-6-ethyl-4- (1,3-dihydroxy-2-propylamino) pyrimidine,
4.6 g (0.02 mol) of p-tolylaldehyde and
0.5 g of p-toluenesulfonic acid hydrate was heated in 100 ml of toluene for 6 hours on a water separator.

After cooling, dilute sodium hydroxide solution and conc. aqueous bisulfite solution stirred and the organic phase dried and concentrated. For cleaning and to separate the cis / trans isomers was carried out on silica gel Chromatograph ethyl acetate / petroleum ether (8: 2). 0.64 g was initially obtained (9.6% of theory) of the trans isomer (colorless crystals, mp: 129-130 ° C), then 3.55 g (53.2% of theory) of the cis isomers (colorless crystals, mp: 107-108 ° C).

Preparation of the starting product 5-chloro-6-ethyl-4- (1,3-dihydroxy-2- propylamino) pyrimidine

27.3 g (0.3 mol) of 2-amino-1,3-propanediol, 53.1 g (0.3 mol) of 4,5-dichloro-6-ethyl pyrimidine and 44.6 g (0.45 mol) of triethylamine were placed in 500 ml of toluene for 6 h Reflux heated. A white precipitate formed from triethylamine Hydrochloride and undissolved product. The toluene was drawn off, the solid Contents of the flask dissolved in methanol and for cleaning and separating the Triethylamine hydrochloride on silica gel with methanol as the eluent  chromatographed. 39.0 g of colorless crystals (56.1% of theory) were obtained, mp: 104-105 ° C.

Example B

4- (2-n-Butyl-2-methyl-1,3-dioxan-5-ylamino) -5-chloro-6-ethyl-pyrimidi-n
2.16 g (9 mmol) 5-chloro-6-ethyl-4- (1,3-dihydroxy-2-propylamino) pyrimidine (Example 1), 1.80 g (18 mmol) 2-hexanone and 500 mg p-Toluenesulfonic acid was heated in 100 ml of toluene for 8 hours on a water separator. After stirring with dilute sodium hydroxide solution, the organic phase was dried and concentrated. The cis / trans isomers were separated by chromatography on silica gel (eluent: ethyl acetate / petroleum ether 4: 1). First 0.29 g of trans isomer (10.3% of theory, colorless oil) was eluted, then 0.49 g of the cis isomer (17.3% of theory, colorless oil).

Example C

5-chloro-6-ethyl-4- (2,2-dimethyl-1,3-dioxan-5-ylamino) pyrimidine
2.65 (15 mmol) 4,5-dichloro-6-ethyl-pyrimidine, 2.40 (18.3 mmol) 5-amino-2,4-dimethyl-1,3-dioxane and 3.03 g (30 mmol) of triethylamine were refluxed in 10 ml of toluene for 4 h. After cooling, the mixture was stirred with water and the organic phase was dried and concentrated. For purification, it was chromatographed on silica gel (ethyl acetate / petroleum ether 4: 1).

0.46 g (11% of theory) of product was obtained as a colorless oil.

Preparation of the precursor 2,2-dimethyl-1,3-dioxan-5-ylamine

6.1 g (47 mmol) of 2,2-dimethyl-1,3-dioxan-5-one (D. Enders, B. Bockstiegel, Synthesis 1989, 493) were in 50 ml ammonia - saturated methanol in Autoclaves at 50 ° C and 100 bar hydrogen pressure with Raney nickel as Reductively aminated catalyst. After filtering off the catalyst and concentrating 4.8 g of a brown oil were obtained, which was reacted further without purification has been.  

Example D

5-chloro-6-ethyl-4- [cis-2- (4-methylphenyl) -1,3-dithian-5-ylamino] pyrimidine
1.77 g (10 mmol) of 4,5-dichloro-6-ethyl-pyrimidine and 2.2 g (10 mmol) of 5-amino-2- (4-methylphenyl) -1,3-dithiane were added with 2.02 g triethylamine stirred at 80-90 ° C for 6 h. The mixture was taken up in water / methylene chloride, the organic phase was dried and concentrated. For purification, it was chromatographed on silica gel (eluent petroleum ether / ethyl acetate 4: 1). 1.0 g of colorless solid (27.3% of theory) was obtained, mp: 138-139 ° C.

Preparation of the educt 5-amino-2- (4-methylphenyl) -1,3-dithiane

22.4 g (0.1 mol) of 2- (4-methylphenyl) -1,3-dithian-5-one and 77.1 g (1.0 mol) Ammonium acetate were in 250 ml of methanol with the addition of 37.5 g of molecular sieve (3 Å) stirred for 30 min and then 6.30 (0.1 mol) sodium cyanoborohydride added in portions at 20 ° C. The mixture was stirred at room temperature for 48 hours, diluted with methanol and filtered. The filtrate was concentrated and the Residue taken up in dilute hydrochloric acid / toluene. 16323 00070 552 001000280000000200012000285911621200040 0002019523906 00004 16204 The hydrochloric acid phase was with conc. Sodium hydroxide solution made basic and etherified. 2.2 g were obtained Product as a colorless oil (9.8% of theory) which is implemented without further purification has been.  

Preparation of 2- (4-methylphenyl) -1,3-dithian-5-one

131 g of 2- (4-methylphenyl) -1,3-dithia-cyclohexan-5-one-4- were heated carboxylic acid methyl ester (0.464 mol) with 350 ml of 2N sulfuric acid for 6 hours with intensive stirring under reflux. After cooling, it was decanted off and the residue taken up in ethyl acetate. The organic phase was with Washed bicarbonate solution and water, dried and concentrated. The firm The residue was slurried with diisopropyl ether for further purification and vacuumed. 62.7 g of yellow crystals (60.2% of theory) were obtained, mp: 112-113 ° C.

Preparation of 2- (4-methylphenyl) -1,3-dithian-5-one-4-carboxylic acid methyl ester

42.30 g of sodium hydride (80% dispersion in oil) (1.41 mol) were in 700 ml Suspended toluene and heated to 90 ° C. At this temperature, 211.2 g (0.67 mol) bis- (5-carbomethoxymethyl) - (4-methylbenzaldehyde) mercaptal slowly added dropwise. Strong hydrogen evolution and yellowing occurred Reaction mixture. If necessary, the reaction could be done by adding a few drops of ethanol are started. Then was 4 h at 100 ° C. stirred. After cooling to room temperature, the destruction of 20 ml of ethanol was added dropwise to excess sodium hydride, water was added, with conc. Hydrochloric acid brought to pH 3 and the organic phase separated. The The water phase was stirred twice with toluene and the combined organic phases with bicarbonate solution.

After drying and concentrating the organic phase, 131.7 g of product (69.4% of theory), which was reacted without further purification.

Preparation of bis (5-carbomethoxymethyl) - (4-methylphenyl) mercaptal

120.1 g (1.0 mol) of p-tolylaldehyde and 201.7 g (1.9 mol) Mercaptoacetic acid methyl ester was mixed with 5 g of p-toluenesulfonic acid hydrate in 600 ml of toluene are heated on a water separator until water has stopped forming.  

The mixture was then stirred twice with bicarbonate solution and water and the organic phase dried and concentrated. To remove excess aldehyde, the crude product was dissolved in ethyl acetate and with concentrated sodium bisulfite solution. After drying and concentration the organic phase, 213.2 g of crude product were obtained (67.8% of theory), which was implemented without further cleaning.

Example E

3-chloro-2-ethyl-4- (2-phenyl-1,3-dioxan-5-ylamino) pyridine
2.3 g (10 mmol) of 5-chloro-6-ethyl-4- (1,3-dihydroxy-2-propylamino) pyridine (prepared analogously to Example A from 2-amino-1,3-propanediol and 3,4 -Dichlor-2-ethyl-pyridine) and 5.0 g of benzaldehyde were heated with 2.1 g of p-toluenesulfonic acid hydrate in 40 ml of toluene on a water separator until the evolution of water had ended. Working up and purification was carried out analogously to Example A. In the chromatography on silica gel (ethyl acetate), 0.6 g of trans isomer (18.8% of theory), mp: 139-140 ° C., then 2.4 g cis isomer (75.2% of theory), mp. 119-120 ° C.

C. Biological examples Use as a fungicide

The effectiveness of the preparations according to the invention was assessed on a 0-4 scale, wherein
0 0-24% infestation suppression
1 25-49% infestation suppression
2 50-74% infestation suppression
3 75-97% infestation suppression
4 97-100% infestation suppression
means.

Example A

Barley plants of the "Maris Otter" variety were sprayed to runoff point in the 2-leaf stage with a solution of the compounds according to the invention in a mixture of 40% acetone and 60% water. 24 hours later, the plants were inoculated with barley powdery mildew (Erysiphe graminis f. Sp. Hordei) and stored in a climatic chamber at 20 ° C and a relative humidity of 75-80%. 7 days after the treatment, the plants were examined for infestation with barley mildew. The following compounds were rated 3 or 4 at 50 mg active ingredient / l spray mixture:
Compounds according to Example Nos. 5, 7, 26, 30, 35, 53, 86.

Example B

Tomato plants of the "First in the Field" variety were in the 3-4 leaf stage a solution of the compounds according to the invention in a mixture of 40% Acetone and 60% water sprayed until dripping wet. 24 hours later Plants with a spore suspension of Phytophthora infestans (20,000 Spores / ml) and in a climatic chamber at 15 ° C for 2 days 99% relative humidity, then 4 days at 75-80% relative humidity kept. 6 days after treatment, the plants were infected Phytophthora infestans examined.

The following compounds were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 35, 53, 54, 85, 86.

Example C

Approx. 6-week-old seedlings of the "Grüner Veltliner" variety were sprayed to runoff point with a solution of the compounds according to the invention in a mixture of 40% acetone and 60% water. 24 hours later, the plants were inoculated by spraying with a zoo spore suspension (100,000 / ml) from Plasmopara viticola and stored in a climatic chamber at 70 ° C. and a relative air humidity of approx. 99%. 14 days after treatment, the plants were examined for their infestation with Plasmopara viticola. The following compounds were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 5, 26, 52, 53.

Example D

Wheat plants of the "Hornet" variety were in the 2-leaf stage with a solution of the compounds according to the invention in a mixture of 40% acetone and 60% water sprayed to drip. The plants were finished 24 hours later Spray with a pycospore suspension (500,000 / ml) from Leptosphaeria nodorum inoculated and in a climatic chamber at 18-20 ° C and a relative Humidity of approx. 99% stored. 14 days after inoculation Plants examined for their infestation with Leptosphaeria nodorum.

The following compounds were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 5, 57, 36.

Example E

Rice plants of the "Nihonbare" variety were in the 1.5-leaf stage with a Solution of the compounds according to the invention in a mixture of 40% Acetone and 60% water sprayed until dripping wet. At the same time there was a Pouring application with a solution of the substances in a mixture of 5% Acetone and 95% water. The plants were finished 24 hours later Spray with a pycnospore suspension (10⁶ / ml) from Pyricularia Oryzae inoculated. The plants were grown in a darkened climate chamber for 2 days 26 ° C and a relative humidity of 99% and then in an illuminated climate chamber with approx. 18 ° C and a relative humidity of 75-80% spent. 7-9 days after inoculation, the plants were on their Infested with Pyricularia oryzae examined.

The following substances were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 5, 7, 36.

Example F

Approx. 3-week-old apple seedlings (Malus sp.) Were treated with a solution of the Compounds according to the invention in a mixture of 40% acetone and 60% water sprayed to drip. After 24 hours the plants were through Spray with a spore suspension (300,000 / ml) from Venturia inaequalis inoculated. The plants were 2 days in the dark at 18-20 ° C and one stored relative humidity of 99%, then in the light for 5 days same humidity and finally 7 days at 75-80% humidity. 14 days after treatment, the plants were infected with Venturia inaequalis examined.

The following substances were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 35, 57.

Example G

Tomato plants of the "First in the Field" variety were sprayed to runoff point in the 2-3 leaf stage with a solution of the compounds according to the invention in a mixture of 40% acetone and 60% water. After 24 hours, the plants were inoculated with a spore suspension (500,000 / ml) of Botrytis cinerea. The plants were stored in a climatic chamber at 18-20 ° C and 99% relative humidity. 5 days after inoculation, the plants were examined for their involvement with Botrytis cinerea. The following substances were rated 3 or 4 at 50 mg active substance / l spray mixture:
Compounds according to Example Nos. 54, 85, 86.

Use as an insecticide / acaricide Example A

Place a petri dish on the inside of the lid and base 1 ml of the formulation to be tested emulsified in water, evenly applied and after drying the covering 10 adults each House fly (Musca domestica) entered. After closing the shells they are kept at room temperature and after 3 hours the Mortality of the test animals determined. At 250 ppm (based on the content of The preparations according to Example Nos. 2, 6, 7, 33, 35, 36, 40, 49, 50, 52, 53, 54, 55, 57, 85, 94, 101, 115 a 100% mortality in the used experimental animals.

Example B

Rice seed is germinated on cotton wool in cultivated glasses and moist after growing to about 8 cm stem length with the leaves in the testing test solution given. After draining, the so treated Rice plants placed separately in the breeding container according to the test concentration and with 10 larvae (L3) each of the species Nilaparvata lugens populated. After storing the sealed breeding containers at 21 ° C can cause mortality after 4 days Cicada larvae can be determined. At a concentration of 250 ppm (related on the content of active ingredient) show the preparations according to Example Nos. 2, 6, 7, 13, 23, 26, 29, 33, 35, 36, 40, 46, 48, 49, 50, 53, 54, 57, 85, 86, 94 a 100% mortality in the test animals used.

Example C

Wheat seeds are pre-germinated under water for 6 hours, then in 10 ml Glass test tubes and covered with 2 ml of soil. After adding The plants remain in the growing jars until they reach 1 ml of water  Stand at a height of approx. 3 cm below room temperature (21 ° C). Subsequently medium-sized Diabrotica undecimpunctata larval stages (10 each) in the Put the glass on the ground and after 2 hours 1 ml of the to be checked Concentration of test liquid on the surface of the earth in the glass pipetted. After standing for 5 days under laboratory conditions (21 ° C), the Earth or the root parts are searched for living Diabrotica larvae and the Mortality found. At 250 ppm (based on the content of active ingredient) show the preparations according to Example No. 2, 6, 7, 13, 13, 26, 29, 33, 36, 38, 40, 52, 53, 54, 57, 85, 86, 92, 94, 101, 127, 129 100% mortality in the experimental animals used.

Example D

Field bean heavily infested with black bean louse (Aphis fabae) (Vicia faba) are with aqueous dilutions of wettable powder concentrates with 250 ppm Active substance content sprayed until the stage of dripping begins. The Mortality of the aphids is determined after 3 days. A 100% kill can with the compounds according to Example No. 2, 6, 7, 12, 13, 23, 26, 29, 33, 35, 36, 38, 40, 48, 50, 52, 53, 54, 57, 85, 86, 92.

Example E

Those heavily infested with bean spider mites (Tetranychus urticae, full population) Bean plants (Phaseolus v.) Were diluted with the water Wettable powder concentrate, which contained 250 ppm of the respective active ingredient, sprayed. The mite's mortality was checked after 7 days. 100% The compounds according to Example Nos. 2, 6, 7, 13, 23, 26, 29, 33, 35, 36, 38, 39, 40, 48, 50, 53, 54, 55, 57, 85, 86, 94.  

Example F

Filter paper discs with eggs of cotton bugs (Oncopeltus fasciatus) are diluted with 0.5 ml of water to be tested Formulation treated. After the topping has dried, the petri dish closed and the interior kept at maximum humidity. After Storage at room temperature became the ovicidal effect after 7 days determined. With an active substance content of 500 ppm, according to Example No. 6, 13, 33, 35, 48, 52, 53, 54, 55, 57, 85, 86, 94, 101, 115 a 100% ovicidal effect achieved.

Example G

Leaves of the Phaseolus vulgaris bean are evenly mixed with white eggs Fly (Trialeurodes vaporariorum) and after a development period of the white fly population to the L2-L3 stage even with the watery Sprayed test emulsions of the formulation. After 4 days the microscopic control of the larvae on the leaves that with the Compounds according to Example Nos. 6, 7, 13, 26, 35, 36, 48, 52, 53, 54, 57, 86 a 100% kill can be achieved.

Example H

L2 larvae of Spodoptera liforalis (Egyptian cotton worm) are found in Petri dishes set, which are covered with filter paper on the bottom and one contain a small amount of nutrient medium. The soil with the nutrient medium and the Larvae are placed on top with the aqueous emulsions of the test substances sprayed and the petri dishes closed with a lid. After 5 days at The effect of the compounds on the larvae is determined at about 23 ° C. It was found that with the method mentioned in Spodoptera literalis larvae with the compounds according to Example Nos. 13, 29, 33 at a concentration  of 250 ppm (based on active ingredient) of the spray mixture has a 100% effect can be achieved.

Use as an anti-parasitic Example A In vitro test on tropical cattle ticks (Boophilus microplus)

The effectiveness of the Detect compounds according to the invention against ticks:

The active ingredients were used to produce a suitable active ingredient preparation 10% (w / v) in a mixture consisting of dimethylformamide (85 g), Nonylphenol polyglycol ether (3 g) and ethoxylated castor oil (7 g), dissolved and the resulting emulsion concentrates with water to a test concentration diluted by 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 Examples Nos. 2, 7, 13, 23, 26, 33, 35, 36, 38, 40, 50, 52, 54, 55, 57, 85 each a 100% Inhibition of egg laying.

Claims (22)

1. Compounds of formula (I) in which
R¹ is hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl or (C₃-C₅) cycloalkyl;
R² and R³ are the same or different and are each hydrogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₂-C₄) alkenyl, (C₂-C₄) haloalkenyl, (C₂-C₄) alkynyl , (C₂-C₄) -haloalkynyl, (C₁-C₄) -alkoxy, (C₁-C₄) -haloalkoxy, (C₁-C₄) -alkoxy- (C₁-C₄) -alkyl, (C₁-C₄) -haloalkoxy- ( C₁-C₄) alkyl, (C₁-C₄) alkoxy- (C₁-C₄) haloalkyl, (C _1- -C₄) haloalkoxy- (C₁-C₄) - haloalkyl, halogen, hydroxy, (C₁-C₄) -Hydroxyalkyl, (C₁-C₄) alkanoyl, (C₁-C₄) alkanoyl- (C₁-C₄) alkyl, (C₁-C₄) haloalkanoyl, (C₃-C₅) cycloalkyl, (C₃-C₅) halocycloalkyl , Cyano, (C₁-C₄) cyanoalkyl, nitro, (C₁-C₄) nitroalkyl, thiocyano, (C₁-C₄) thiocyanoalkyl, (C₁-C₄) alkoxycarbonyl, (C₁-C₄) alkoxycarbonyl- (C₁- C₄) alkyl, (C₁-C₄) haloalkoxycarbonyl, (C₁-C₄) alkylthio, (C₁-C₄) alkylthio- (C₁-C₄) alkyl, (C₁-C₄) haloalkylthio, (C₁-C₄) -Alkylsulfinyl, (C₁-C₄) - haloalkylsulfinyl, (C -C₄) alkylsulfonyl, or (C₁-C₄) - haloalkylsulfonyl group; 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 which 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 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;
Y and Z are oxygen or a group S (O) _m with m = 0.1 or 2,
R⁴, R⁴ ′ and R⁵ are substituents of the heteroaliphatic ring system;
R⁴ and R⁴ are hydrogen, halogen, (C₁-C₄) alkyl, (C₁-C₄) haloalkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkylthio;
R⁵ denotes alkyl, alkenyl, alkynyl, aryl or heterocyclyl, where the aryl or heterocyclyl radicals listed can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different radicals and in the alkyl mentioned, Alkenyl or alkynyl radicals one or more non-adjacent saturated carbon units can be replaced by a carbonyl group or by heteroatom units, such as oxygen, S (O) _x , with x = 0, 1 or 2, NR⁶ or SiR⁷R⁸ , wherein R⁶ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkanoyl and R⁷ and R⁸ are (C₁-C₄) alkyl;
and in which, in addition, 3 to 12 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle and these hydrocarbon radicals with or without the stated variations, optionally with one or more, in the case of fluorine, up to the maximum number of identical or different radicals selected from halogen, aryl, aryloxy, arylthio, cycloalkoxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, alkanoyl, cycloalkanoyl, haloalkanoyl, aroyl, arylalkanoyl, cycloalkylalkanoyl, heterocyclylalkanoyl, alkoxycarbonyl, haloalkoxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, arylalkoxycarbonyl, heterocyclylalkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl , Alkanoyloxy, haloalkanoyloxy, cycloalkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, heterocycloylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, hydroxy, cyano, thiocyano or nitro, where the cycloaliphatic can be substituted n, aromatic or heterocyclic ring systems can be unsubstituted under the just mentioned substituents or can be provided with up to three, in the case of fluorine also up to the maximum number of identical or different substituents, or
R⁴ and R⁵ alkyl together form a three- to eight-membered ring system and in which one or two CH₂ groups, preferably a CH₂ group by heteroatom units such as oxygen, S (O) _n with n = 0.1 or 2 or NR⁹ can be replaced, where R⁹ is hydrogen, alkyl, alkoxy, alkanoyl, benzoyl, aryl or heteroaryl, the benzoyl, aryl or heteroaryl radicals unsubstituted or with up to three, in the case of fluorine, up to the maximum number of the same or can be provided with different substituents, and the ring system formed from R⁴ and R⁵ can be unsubstituted or can be provided with up to three substituents and these substituents are the same or different and are each alkyl, haloalkyl, alkoxy, alkylthio, aryl, aryloxy, arylthio, arylalkyl, arylalkoxy , Arylalkylthio, cycloalkyl, cycloalkoxy, cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, trialkylsilyl or alkoxycarbonyl, where the cycloaliphatic, aromatic or h heterocyclic ring systems may be unsubstituted under the just mentioned substituents or may be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents,
or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring forms a condensed ring system and the benzene ring in these condensed systems can be unsubstituted or provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents , or their salts. 2. Compounds of formula I according to claim 1, in which
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, aryl or heterocyclyl means, the aryl or heterocyclyl radicals listed unsubstituted or with up to three, in the case of fluorine can also be provided up to the maximum number of the same or different radicals and in the alkyl, alkenyl or alkynyl radicals mentioned one or more non-adjacent saturated carbon units by a carbonyl group or by heteroatom units, such as oxygen, S ( O) _x , with x = 0, 1 or 2, NR⁶ or SiR⁷R⁸ can be replaced, where R⁶ is hydrogen, (C₁-C₄) alkyl, (C₁-C₄) alkoxy or (C₁-C₄) alkanoyl and R⁷ and R⁸ (C₁-C₄) alkyl, preferably methyl, and in which, in addition, 3 to 12 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle and these hydrocarbon radicals with or without the stated variations, optionally with a or more eren, in the case of halogen to the maximum number of identical or different radicals from the series halogen, aryl, aryloxy, arylthio, (C₃-C₈) - cycloalkoxy, (C₃-C₈) -cycloalkylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio, (C₁- C₁₂) alkanoyl, (C₃-C₈) cycloalkanoyl, (C₂-C₁₂) haloalkanoyl, aroyl, aryl- (C₁-C₄) alkanoyl, (C₃-C₈) cycloalkyl- (C₁-C₄) alkanoyl, heterocyclyl - (C₁-C₄) alkanoyl, (C₁-C₁₂) alkoxycarbonyl, (C₁-C₁₂) haloalkoxycarbonyl, (C₃-C₈) cycloalkoxycarbonyl₁ (C₃-C₈) - cycloalkyl- (C₁ C₄) alkoxycarbonyl-, aryl - (C₁-C₄) alkoxycarbonyl, heterocyclyl- (C₁-C₄) alkoxycarbonyl, aryloxycarbonyl, heterocyclyloxycarbonyl, (C₁-C₁₂) alkanoyloxy, (C₂-C₁₂) - haloalkanoylalkoxy, (C₃-C₈) -cycloalkanoyloxy C₈) -cycloalkyl- (C₁-C₄) -alkanoyloxy, aroyloxy, aryl- (C₁-C₄) -alkanoyloxy, heterocyclyl- (C₁-C₄) -alkanoyloxy, (C₁-C₁₂) alkylsulfonyloxy, arylsulfonyloxy, hydroxy, cyan o, thiocyano or nitro can be substituted, the cycloaliphatic, aromatic or heterocyclic ring systems being unsubstituted or given up to three, in the case of fluorine, up to the maximum number of the same or different substituents under the just mentioned substituents,
or R⁴ and R⁵ together form a three- to eight-membered ring system and in which one or two CH₂ groups, preferably a CH₂ group, are replaced by heteroatom units such as oxygen, S (O) _n with n = 0, 1 or 2 or NR⁹ can be where R⁹ is hydrogen, (C₁-C₈) alkyl, (C₁-C₈) alkoxy, (C₁-C₈) alkanoyl, benzoyl, aryl or heteroaryl, the benzoyl, aryl or heteroaryl radicals being unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents and the ring system formed from R⁴ and R⁵ can be unsubstituted or can be provided with up to three substituents and these substituents are identical or different and each ( C₁-C₈) alkyl, (C₁-C₈) haloalkyl, (C₁-C₈) alkoxy, (C₁-C₈) alkylthio, (C₃-C₈) cycloalkyl, (C₃-C₈) cycloalkoxy, (C₃- C₈) cycloalkylthio, aryl, aryloxy, arylthio, aryl- (C₁-C₄) alkyl, aryl- (C₁-C₄) alkoxy, aryl- (C₁- C₄) alkylthio, heterocycyl, heterocyclyloxy, heterocyclylthio, (C₁-C₈) - trialkylsilyl, preferably (C₁-C₈) alkyl-dimethylsilyl- or (C₁-C₈) - alkoxycarbonyl, the cycloaliphatic, aromatic or heterocyclic rings just mentioned substituents and substituted or can be provided with up to three, in the case of fluorine also up to the maximum number of identical or different substituents,
or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring forms a condensed ring system and the benzene ring in these condensed systems can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents, or 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, (C₁-C₄ alkenyl, (C₁-C₄) alkynyl, (C₁-C₄) haloalkyl, cyclopropyl, halocyclopropyl, methoxymethyl or cyano;
R³ is hydrogen, halogen, methyl, ethyl, ethynyl, methoxy, ethoxy, cyano, trifluoromethyl, fluoromethylthio or methoxycarbonyl; 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 can contain a sulfur or an oxygen atom instead of a CH₂ unit;
A represents CH or N;
X represents NH or oxygen;
Y and Z each represent oxygen or sulfur;
R⁴ represents hydrogen, (C₁-C₄) alkyl, trifluoromethyl or (C₁-C₄) alkoxy;
R⁴ means hydrogen,
or 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, (C₁-C₂) fluoroalkyl, cyclopropyl or methoxymethyl;
R³ is halogen, methyl, ethyl, ethynyl, methoxy, ethoxy, trifluoromethyl, fluoromethylthio, methoxycarbonyl or cyano; or
R² and R³ together with the ring system to which they are attached form the quinazoline or quinoline system which can 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;
R⁴ is hydrogen or methyl, or their salts. 5. Compounds of formula I according to any one of claims 1 to 4, in which
R1 is hydrogen;
R² is ethyl, propyl, isopropyl, 1-fluoroethyl or methoxymethyl;
R³ represents fluorine, chlorine, bromine, cyano or methoxy; or
in the event that 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;
A represents CH or N;
X represents NH;
Y and Z represent oxygen or sulfur;
R⁴ represents hydrogen or methyl;
R⁴ means hydrogen,
or 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
A represents CH or N;
X represents NH;
Y and Z are oxygen;
R⁴ and R⁴ ′ are hydrogen;
R⁵ (C₁-C₂₀) alkyl, (C₂-C₂₀) alkenyl, (C₂-C₂₀) alkynyl, aryl or heterocyclyl means, the aryl or heterocyclyl radicals listed unsubstituted or with up to three, in the case of fluorine can also be provided up to the maximum number of identical or different radicals and in the alkyl, alkenyl or alkynyl radicals mentioned one or more, preferably up to three non-adjacent saturated carbon units can be replaced by heteroatom units, such as oxygen or SiR⁷R⁸ where R wobei and R⁸ are (C₁-C₄) alkyl, preferably methyl,
and in which in addition 3 to 6 atoms of these hydrocarbon radicals, optionally modified as above, can form a cycle and these hydrocarbon radicals with or without the stated variations, optionally with one or more, in the case of halogen, up to the maximum number of identical or different radicals from the series halogen, aryl, aryloxy, arylthio, (C₃-C₈) - cycloalkoxy, (C₃-C₈) -cycloalkylthio, heterocyclyl, heterocyclyloxy or (C₁-C₂) -alkoxycarbonyl, which may be the cycloaliphatic, aromatic or heterocyclic ring systems under the just mentioned substituents can be unsubstituted or can be provided with up to three, in the case of fluorine also up to the maximum number of identical or different substituents,
or R⁴ and R⁵ together form a five- or six-membered ring system and in which a CH₂ group can be replaced by heteroatom units such as oxygen, S (O) _n with n = 0, 1 or 2 or NR⁹, where R⁹ is hydrogen (C₁ -C₈) alkyl, (C₁-C₈) alkanoyl, benzoyl, aryl or heteroaryl means, the benzoyl, aryl or heteroaryl radicals unsubstituted or with up to three, in the case of fluorine also up to the maximum number of the same or can be provided with various substituents, and the ring system formed from R⁴ and R⁵ can be unsubstituted or can be provided with up to three substituents and these substituents are the same or different and are each (C₁-C₈) alkyl, (C₃-C₈) cycloalkyl, aryl or aryl- (C₁-C₄) -alkyl, where the cycloaliphatic, aromatic or heterocyclic ring systems are unsubstituted under the just mentioned substituents or with up to three in the case of fluorine also up to the maximum number of the same or different can be provided with each substituent,
or the ring system formed from R⁴ and R⁵ together with a further benzene ring or cyclohexane ring forms a condensed ring system, preferably the indane, 1,2,3,4-tetrahydronaphthalene, decahydronaphthalene or benzocycloheptane system, and the benzene ring in these condensed systems is unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different substituents,
or their salts. 7. Compounds of formula I according to any one of claims 1 to 5, in which
R⁵ (C₁-C₁₅) alkyl, aryl or heterocyclyl in the sense of heteroaromatic ring system, where the aryl or heterocyclyl radical can be unsubstituted or can be provided with up to three, in the case of fluorine, up to the maximum number of identical or different radicals and in said alkyl radical one or more non-adjacent saturated carbon units can be replaced by oxygen, and in addition 3 to 8 atoms of this optionally modified alkyl radical can form a cycle and this alkyl radical with or without the specified variations, optionally with one or more halogen atoms, in the case of fluorine can also be substituted up to the maximum number or with an aryl radical and this aryl radical can be unsubstituted or with up to three, in the case of fluorine also up to the maximum number of the same or can be provided with various substituents,
or their salts. 8. A compound of formula I according to any one of claims 1 to 7, in which for the case R⁴ = hydrogen, the substituents X and R⁵ are cis- are constant, or their salts. 9. A process for the preparation of compounds of formula I according to any one of claims 1 to 8, 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 represents a leaving group with a nucleophile of the formula III wherein X, Y, Z, R⁴, R⁴ 'and R⁵ have the meanings given above under formula I, or
to obtain a compound of formula IV in which R¹, R², R³, R⁴ ', A, X, Y and Z have the meanings given above for formula I, reacted with a compound of formula V. in which R⁴ and R⁵ have the meanings given above for formula I,
and in the compounds of the formula I obtained in this way or in another way, the nitrogen heterocycle or the side chain R⁵ is further varied, and the compounds of the formula I are optionally converted into their salts. 10. Compositions containing at least one compound according to one of the Claims 1 to 8 and at least one formulation agent. 11. Fungicidal composition according to claim 10, containing a fungicidally active Amount of at least one compound according to one of claims 1 to 8 together with the usual additives for this application. 12. Insecticidal, acaricidal, ixodicidal or nematicidal agent according to Claim 10, containing an effective amount of at least one compound according to one of claims 1 to 8 together with those for this application usual additives. 13. Plant protection products containing a fungicidal, insecticidal, acaricidal or nematicidal amount of at least one compound according to one of the Claims 1 to 8 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.   14. 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 8 together with those for these applications usual auxiliaries and additives. 15. A compound according to any one of claims 1 to 8 or means according to Claim 10, for use as a veterinary medicinal product, preferably in the Control of endo- or ectoparasites. 16. A method for producing an agent according to any one of claims 10 to 15, characterized in that the active ingredient and the other additives together and brings it into a suitable form of application. 17. Use of a compound according to any one of claims 1 to 9 or Agent according to one of claims 10, 11, 13 and 14 as a fungicide. 18. Use of a compound according to any one of claims 1 to 8 or an agent according to any one of claims 10, 11 and 14 as a wood preservative or as a preservative in sealants, in paints, in Cooling lubricants for metalworking or in drilling and cutting oils. 19. A method of 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 8 or an agent according to one of claims 10, 11, 13 and 14 applied. 20. 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 8 or an agent according to one of claims 10, 11 and 13 applied. 21. Use of compounds according to one of claims 1 to 8 or an agent according to any one of claims 10, 11 and 13 for combating Insect pests, acarina, mollusks and nematodes. 22. Seeds treated or coated with an effective amount of one A compound according to any one of claims 1 to 8 or an agent according to one of claims 10, 11 and 13.