EP0785934A1 - Substituted spiroalkylamino and spiroalkoxy-heterocycles, process for preparing the same and their use as pesticides and fungicides - Google Patents

Abstract

Compounds have the formula (a), in which Het stands for optionally susbstituted 4-pyridyl or 4-pyrimidinyl; X stands for NH, O or S(O)0-2; E stands for a bond or alkanidyl; Y and Z stand for CH2, O and or S(O)0-2; W stands for (CH2)0-4; R?4 and R5¿ stand for halogen, alkyl (halide), alkoxy (halide) or alkylthio; r and s = 0-2; U stands for a bond, O, S(O)¿0-2? or optionally substituted imino; and V stands for a bond CO, SO2, -CQ-T- or -CT' = N-; or U+V represent together a double bond; and R?6¿ is defined as in the description. Also disclosed are a process for preparing these compounds and their use as pesticides and fungicides.

Description

 description

Substituted spiroalkylamino and alkoxy heterocycles, processes for their preparation and their use as pesticides and

Fungicides

The invention relates to new substituted spiroalkylamino and alkoxy nitrogen heterocycles, processes for their preparation and their use as

Pesticides and fungicides.

It is already known that certain spiroalkylamino and alkoxy pyrimidines have fungicidal, acaricidal and insecticidal activity (DE-A-4208254). However, the biological action of these compounds, particularly at low application rates and concentrations, is not satisfactory in all areas of application.

New substituted spiroalkylamino and alkoxy nitrogen heterocycles of the general formula I have been found

in which

R ^{1 is} hydrogen, halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₃ -C ₅ ) -

Means cycloalkyl or (C ₃ -C ₅ ) halocycloalkyl;

R ² and R ^{3 are} identical or different and are each hydrogen, (C ₁ -C ₄ ) -alkyl,

(C ₁ -C ₄ ) haloalkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) haloalkenyl, (C ₂ -C ₄ ) - Alkynyl, (C ₂ -C ₄ ) haloalkynyl, tri- (C ₁ -C ₄ ) alkylsilyl- (C ₂ -C ₄ ) alkynyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) -Halogenalkoxy, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -haloalkoxy- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₄ ) -Alkoxy- (C ₁ -C ₄ ) -haloalkyl, (C ₁ -C ₄ ) -haloalkoxy- (C ₁ -C ₄ ) -haloalkyl, halogen, hydroxy, (C ₁ -C ₄ ) - hydroxyalkyl, (C ₁ -C ₄ ) alkanoyl, (C ₁ -C ₄ ) alkanoyl- (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkanoyl, (C ₃ -C ₅ ) cycloalkyl, (C ₃ -C ₅ ) halocycloalkyl, cyano, (C ₁ -C ₄ ) cyanoalkyl, nitro, (C ₁ -C ₄ ) nitroalkyl, thiocyano, (C ₁ -C ₄ ) thiocyanoalkyl, (C ₁ -C ₄ ) alkoxycarbonyl, (C ₁ -C ₄₎ alkoxycarbonyl (C ₁ -C ₄₎ - alkyl, (C ₁ -C ₄₎ haloalkoxycarbonyl, (C ₁ -C ₄₎ alkylthio, (C ₁ -C ₄ ) Alkylthio- (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkylthio, (C ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C ₄ ) haloalkylsulfinyl, (C ₁ -C ₄ ) Alkylsulfonyl or (C ₁ -C ₄ ) haloalkylsulfonyl; or

R ² and R ³ 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 CH ₂ , or which, if it is a 6-ring, can 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 (C ₁ -C ₄ ) - alkyl, (C ₁ -C ₄ ) haloalkyl, preferably trifluoromethyl, halogen, (C ₁ -C ₄ ) alkoxy or (C ₁ -C ₄ ) haloalkoxy, or

R ² and R ³ together with the carbon atoms to which they are attached form a saturated 5-, 6- or 7-membered isocyclic ring which can contain oxygen and / or sulfur instead of one or two CH ₂ groups and which is optionally substituted by 1, 2 or 3 (C ₁ -C ₄ ) alkyl groups;

 A represents CH or N;

X represents NH, oxygen or S (O) _q , with q = 0, 1 or 2;

E represents a direct bond or a straight-chain or branched (C ₁ -C ₄ ) alkanediyl group, preferably a direct bond;

Y and Z are identical or different and each independently represent CH ₂ , oxygen or a group S (O) _x with x = 0, 1 or 2; W is a group (CH ₂ ) _n , where n is an integer from 1 to 4, or

W in the event that Y and / or Z are CH ₂ , a direct bond

 can mean between Y and Z;

wherein in the grouping -YWZ- one or more hydrogen atoms, as shown in formula I and described below, by

and are optionally replaced by R ⁵ ;

a and b are the same or different and, independently of one another, the numbers 0,

1, 2 or 3, where a and b do not simultaneously mean 0;

R ⁴ and R ^{5 are the} same or different and each independently

Are halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio;

r and s are the same or different and are independently 0, 1 or 2;

U is a single bond, oxygen, a group S (O) _y , with y = 0, 1 or 2 or a group NR ⁷ , where R ^{7 is} hydrogen, (C ₁ -C ₄ ) -alkyl or

Is (C ₁ -C ₄ ) alkoxy;

V represents a single bond, carbonyl or a grouping of the formula or, where Q is oxygen, sulfur or (C ₁ -C ₄ ) - Alkylimino, T oxygen, sulfur or a group NR ^{7 '} , and T'

(C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio or NR ^{7 '} R ^{7 "} , and where R ^7' and R ^{7" are} identical or different and have the meanings given above for R ⁷ ; or

 U and V together represent a double bond; and

a) R ⁶ denotes alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl or cyano, or, in the event that U and V together stand for a direct single bond,

b) R ^{6 is} as defined above or is halogen, hydroxy, carboxy, nitro or a group SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ and R ⁹ (C ₁ -C ₄ ) alkyl and R ¹⁰ alkyl or optionally substituted aryl mean, or, in the event that U and V together represent a double bond, c) R ^{6 represents} alkylidene or alkyloximino;

and the alkyl, alkenyl, alkynyl, alkylidene or alkyloximino radicals mentioned under R ⁶ , R ⁸ , R ⁹ and R ¹⁰ under a), b) or c) may have at least one of the following features:

 i, one or more, preferably up to three non-adjacent ones

CH ₂ groups are replaced by CO and / or heteroatom units, such as O, S (O) _y with y = 0, 1 or 2, NR ^{7 "} or SiR ⁸ R ⁹ , where R ^{7" is} the same as R ⁷ has the meanings given and where R ⁸ and R ^{9 have} the meanings given above for R ⁸ and R ⁹ ;

 ii. 3 to 12 atoms of these radicals form an up to 12-membered cycle;

 iii. the hydrocarbon radicals are with or without the specified variations, optionally with one or more, preferably up to three, in the case of fluorine, up to the maximum number of identical or different radicals from the series halogen, aryl, aryloxy, arylthio, cycloalkoxy, cycloalkylthio, Heterocyclyl, heterocyclyloxy,

 Heterocyclylthio, alkanoyl, cycloalkanoyl, haloalkanoyl, aroyl, arylalkanoyl, cycloalkylalkanoyl, heterocyclylalkanoyl, alkoxycarbonyl, haloalkoxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, arylalkoxycarbonyl, heterocycylloxycarbonyl, heterocyclylalkoxy

 Heterocyclyloxycarbonyl, alkanoyloxy, haloalkanoyloxy,

 Cycloalkanoyloxy, Cycloalkylalkanoyloxy, Aroyloxy, Arylalkanoyloxy, Heterocycloylalkanoyloxy, Alkylsulfonyloxy, Arylsulfonyloxy, Hydroxy, Cyano, Thiocyano or Nitro substituted, whereby the cycloaliphatic, aromatic or heterocyclic ring systems in the case of the above, in the case of the above-mentioned, preferably fluorine can also be provided up to the maximum number of identical or different substituents;

and furthermore, in the event that R ⁵ and R ^{6 are} alkyl radicals, these can be cyclically or spirocyclically linked;

and their salts, preferably acid addition salts. Compounds of the formula I in which

R ⁴ and R ^{5 are} halogen, preferably fluorine, chlorine and bromine, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) -Haloalkoxy or (C ₁ -C ₄ ) alkylthio; and

a) R ⁶ (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₂ -C ₂₀ ) alkynyl, if appropriate

 substituted aryl, optionally substituted heterocyclyl, or cyano, or, in the event that U and V together represent a single bond,

b) R ^{6 is} as defined above or halogen, hydroxyl, carboxy, nitro or a group SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ and R ⁹ (C ₁ -C ₄ ) alkyl and R ¹⁰ (C ₁ -C ₂₀ ) alkyl or optionally substituted aryl, or in the event that U and V together represent a double bond, c) R ^{6 is} (C ₁ -C ₂₀ ) alkylidene or (C ₁ -C ₂₀ ) alkyloximino;

and the alkyl, alkenyl, alkynyl, alkylidene or alkyloximino radicals mentioned for R ⁶ , R ⁸ , R ⁹ and R ¹⁰ under a), b) and c), if appropriate, have at least one of the following features:

 i. one or more, preferably up to three, not adjacent

CH ₂ groups are replaced by CO and / or heteroatom units such as O, S (O) _y with y = 0, 1 or 2, NR ^{7 "} or SiR ⁸ R ^{9 '} , R ^{7-' being} the above has the meanings given for R ⁷ and where R ⁸ and R ^{9 have} the meanings given above for R ⁸ and R ⁹ ;

ii. 3 to 8 atoms of these radicals form an up to 8-membered cycle; iii. the hydrocarbon radicals are with or without the specified variations, optionally with one or more, preferably up to three, in the case of halogen up to the maximum number of identical or different radicals from the series halogen, aryl, aryloxy, arylthio, (C ₃ - C ₈ ) -cycloalkoxy, (C ₃ -C ₈ ) -cycloalkylthio, heterocyclyl,

Heterocyclyloxy, heterocyclylthio, (C ₁ -C ₁₂ ) alkanoyl, (C ₃ -C ₈ ) cycloalkanoyl, (C ₂ -C ₁₂ ) haloalkanoyl, aroyl, aryl- (C ₁ -C ₄ ) alkanoyl, (C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) alkanoyl, heterocyclyl- (C ₁ -C ₄ ) alkanoyl, (C ₁ -C ₁₂ ) alkoxycarbonyl, (C ₁ -C ₁₂ ) haloalkoxycarbonyl, (C ₃ -C ₈ ) cycloalkoxycarbonyl, (C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) alkoxycarbonyl-, aryl- (C ₁ -C ₄ ) alkoxycarbonyl, heterocyclyl- (C ₁ -C ₄ ) alkoxycarbonyl,

Aryloxycarbonyl, heterocyclyloxycarbonyl, (C ₁ -C ₁₂ ) alkanoyloxy, (C ₂ -C ₁₂ ) haloalkanoylalkoxy, (C ₃ -C ₈ ) cycloalkanoyloxy, (C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) -alkanoyloxy, aroyloxy, aryl- (C ₁ -C ₄ ) -alkanoyloxy, heterocyclyl- (C ₁ -C ₄ ) -alkanoyloxy, (C ₁ -C ₁₂ ) -alkylsulfonyloxy,

 ARylsulfonyloxy, hydroxy, cyano, thiocyano or nitro substituted, the cycloaliphatic, aromatic or heterocyclic

Ring systems under the just mentioned substituents may be unsubstituted or may be provided with up to three, in the case of halogen, preferably fluorine, up to the maximum number of identical or different substituents, and furthermore, in the case that R ⁵ and R ^{6 are} alkyl radicals, these are cyclic, or can also be linked spirocyclically, and the remaining radicals and variables are as defined above; and their salts, preferably acid addition salts.

Compounds of the formula I in which are more preferred

R ^{1 represents} hydrogen, chlorine or fluorine;

R ² (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, trimethylsilylethynyl, (C ₂ -C ₄ ) Haloalkenyl, cyclopropyl,

 Is halocyclopropyl, methoxymethyl or cyano;

R ^{3 is} hydrogen, halogen, methyl, ethyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl, trimethylsilylethynyl, (C ₂ -C ₄ ) haloalkenyl, methoxy, ethoxy, cyano or (C ₁ -C ₄ ) alkoxycarbonyl; or

R ² and R ³ 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 CH ₂ unit, or

R ² and R ³ , 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 CH ₂ unit;

A represents CH or N; X represents NH or oxygen;

E stands for a direct bond;

Y and Z are identical or different and each represent CH ₂ , oxygen or sulfur and the group -YWZ- is substituted as described above;

a and b each represent the number 2,

R ⁴ and R ^{5 are the} same or different and each represents (C ₁ -C ₄ ) alkyl, trifluoromethyl or (C ₁ -C ₄ ) alkoxy;

and the remaining residues and variables are as defined above;

and their salts;

in particular those compounds in which

R ^{1 represents} hydrogen or fluorine;

R ^{2 is} methyl, ethyl, propyl, isopropyl, (C ₁ -C ₂ ) fluoroalkyl, ethynyl,

 Trimethylsilylethynyl, cyclopropyl or methoxymethyl;

R ^{3 is} halogen, methyl, ethyl, ethynyl, trimethylsilylethynyl, methoxy, ethoxy or cyano, or

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline or quinoline system, which may be substituted by fluorine in the carbocyclic part, or

R ² and R ³ together with the carbon atoms to which they are attached form a saturated 6-membered ring which can contain an oxygen or sulfur atom instead of a CH ₂ group;

Y and Z are identical or different and each represent CH ₂ or oxygen and the group -YWZ- is substituted as described above;

r = 0;

R ^{5 represents} methyl or trifluoromethyl;

U represents a direct bond or oxygen;

 Y represents a direct bond; or

 U and V together represent a double bond; and the remaining residues and variables are as defined above;

as well as their salts. Those compounds of the formula I in which

R ^{1 represents} hydrogen;

R ^{2 is} ethyl, propyl, isopropyl, 1-fluoroethyl, ethynyl, trimethylsilylethynyl,

 Trifluoromethyl or methoxymethyl means

R ^{3 represents} fluorine, chlorine, bromine, ethynyl, trimethylsilylethynyl or methoxy; or if A is nitrogen,

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline system, which may be substituted with a fluorine atom, or

R ² and R ³ together with the ring system to which they are attached, the

 Form 5,6,7,8-tetrahydroquinazoline system;

A represents CH or N;

X represents NH or oxygen;

E stands for a direct bond;

Y and Z are the same or different and each represents CH ₂ or oxygen; W is a group (CH ₂ ) _n , where n is 2 or 3, or

W in the event that Y and / or Z are CH ₂ , a direct bond

 can mean between Y and Z;

wherein in the grouping -YWZ- one or more hydrogen atoms, as shown in formula I and described above, by and are optionally replaced by R ⁵ ;

a and b represent the number 2;

r = 0;

s is 0, 1 or 2;

R ^{5 represents} methyl;

U denotes a single bond or oxygen,

 Y represents a single bond;

 and the remaining radicals are as defined above;

 and their salts;

especially those in which

Y represents CH ₂ ;

Z means CH ₂ or oxygen, and in this case W represents a direct bond between Y and Z;

or Y and Z are oxygen, and in this case

W represents a group (CH ₂ ) _n and n represents 2 or 3;

 U and V together stand for a direct single bond;

 and the remaining residues and variables are as defined above;

 as well as their salts.

Most preferred are those compounds of the formula I in which

R ^{1 represents} hydrogen;

R ^{2 represents} ethyl or methoxymethyl;

R ^{3 is} fluorine, chlorine, bromine or methoxy, or

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline or the 5,6,7,8-tetrahydroquinazoline system;

 A represents CH or N;

 X represents NH or oxygen;

a and b are each 2, and r and s are each 0;

 E stands for a direct bond;

Y CH ₂ and

Z represents CH ₂ or oxygen,

 U and V together represent a single bond;

 and in this case

 W means a direct bond between Y and Z,

or Y and Z each represent oxygen, and for this case

W represents a group (CH ₂ ) _n substituted as described above and n represents the numbers 2 or 3;

 -Y-W-Z- is substituted as described;

r and s are each = 0;

R ⁶ (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₂ -C ₂₀ ) alkynyl, optionally

is substituted aryl or optionally substituted heterocyclyl, and in the alkyl, alkenyl or alkynyl radicals mentioned one or more, preferably up to two, non-adjacent CH ₂ groups can be replaced by oxygen or sulfur, and in addition 3 to 6 atoms of these alkyl, alkenyl or alkynyl radicals, with or without the above variations, can form a cycle and these alkyl, alkenyl or alkynyl radicals, with or without the above

 Variations including the formation of a cycle, optionally with one, in the case of halogen up to the maximum number of residues from the series

 Halogen, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy,

 Heterocyclylthio or hydroxy may be substituted; and

the remaining residues and variables are as defined above;

especially those in which

R ^{2 is} methoxymethyl and R ^{3 is} methoxy, or

R ^{2 is} ethyl and R ^{3 is} chlorine or bromine;

 X represents NH;

 A means nitrogen

 Y and Z are oxygen;

W represents an optionally substituted group (CH ₂ ) _n as described above and n represents the number 2;

R ⁶ denotes (C ₁ -C ₂₀ ) alkyl, aryl or heterocyclyl, all of which are optionally substituted, and wherein one or more, preferably up to two, non-adjacent CH ₂ groups in the alkyl radical mentioned are replaced by oxygen or sulfur and can also form 3 to 6 atoms, with or without the above substitution, in a cycle; and

the remaining residues and variables are as defined above;

as well as their salts.

In the above formula, "halogen" means a fluorine, chlorine, bromine or iodine atom;

under the expression "(C ₁ -C ₄ ) alkyr 'an unbranched or branched

 Hydrocarbon residue with 1 to 4 carbon atoms, e.g. the methyl,

To understand ethyl, propyl, isopropyl, 1-butyl, 2-butyl, 2-methylpropyl or tert-butyl radical;

under the expression "(C ₁ -C ₈ ) alkyl" the aforementioned alkyl radicals, such as the pentyl, 2-methylbutyl, 1, 1-dimethylpropyl, hexyl, heptyl, octyl or the 1, 1, 3,3-tetramethylbutyl radical;

under the expression "(C ₁ -C ₂₀ ) alkyl" the abovementioned alkyl radicals and, for example, nonyl, 1-decyl, 2-decyl, undecyl, dodecyl, pentadecyl or eicosyl radical; under the expression "(C ₁ -C ₄ ) haloalkyl" an alkyl group mentioned under the expression "(C ₁ -C ₄ ) alkyl" in which one or more hydrogen atoms are replaced by the above-mentioned halogen atoms, preferably chlorine or fluorine such as the 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 "(C ₁ -C ₂ ) fluoroalkyl", for example the mono-, di- and trifluoromethyl group, 1-fluoroethyl, 2-fluoroethyl, 1, 1-difluoroethyl, 2,2,2-trifluoroethyl or to understand the pentafluoroethyl group;

under the expression "(C ₁ -C ₂₀ ) alkylidene", for example the exo-methylene, ethylidene, propylidene, 1-methyl-propylidene, butylidene, octylidene or dodecylidene group under the expression "(C ₁ -C ₂₀ ) -Alkyloximino "an oximino group which is linked to the oxygen with one of the under the expression" (C ₁ -C ₂₀ ) alkyl "

Alkyl groups are etherified;

under the term "cycloalkyl" preferably (C ₃ -C ₈ ) cycloalkyl;

under the term "cycloalkoxy" preferably (C ₃ -C ₈ ) cycloalkoxy;

under the term "cycloalkylthio" preferably (C ₃ -C ₈ ) cycloalkylthio;

under the expression "(C ₃ -C ₅ ) cycloalkyl" the cyclopropyl, cyclobutyl or cyclopentyl group;

under the expression "(C ₃ -C ₈ ) cycloalkyl" the radicals mentioned above under "(C ₃ -C ₅ ) cycloalkyr, as well as the cyclohexyl, cycloheptyl or cyclooctyl radical, but also bicyclic systems such as, for example, the norbornyl - or bicyclo [2,2,2] octyl radical;

under the expression "(C ₃ -C ₅ ) halocycloalkyl" one of the above (C ₃ -C ₅ ) cycloalkyl radicals in which one or more, in the case of fluorine, if appropriate also all hydrogen atoms, by halogen, preferably fluorine or chlorine , are replaced, such as the 2,2-difluoro or

2,2-dichlorocyclopropane group or the fluorocyclopentane residue; under the expression "(C ₂ -C ₄ ) alkenyl", for example the vinyl, allyl, 2-methyl-2-propene or 2-butenyl group;

under the expression "(C ₂ -C ₂₀ ) alkenyl" the abovementioned radicals and, for example, the 2-pentenyl, 2-decenyl or the 2-eicosenyl group;

under the expression "(C ₂ -C ₄ ) haloalkenyl" a (C ₂ -C ₄ ) 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 "(C ₂ -C ₄ ) alkynyl", for example the ethynyl, propargyl, 2-methyl-2-propyne or 2-butynyl group;

under the expression "(C ₂ -C ₂₀ ) alkynyl" the abovementioned radicals and, for example, the 2-pentynyl or the 2-decynyl group;

under the expression "(C ₂ -C ₄ ) haloalkynyl" a (C ₂ -C ₄ ) alkynyl group in which the hydrogen atoms are partially, in the case of fluorine, also completely

Halogen atoms, preferably fluorine or chlorine, are replaced; under the expression

"Tri- (C ₁ -C ₄ ) alkylsilyl- (C ₂ -C ₄ ) alkynyl preferably the trimethylsilyl group under the expression" (C ₁ -C ₄ ) -hydroxyalkyl ", for example the hydroxymethyl,

 1-hydroxyethyl, 2-hydroxyethyl, 1-hydroxy-1-methyl-ethyl or

 1-hydroxypropyl group;

under the expression "(C ₁ -C ₄ ) alkanoyl", for example the formyl, acetyl, propionyl,

2-methylpropionyl or butyryl group;

under the expression “(C ₁ -C _{l 2} ) alkanoyl”, for example the abovementioned radicals and, for example, the valeroyl, pivaloyl, hexanoyl, decanoyl or the

 Dodecanoyl group;

under the expression "(C ₂ -C ₄ ) -haloalkanoyl" a (C ₁ -C ₄ ) -alkanoyl group in which the hydrogen atoms are partially, in the case of fluorine, completely

Halogen atoms, preferably fluorine or chlorine, are replaced;

under the expression "(C ₂ -C ₁₂ ) haloalkanoyl" a (C ₁ -C ₂₀ ) alkanoyl group in which the hydrogen atoms are partially, in the case of fluorine, completely

Halogen atoms, preferably fluorine or chlorine, are replaced;

under the term "cyano (C ₁ -C ₄ ) alkyl" a cyanoalkyl group whose

Hydrocarbon radical that specified under the expression "(C ₁ -C ₄ ) alkyl"

Has meanings; under the expression "(C ₁ -C ₄ ) alkoxycarbonyl", for example the methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, butoxycarbonyl or tert-butoxycarbonyl group;

under the expression "(C ₁ -C ₁₂ ) alkoxycarbonyl" the abovementioned radicals and, for example, the hexyloxycarbonyl, 2-methylhexyloxycarbonyl,

Decyloxycarbonyl or dodecyloxycarbonyl group;

under the expression "(C ₁ -C ₄ ) haloalkoxycarbonyl" a (C ₁ -C ₄ ) alkoxycarbonyl group in which one or more, in the case of fluorine

optionally all hydrogen atoms are replaced by halogen, preferably fluorine or chlorine;

under the expression "(C ₁ -C ₄ ) alkylthio" an alkylthio group, the

Hydrocarbon radical has the meaning given under the expression "(C ₁ -C ₄ ) alkyl";

under the expression "(C ₁ -C ₄ ) haloalkylthio" a (C ₁ -C ₄ ) alkylthio group in which one or more, in the case of fluorine, if appropriate, all of them

Hydrogen atoms of the hydrocarbon part are replaced by halogen, in particular chlorine or fluorine;

the term "fluoromethylthio" means the mono-, di- and trifluoromethylthio group;

under the expression "(C ₁ -C ₄ ) alkylsulfinyl", for example the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butylsulfinyl group;

under the expression "(C ₁ -C ₄ ) alkylsulfonyr ', for example the methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl or tert-butylsulfonyl group;

under the terms "(C ₁ -C ₄ ) haloalkylsulfinyl" and "(C ₁ -C ₄ ) haloalkylsulfonyl" (C ₁ -C ₄ ) alkylsulfinyl and sulfonyl radicals with the meanings given above, in which one one or more, in the case of fluorine, optionally all the hydrogen atoms in 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 expression "(C ₁ -C ₄ ) alkoxy" an alkoxy group whose

Hydrocarbon radical that specified under the expression "(C ₁ -C ₄ ) alkyl" Has meaning;

the term "(C ₁ -C ₄ ) haloalkoxy" means a haloalkoxy group whose halogenated hydrocarbon radical has the meaning given under the term "(C ₁ -C ₄ ) haloalkyl";

for example, under the expression "(C ₁ -C ₄ ) alkoxy- (C ₁ -C ₄ ) alkyl"

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 "(C ₁ -C ₄ ) haloalkoxy- (C ₁ -C ₄ ) alkyl," (C ₁ -C ₄ ) alkoxy- (C ₁ -C ₄ ) haloalkyl "and" (C ₁ -C ₄ ) haloalkoxy- (C ₁ -C ₄ ) haloalkyl "

(C _l -C ₄₎ alkoxy (C ₁ -C ₄₎ alkyl radicals having the abovementioned meanings where one or more, in the case of fluorine optionally also all,

Hydrogen atoms of the corresponding hydrocarbon fractions

Halogen, preferably chlorine or fluorine are replaced;

under the expression "(C ₁ -C ₄ ) alkylthio- (C ₁ -C ₄ ) alkyl" for example

Methylthiomethyl, ethylthiomethyl, propylthiomethyl, 2-methylthioethyl,

2-ethylthioethyl or 3-methylthiopropyl;

under the term "aryl" with an isocyclic aromatic radical

preferably 6 to 14, in particular 6 to 12 carbon atoms, such as, for example, phenyl, naphthyl or biphenylyl, preferably phenyl;

under the term "heterocyclyl" a heteroaromatic or

heteroaliphatic ring system, where "heteroaromatic ring system" means 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, e.g. 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, pyridin, pyrazine 1, 3,5-triazine, 1, 2,4-triazine, 1, 2,4,5-triazine, quinoline, isoquinoline, quinoxaline, quinazoline, Cinnolin, 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 (C ₃ -C ₈ ) cycloalkyl radical in which at least one carbon unit is represented by O, S or a

Group NR ^{1 1 is} replaced and R ^{1 1 is} hydrogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or aryl;

under the term "arylthio" e.g. the phenylthio or the 1- or

 2-naphthylthio group;

under the term "aryloxy" e.g. 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 "(C ₃ -C ₈ ) -cycloalkoxy" or "(C ₃ -C ₈ ) -cycloalkylthio" one of the above-mentioned (C ₃ -C ₈ ) -cycloalkyl radicals, which via an oxygen or

Sulfur atom are linked;

under the expression "aroyl" e.g. the benzoyl, naphthoyl or the

 Biphenylcarbonyl group;

under the expression "aryl- (C ₁ -C ₄ ) -alkanoyl", for example the phenylacetyl-, 3-

Phenylpropionyl-, 2-phenylpropionyl-, 2-methyl-2-phenyl-propionyl-, 4-

Phenylbutyryl or the naphthylacetyl group;

under the expression "(C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) alkanoyl", for example the

 Cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl,

Cyclohexylcarbonyl, cyclohexylacetyl or the cyclohexylbutyryl group; under the expression "heterocyclyl- (C ₁ -C ₄ ) -alkanoyl", for example the thenoyl, furoyl,

Nicotinoyl, thienylacetyl or the pyridine propionyl group;

under the expression "(C ₃ -C ₈ ) cycloalkoxycarbonyl" for example the

 Cyclobutyloxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl or the cycloheptyloxycarbonyl group;

under the expression "(C ₃ -C ₈ ) cycloalkyl (C ₁ -C ₄ ) alkoxycarbonyl" for example the

Cyclopropylmethoxycarbonyl, cyclobutylmethoxycarbonyl,

Cyclopentyloxymethoxycarbonyl, cyclohexyloxymethoxycarbonyl-, 1- (cyclohexyl) ethoxycarbonyl or the 2- (cyclohexyl) ethoxycarbonyl group; under the expression "aryl- (C ₁ -C ₄ ) alkoxycarbonyl", for example the benzyloxycarbonyl,

1-naphthylmethoxycarbonyl-, 2-naphthylmethoxycarbonyl-,

 1-phenyl-ethoxycarbonyl or the 2-phenyl-ethoxycarbonyl group; under the

Expression "heterocyclyl- (C ₁ -C ₄ ) alkoxycarbonyl", for example the

 Thienylmethoxycarbonyl, furylmethoxycarbonyl,

 Tetrahydrofurylmethoxycarbonyl or the pyridylethoxycarbonyl group;

under the term "aryloxycarbonyl" e.g. the phenoxycarbonyl,

 Naphthoxycarbonyl or the biphenyloxycarbonyl group;

under the term "hetercyclyloxycarbonyl" e.g. the tetrahydropyran-4-oxycarbonyl group;

under the expression "(C ₁ -C ₂₀ ) alkanoyloxy", for example formyloxy, acetoxy,

Propionyloxy, butyryloxy, pivaloyloxy, valeroyloxy or the hexanoyloxy

Group;

under the expression "(C ₂ -C ₂₀ ) haloalkanoyloxy" a (C ₂ -C ₂₀ ) alkanoyloxy

Group in which one or more, in the case of fluorine, if necessary, all

Hydrogen atoms of the hydrocarbon part through halogen, in particular

Fluorine or chlorine are replaced;

under the expression "(C ₃ -C ₈ ) cycloalkanoyloxy", for example the cyclopropanoyloxy,

Cyclobutenoyloxy, cyclopentanoyloxy, cyclohexanoyloxy or the

 Cycloheptanoyloxy group;

under the expression "(C ₃ -C ₈ ) cycloalkyl (C ₁ -C ₄ ) alkanoyloxy" for example the

 Cyclopropylcarbonyloxy, cyclopropylacetoxy, cyclobutylcarbonyloxy,

 Cyclopentylcarbonyloxy, Cyclohexylcarbonyloxy, Cyclohexylacetoxy- or die

4-cyclohexyl-butyryloxy group;

under the term "aroyloxy" e.g. the benzoyloxy or the naphthoyloxy group;

under the expression "aryl- (C ₁ -C ₄ ) -alkanoyloxy", for example the benzoyloxy-,

 Naphthoyloxy, biphenylcarbonyloxy, phenylacetoxy or the

 Phenylbutyryloxy group;

under the expression "heterocyclyl- (C ₁ -C ₄ ) alkanoyloxy" for example the

Thienylcarbonyloxy, thienylacetoxy, pyridylcarbonyloxy or die Pyrimidinylcarbonyloxy group;

under the expression "(C ₂ -C ₂₀ ) alkylsulfonyloxy", for example the methane, ethane,

Butane or hexanesulfonyloxy group;

under the term "arylsulfonyloxy" e.g. the phenylsulfonyloxy or the

Toluenesulfonyloxy group.

The substituents with which the various aliphatic, aromatic and heterocyclic ring systems can be provided include, for example, halogen, nitro, cyano, di- (C ₁ -C ₄ ) -alkylaminio, (C ₁ -C ₄ ) -alkyl, (C ₃ -C ₈ ) -cycloalkyl, (C ₁ -C ₄ ) -trialkylsilyl, (C ₁ -C ₄ ) -alkoxy, (C ₁ -C ₄ ) -alkoxy- (C ₁ -C ₄ ) -alkyl, (C ₁ -C ₂ ) alkoxy- [CH ₂ CH ₂ O] _{1, 2} -ethoxy, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C ₄ ) alkylsulfonyl, Thiocyano, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) haloalkoxy, (C ₁ -C ₄ ) haloalkylthio, (C ₂ -C ₄ ) haloalkylsulfinyl, (C ₁ -C ₄ ) - Haloalkylsulfonyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) haloalkenyl, trimethylsilylethynyl, (C ₁ -C ₄ ) alkanoyl, (C ₁ -C ₄ ) alkoxycarbonyl, 4-acetylpiperazin-1 - yl, phenyl, benzyl, phenoxy, halophenoxy, (C ₁ -C ₄ ) alkylphenoxy, (C ₁ -C ₄ ) alkoxyphenoxy, phenylthio, heterocyclyl, heterocylylthio or heterocyclyloxy, with one or more in the alkyl radicals and the radicals derived therefrom Water off-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 (C ₁ -C ₄ ) -alkyl, these can also be cyclically linked and in these condensed ring systems such as indane, 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 also up to the maximum number, by halogen or (C ₁ -C ₄ ) alkyl can be replaced.

Furthermore, under the definition that "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, NR ⁶ or SiR ⁷ R ⁸ can be replaced, where R ^{6 is} hydrogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) alkoxy or (C ₁ -C ₄ ) alkanoyl and R ⁷ and R ⁸ ( C ₁ -C ₄ ) -Alkyl, preferably methyl, and in which, in addition, 3 to 12 atoms of these hydrocarbon radicals, which may have been 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 of identical or different radicals from the series 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 can be substituted, the cycloaliphatic, aromatic or heterocyclic ring systems being unsubstituted under the just mentioned substituents or with up to three, in the case of fluorine also up to the maximum number of identical or different substituents can be provided, the cycloaliphatic, aromatic or heterocyclic ring systems being unsubstituted under the just mentioned substituents or having up to three, in the case of fluorine also up to the maximum number of identical or different substituents ", for example to understand:

Alkoxyalkyl radicals, such as e.g. the methoxymethyl, methoxyethyl or

Ethoxyethyl group; or

Alkoxy-alkoxy-alkyl radicals, such as, for example, the methoxy or the ethoxy-ethoxyethyl group; or Alkylthioalkyl radicals, such as, for example, the methyl or the ethylthioethyl group; or

Alkylsulfinyl-alkyl residues, e.g. the methyl or ethylsulfinylethyl group; or

 Alkylsulfonyl-alkyl radicals, such as e.g. the methyl or ethylsulfonylethyl group; or

 Alkyl-dialkylsilyl-alkyl, preferably alkyl-dimethylsilyl-alkyl radicals, such as e.g. the

Trimethylsilylmethyl or the trimethylsilylethyl group; or

 Trialkylsilyl, preferably alkyldimethylsilyl, e.g. the trimethylsilyl,

Ethyldimethylsilyl, tert-butyldimethylsilyl or the octyldimethylsilyl group; or

 Cycloalkyldialkylsilyl, preferably cycloalkyldimethylsilyl, such as e.g. the

Cyclohexyldimethylsilyl group; or

 Aryldialkylsilyl, preferably aryldimethylsilyl residues such as e.g.

 Phenyldimethylsilyl group; or

 Arylalkyl dialkylsilyl, preferably aryldimethylsilyl residues such as e.g. the

 Benzyldimethylsilyl or the phenylethyldimethylsilyl group; or

 Alkanoylalkyl residues such as e.g. the acetylmethyl or the pivaloylmethyl group; or

 Cycloalkanoylalkyl residues such as e.g. the cyclopropylcarbonylmethyl or the

Cyclohexylcarbonylmethyl group; or

 Halogenalkanoylalkyl residues such as e.g. the trifluoro or trichloroacetyimethyl group; or

 Aroylalkyl residues such as e.g. the benzoyl or naphthoylalkyl residues such as e.g. the

Phenylacetylmethyl group; or

 Heterocyclylcarbonylalkyl residues such as e.g. the thienyl or pyridylacetylmethyl group; or

 Aryl-alkyl residues, e.g. 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-phenyl-ethyl group or the 1-methyl or 2-methyl-naphthyl group; or

 Heterocyclylalkyl residues, e.g. the thienylmethyl, pyridylmethyl, furfuryl,

Tetrahydrofurfuryl, tetrahydropyranylmethyl or 1,3-dioxalane-2-methyl Group; or

 Aryloxyalkyl radicals, such as e.g. the phenoxymethyl or naphthoxymethyl group; or

Cycloalkyl residues, monocyclic such as e.g. the cyclopropyl, cyclobutyl,

 Cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl radical, bicyclic such as e.g. the norbornyl radical or the bicyclo [2.2.2] octane radical or condenses as that

Decahydronaphthyl residue;

 Alkyl-cycloalkyl residues such as e.g. the 4-methyl or the 4-tert-butylcyclohexyl group or the 1-methyl-cyclopropyl, cyclobutyl, cyclopentyl or

 -cyclohexyl group;

 Cycloalkyl-alkyl residues such as e.g. the cyclohexylmethyl or ethyl group;

or also haloalkyl derivatives of the corresponding groups, for example

Haloalkyl, haloalkoxyalkyl, alkoxy haloalkyl, haloalkyl cycloalkyl or

 Halocycloalkyl residues.

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

The present invention relates to the compounds of formula I in the form of the free base or an acid addition salt. Acids that can be used for salt formation are inorganic acids, such as hydrochloric acid,

Hydrogen bromide 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.

Some of the compounds of the formula I have one or more asymmetric carbon atoms or stereoisomers on double bonds. Enantiomers or diastereomers can therefore occur. The invention encompasses both the pure isomers and their mixtures. The mixtures of diasteromers can be prepared using customary methods, for example by selective crystallization suitable solvents or by chromatography in the components. Racemates can be added to the

Enantiomers are separated, e.g. by salt formation with an optically active acid, separation of the diastereomeric salts and release of the pure enantiomers using a base.

The invention further relates to a process for the preparation of compounds of the formula I, which is characterized in that a compound of the formula II

wherein A, R ¹ , R ² and R ^{3 have} the meanings given under formula I and L is a leaving group, such as halogen, alkylthio, alkanesulfonyloxy or arylsulfonyloxy, alkylsulfonyl or arylsulfonyl, with a

Nucleophile of formula III

wherein a, b, r, s, E, U, V, W, X, Y, Z, R ⁴ , R ⁵ and R ^{6 have} the meanings given above under formula I, and the compounds obtained in this way or otherwise of the formula I, optionally derivatized on the heterocycle and / or in the side chain R ⁶ , and the compounds optionally converted into their salts. The substitution reaction described above is known in principle. The

Leaving group Z can be varied within wide limits and can mean, for example, a halogen atom, such as fluorine, chlorine, bromine or iodine; or alkylthio, such as methyl or ethylthio; 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 aforementioned reaction is carried out in a temperature range of 20-150 ° C., advantageously in the presence of a base and optionally in an inert organic solvent, 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. Mixtures of the solvents mentioned can also be used.

Suitable bases for the case where X is oxygen or S (O) _x are, for example, alkali or alkaline earth metal carbonates, hydrogen carbonates, amides or hydrides such as sodium carbonate, sodium hydrogen carbonate, potassium carbonate, sodium amide or sodium hydride, in the event that X is NH means, for example, alkali or alkaline earth metal carbonates, hydrogen carbonates, hydroxides, amides or hydrides such as sodium carbonate,

 Sodium bicarbonate, potassium carbonate, sodium hydroxide, sodium amide or sodium hydride or organic bases, such as triethylamine or pyridine, or a second equivalent of the nucleophile with X = NH.

The invention further relates to a process for the preparation of compounds of formula I, wherein Y and Z are oxygen and W is a group (CH ₂ ) _n with n = 2, 3, 4, which is characterized in that one

Compound of the general formula IV, in which a, b, r, A, X, E, R ¹ , R ² , R ³ and R ^{4 have} the meanings given above for formula I, in the presence of an acid catalyst, with a diol of the general formula V,

wherein U, V, R ⁵ , R ⁶ and s have the meanings given above and n denotes the numbers 2, 3 or 4, and with elimination of water, the compounds of the formula I are obtained and, if appropriate, these continue in the side chain R ⁶

derivatized.

The ketalization reaction described above is known in principle. It is carried out in a temperature range of 20-200 °, preferably between 60 and 150 °, in the presence of an acidic dehydration catalyst, in bulk or in an inert solvent. Suitable catalysts are, for example, 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 acidic ion exchangers such as Amberlite IR-120 . The water formed in the reaction is expediently distilled off, if appropriate under reduced pressure, or removed from the reaction mixture by azeotropic distillation using an entrainer. Suitable entraining agents are, for example, benzene, toluene, xylene or petroleum ether.

The invention further relates to a process for the preparation of compounds of the formula I in which Y and Z are oxygen and W is a group (CH ₂ ) _n with n = 2, 3, 4, which is characterized in that a compound of the formula I '

for the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a, b, r, s, A, X and E those for the formula I.

have the meanings indicated, n = 2, 3 or 4 and s = 0, in the presence of an acidic catalyst with a diol of the general formula V and thereby obtains the end products with transketalization.

The reaction temperature, solvents and catalysts correspond to those described in the reaction of the compounds of the formula IV with the compounds of the formula V. The diol V is advantageously used in excess.

If X is oxygen, the nucleophiles of the formula III required as starting products can be prepared by known processes, for example by reducing a carbonyl group with a suitable reducing agent, such as a complex metal hydride or in the case of a

Aldehydes or ketones, for example with hydrogen and a hydrogenation catalyst. Other possibilities are the implementation of an organometallic compound with a carbonyl group or an oxirane. If X is NH, the nucleophiles of the formula III required as starting products can be prepared by known processes, for example by reducing an oxime or a nitrile with a suitable reducing agent, for example a complex metal hydride or hydrogen in the presence of a hydrogenation catalyst, reductive amination or Leuckart-Wallach reaction of an aldehyde or ketone or Gabriel reaction of an alkyl halide or tosylate.

Those nucleophiles of the formula III which act as starting materials for the preferred

Compounds of the general formula I are used in which E denotes a direct bond, are described from the corresponding ones as described above

Cycloalkanones of the formula VI,

wherein a, b, r, s, U, V, W, Y, Z, R ⁴ , R ⁵ and R ⁶ have the formula I above

have the meanings given, e.g. by reductive amination or

Obtain reduction with a complex hydride.

Depending on a, b, r, s, W, Y and Z, these compounds of the formula VI can be prepared by reactions which are known in principle.

For example, spiro derivatives of cyclohexanone (a = b = 2) can be obtained by the following methods:

The reactions described under a), b), c) and e) can, although with poorer yields, also be used with cyclohexane-1,4-dione as starting material

carry out.

Suitable starting materials with other ring sizes (a, b ≠ 2) are also described (Tetrahedron Lett. 28 (1987) 551).

All reactions starting from cyclohexane-1,4-dione-monoketal (VII) are also possible with the 4-keto-cyclohexylamine derivative IV.

Epoxy derivatives (X = CH ₂ , Z = O, W = direct bond between Y and Z) can best be produced from ketones IV or exo-alkylene derivatives XII.

The preparation of the starting materials of the formulas IV and XII is described in DE-A-43 31 179.

The active ingredients are suitable for good plant tolerance and cheaper

Warmblood toxicity to control animal pests, in particular

Insects, arachnids, helminths and molluscs, very particularly preferably for controlling insects and arachnids, which occur in agriculture, animal husbandry, forestry, in the protection of stored goods and materials, and in the hygiene sector. They are normally sensitive and resistant

Species as well as all or individual stages of development are effective. The pests mentioned above include:

 From the order of the Acarina e.g. 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 e.g. Oniscus asselus, Armadium vulgar, Porceilio scaber.

 From the order of the Diplopoda e.g. Blaniulus guttulatus.

 From the order of the Chiiopoda e.g. Geophilus carpophagus, Scutigera spp ..

From the order of the Symphyla e.g. Scutigerella immaculata.

 From the order of the Thysanura e.g. Lepisma saccharina.

From the order of the Collembola, for example Onychiurus armatus. From the order of the Orthoptera, for example 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 e.g. Reticulitermes spp ..

 From the order of the anoplura e.g. Phylloera vastatrix, Pemphigus spp.,

 Pediculus hυmanus corporis, Haematopinus spp., Linognathus spp ..

 From the order of the Mallophaga e.g. Trichodectes pp., Damalinea spp ..

 From the order of the Thysanoptera e.g. Hercinothrips femoralis, Thrips tabaci.

From the order of the Heteroptera e.g. Eurygaster spp., Dysdercus intermedius,

Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp ..

 From the order of the Homoptera e.g. Aleurodes brassicae, Bemisia tabaci,

Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doraiis 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 e.g. 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, Heiiothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni,

Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria melionella, Cacoecia podana, Capua reticulana,

 Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana.

 From the order of the Coleoptera e.g. 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 psylioides,

 Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica.

 From the order of the Hymenoptera e.g. Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp ..

 From the order of the Diptera e.g. 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 e.g. Xenopsylla cheopsis, Ceratophyllus spp ..

 From the order of the Arachnida e.g. Scorpio maurus, Latrodectus mactans.

From the class of the helminths e.g. Haemonchus, Trichostrongulus, Ostertagia,

Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus,

Ancylostoma, Ascaris and Heterakis as well as Fasciola and plant-damaging

Nematodes e.g. those of the genera Meloidogyne, Heterodera, Ditylenchus,

Aphelenchoides, Radopholus, Globodera, Pratylenchus, Longidorus and

 Xiphinema.

 From the class of the Gastropoda e.g. Deroceras spp., Arion spp., Lymnaea spp.,

Galba spp., Sυccinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp ..

From the class of the Bivalva e.g. Dreissena spp ..

The plant-parasitic nematodes that can be controlled according to the invention include, for example, the root-parasitic soil nematodes, e.g. those of the genera Meloidogyne (root-bile nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica),

Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera schachtii, Heterodera avenae, Heterodera glycines and Heterodera trifolii) as well as the genera Radopholus such as Radopholus similis, Pratylenchus such as Pratyglenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus; Tylenchulus like Tylenchulus

semipenetrans, Tylenchorhynus, such as Tylenchorhynchus dubius and

Tylenchorhynchus claytoni, Rotylenchus like Rotylenchus robustus,

Helicotylenchus like Helicotylenchus multicinctus, Belonoaimus like Belonoaimus longicaudatus, Longidorus like Longidorus elongatus, Trichodorus like

Trichodorus primitivus and Xiphinema like Xiphinema index.

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

Combat Aphelenchoides ritzemabosi) and Anguina (flower nematodes, such as Anguina tritici).

The invention also relates to compositions, in particular insecticidal and nematocidal acaricidal compositions, which contain the compounds of the formula I in addition to suitable ones

Formulation aids included.

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

They can be formulated in different ways, depending on how it is specified by the biological and / or chemical-physical parameters. Possible formulations are therefore:

Wettable powder (WP), emulsifiable concentrates (EC), aqueous solutions (SD, emulsions, sprayable solutions, oil or water-based dispersions (SO, suspoemulsions (SE), dusts (DP), mordants, 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 N.Y., 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 N.J .; H. v. Olphen, "Introduction to Clay Colloid

Chemistry ", 2nd Ed., J. Wiley & Sons, NY; Marschen," Solvente 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,

"Surface-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 with other pesticidally active substances, fertilizers and / or can also be made

Create growth regulators, e.g. in the form of a finished formulation or as a tank mix. Spray powders are preparations which are uniformly dispersible in water and which, in addition to the active substance, contain wetting agents, e.g. polyoxethylated alkylphenols, polyoxethylated fatty alcohols, alkyl or alkylphenol sulfonates and dispersants, e.g. sodium lignosulfonate, 2,2'-dinaphthylmethane-6,6'-disulfonic acid sodium.

Emulsifiable concentrates are prepared by dissolving the active ingredient in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or even higher-boiling aromatics or hydrocarbons with the addition of one or more emulsifiers. 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 solid substances, e.g. Talc, natural clays such as kaolin, bentonite, pyrophillite or diatomaceous earth. Granules can be obtained either by spraying the

Active ingredient can be prepared on adsorbable, granulated inert material or by applying active ingredient concentrates by means of adhesives, e.g. Polyvinyl alcohol, sodium polyacrylic acid or mineral oils, on the surface of carriers such as sand, kaolinite or granulated

Inert material. Suitable active ingredients can also be granulated in the manner customary for the production of fertilizer granules, if desired in a mixture with fertilizers.

The active substance concentration in wettable powders is e.g. about 10 to 90% by weight, the remainder to 100% by weight consists of conventional formulation components. In the case of emulsifiable concentrates, the active substance 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 .-%. In the case of granules, the active ingredient content depends in part on whether the active compound is in liquid or solid form and which granulation aids, fillers, etc. are used.

In addition, the active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetrating,

Solvents, fillers or carriers. For use, the concentrates present in the commercial form are optionally diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also in the case of microgranules, using water. Dust-like and granulated preparations as well as sprayable solutions are usually no longer diluted with other inert substances before use.

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

Forms of use 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, etc.

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, Dichlorophos, Dicrotophos O, O-1, 2,2,2-Tetrachlorethylphosphorthioate (SD 208 304), Dimethoate, Disulfoton, EPN, Ethion, Ethoprophos, Etrimfos, Famphur, Fenamiphos, Fenitriothion, Fensulfothion, Fenthion, Fonofos,

Formothion, Heptenophos, Isozophos, Isothioate, Isoxathion, Malathion,

Methacrifos, Methamidophos, Methidathion, Salithion, Mevinphos, Monocrotophos, Naled, Omethoate, Oxydemeton-methyl, Parathion, Parathion-methyl, Phenthoate, Phorate, Phosalone, Phosfolan, Phosmet, Phosphamidon, Phoxim, Pirimiphos, Primiphos-ethyl, Pirimiphos-methyl, Profenofos, Propaphos, Proetofphos, Prothofofos, Prothiophos Pyridapenthion, quinalphos, sulprofos, temephos, terbufos, tetrachlorvinphos, thiometone, triazophos, trichlorphone, vamidothione;

2. from the group of carbamates

 Aldicarb, 2-sec-Butylphenylmethylcarbamate (BPMC), Carbaryl, Carbofuran, Carbosulfan, Cloethocarb, Benfuracarb, Ethiofencarb, Furathiocarb, Isoprocarb, Methomyl, 5-Methyl-m-cumenylbutyryl (methyl) carbamate, Oxamyl, Propimioxoxarbox, pirimiarbox , Ethyl-4,6,9-triaza-4-benzyl-6, 10-dimethyl-8-oxa-7-oxo-5,1 1-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) - (1 R) -cis, 2,2-dimethyl-3- (2-oxothiolan-3-ylidenemethyl) cyclopropanecarboxylate, bioallethrin,

Bioallethrin ((S) -cyclopentyl isomer), bioresmethrin, biphenates, (RS) -1-cyano-1- (6-phenoxy-2-pyridyl) methyl- (1 RS) -trans-3- (4-tert.butylphenyl) -2,2-dimethylcyclopropane decarboxylate (NCI 85193), cycloprothrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin,

Esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D-isomer), permethrin, pheothrin ((R) -isomer), d-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-chlorophenyl) -4,5-diphenylthiophene (UBI-T 930), chlororfentezine,

Cyclopropanecarboxylic acid (2-naphthylmethyl) ester (Rol 2-0470), 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), granular 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-ylcarbamaldehyde (WL 108477), propargite, teflubenzuron, tetradifon, tetrasul, thiocyclam, trifumuron, imidacloprid.

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

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

The active compounds according to the invention are also suitable for combating endoparasites and ectoparasites in the veterinary field or in the field of animal husbandry. The active compounds according to the invention are used here in a known manner, such as by oral use in the form of, for example, tablets, capsules, drinkers, granules, by dermal use in the form

for example diving (dipping), spraying (spraying), pouring on (pour-on and spot-on) and powdering, and by parenteral use in the form of, for example, injection.

The new compounds of formula I according to the invention can accordingly also be used particularly advantageously in livestock farming (e.g. cattle, sheep, pigs and poultry such as chickens, geese, etc.) In a preferred embodiment of the invention, the animals are given the new compounds, if appropriate in suitable formulations (see above) and if appropriate with the drinking water or feed orally. Since excretion in the faeces is effective, the development of insects in the faeces of the animals can be prevented very easily in this way. The suitable dosages and formulations are in particular of the type and

Developmental stage of the farm animals and also dependent on the infestation pressure and can be easily determined and determined according to the usual methods. The new compounds can e.g. in doses of 0.01 to 1 mg / kg body weight.

The compounds of the formula I according to the invention are also notable for an excellent fungicidal action. Fungal pathogens that have already penetrated into the plant tissue can be successfully combated curatively. 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

The spectrum of activity of the claimed compounds covers various economically important phytopathogenic fungi, such as, for example, Piasmopara viticola, Erysiphe graminis and Puccinia recondita. The compounds according to the invention are also suitable for use in technical fields, 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.

Examples of fungicides known from the literature which can be combined according to the invention with the compounds of the formula I are, for example 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, Dichlobrazine, Dichlobrazine Diethofencarb, Difenconazole (CGA 169374), Difluconazole, Dimethirimol, Dimethomorph, Diniconazole, Dinocap, Dithianon, Dodemorph, Dodine, Edifenfos, Ethirimol, Etridiazol, Fenarimol, Fenfuram, Fenpiclonil, Fenpropidine, Fentinimimidone, Fentinpimidone, Fentinpimidone, Fentinpimidone, Fentinpimidone, Fentinpimidone, Fentinpimidone , Fiuobenzimine.Fluquinconazole, Fluorimide, Flusilazole, Flutolanil, Flutriafol, Folpet, Fosetylaluminium.Fuberidazole, Fulsulfamide (MT-F 651), Furalaxyl, Furconazole, Furmecyclox, Guazatine, Hexaconazole, Imazalazole Ipone, Icazoprilone, ICI550 Iodine, ICI550 I450 Iodine, ICI5504 I450I, KNF 317, copper compounds such as Cu-oxychloride, Oxine-Cu, Cu-oxide, Mancozeb, Maneb, Mepanipyrim (KIF 3535), Metconazol, Mepronil, Metalaxyl, Methasulfoca rb, Methfuroxam, MON 24000, Myclobutanil, Nabam, Nitrothalidopropyl, Nuarimol, Ofurace, Oxadixyl, Oxycarboxin, Penconazol, Pencycuron, PP 969, Probenazole, Propineb, Prochloraz, Procymidon, Propamocarb, Propiconazol, Pyrailoxonif, Pyrothilonox, Pyrothilonox, Pyrothilonox, Pyrothilonox, Pyrothilonoxa Rabenzazole, RH7592,

Sulfur, tebuconazole, TF 167, thiabendazole, thicyofen, thiofanatemethyl, thiram, tolclofos-methyl, tolylfluanid, triadimefon, triadimenol, tricyclazole, tridemorph, triflumizole, triforine, validamycin, vinchlozolin, sodium-dodecylate, Sodium C13 / C15 alcohol ether sulfonate, sodium cetostearyl phosphatester, dioctyl sodium sulfosuccinate, sodium-isopropyl-naphthalenesulfonat, sodium methylenebisnaphthalenesulfonat, Cetyl-trimethyl-ammonium chloride, salts of primary long-chain, secondary or tertiary amines, alkyl-propyleneamine, lauryl pyrimidiniumbromid, ethoxylated quaternized Fatty amines, alkyl-dimethyl-benzyl-ammonium chloride and 1-hydroxyethyl-2-alkyl-imidazoline.

The above-mentioned combination partners are known active ingredients, which are largely 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 explain the invention, without this being restricted thereto.

A. Formulation examples a) A dusting agent is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc as an inert substance and comminuting them in a hammer mill. b) A wettable powder which is readily dispersible in water is obtained by adding 25 parts by weight of active compound, 65 parts by weight of kaolin-containing quartz as the inert substance, 10 parts by weight of lignosulfonic acid potassium and 1 part by weight of oleoylmethyl tauric acid sodium as the wetting agent. and dispersant mixes and grinds in a pin mill. c) A dispersion concentrate which is easily dispersible in water is prepared by mixing 40 parts by weight of active compound with 7 parts by weight of a

 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 of oxyethylated nonylphenol (10 AEO) as an emulsifier. e) Granules can be produced from 2 to 15 parts by weight of active ingredient and an inert granule carrier material such as attapulgite, pumice granules 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, dried and mixed intimately. The proportion by weight of the wettable powder is approximately 5% and that of the inert carrier material approximately 95% of the finished granulate.

B. Biological examples

Fungicidal effect

Example 1: Puccinia recondita

Wheat of the "Jubilar" variety is treated to runoff point in the 2-leaf stage with aqueous suspensions of the claimed compounds.

After the spray coating has dried on, plants are inoculated with an aqueous spore suspension of Puccinia recondita. The plants are dripping wet for approx. 15 hours in a climate chamber at 20 ° C. and approx. 100% rel. Humidity set. Then they are in a greenhouse at a temperature of 22-25 ° C and 50-70% rel. Humidity continued to be cultivated.

After an incubation period of approx. 2 weeks, the fungus sporulates on the entire leaf surface of the untreated control plants (100% infection), so that an evaluation of the infection of the test plants can be carried out. The degree of infestation is expressed in% affected leaf area in comparison to the untreated, infected control plants.

For 500 mg / l spray liquid, the following example numbers show one

Complete infection suppression:

 503, 530, 539, 546, 803, 804, 815, 853.

Acaricidal and insecticidal effects

Example 2: Common spider mite

Bean plants heavily infested with common spider mites (Tetranychus urticae, full population) (Phaseolus vulgaris ssp. Vulgaris var. Nanus) were sprayed with an aqueous preparation which contained 250 ppm of the respective active ingredient until drip started. After cultivating the plants in the greenhouse for 7 days, the mortality of the spider mites (full population) was checked. 100% mortality was found in the following sample numbers:

359, 360, 361, 362, 382, 387, 388, 391, 392, 399, 405, 412, 416, 424, 431, 438, 502, 503, 530, 538, 537, 539, 540, 544, 545, 546, 549, 803,

804, 806, 807, 809, 811, 812, 813, 814, 815, 817, 818, 822, 841, 843, 853, 855, 1049, 1050, 1069. Example 3: Fruit tree spider mite

Apple plants heavily infested with fruit tree spider mites (Panonychus ulmi, full population) (Malus domestica) were sprayed with an aqueous preparation which contained 250 ppm of the respective active ingredient until they began to drip. After cultivating the plants in the greenhouse for 9 days, the mortality of the fruit tree spider mites (full population) was checked. 100%

Mortality was found in the following sample numbers:

278, 359, 360, 361, 362, 382, 388, 391, 392, 399, 405, 412, 416, 431, 438, 502, 503, 530, 536, 537, 538, 539, 540, 544, 545, 546, 549, 803, 804, 806, 807, 809, 81 1, 812, 813, 814, 815, 817, 818, 819, 822, 824, 825, 841, 843, 853, 855, 1049, 1050, 1066 , 1069.

Example 4: Black bean aphid

Field bean plants (Vicia faba) heavily infested with black bean aphids (Aphis fabae, full population) were sprayed with an aqueous preparation which contained 250 ppm of the respective active ingredient until they began to drip. After cultivating the plants in the greenhouse for 3 days, the mortality of the aphids (full population) was checked. 100% mortality was found in the following sample numbers:

 267, 359, 360, 361, 362, 382, 388, 392, 399, 405, 412, 416, 424, 431, 438, 503, 530, 536, 537, 538, 539, 545, 546, 549, 803, 804, 807, 809, 811, 812, 813, 815, 817, 818, 819, 824, 841, 843, 853, 855, 1049, 1066.

Example 5: American Cotton Bug (Eggs)

Filter paper discs with laying eggs (egg age: 2 days) of the American cotton bug (Oncopeltus fasciatus) were each treated with 1 ml of an aqueous preparation which contained 250 ppm of the respective active ingredient. To To dry the covering, the filter paper discs were stored in petri dishes at room temperature and maximum humidity. The ovicidal activity was determined after 7 days. 100% ovicidal activity (egg mortality) was found in the following sample numbers:

 359, 360, 361, 362, 382, 392, 399, 405, 412, 416, 424, 438, 530, 533, 536, 537, 538, 539, 545, 546, 549, 803, 804, 806, 807, 809, 811, 812, 813, 814, 815, 817, 818, 819, 824, 841, 843, 853, 1049, 1064, 1066, 1069.

Example 6: Effect on the whitefly

Bean plants heavily infested with whiteflies (Trialeurodes vaporariorum, 3-day-old eggs) (Phaseolus vulgaris ssp. Vulgaris var. Nanus) were sprayed with an aqueous preparation which contained 250 ppm of the respective active ingredient until dripping started. After cultivating the plants in the greenhouse for 14 days, the mortality of the whitefly (full population) was checked. 100% mortality was found in the following sample numbers: 382, 399, 412, 424, 431, 438, 503, 530, 536, 539, 545, 546, 549, 803, 804, 809, 812, 813, 815, 819, 841 , 842, 853, 855, 1066.

Example 7: Citrus Mealybug

Bean plants heavily infested with citrus smear lice (Planococcus citri, second-stage larvae) (Phaseolus vulgaris ssp. Vulgaris var. Nanus) were sprayed with an aqueous preparation which contained 250 ppm of the respective active ingredient until they began to drip. After the plants had been cultivated in the greenhouse for 7 days, the mortality of the citrus lubricating lice (full population) was checked. 100% mortality was found in the following

Example numbers found:

359, 360, 362, 382, 392, 399, 412, 424, 438, 530, 536, 537, 538, 539, 546, 549, 803, 804, 807, 809, 81 1, 812, 813, 815, 817, 818, 819, 824, 843, 853, 855, 1049.

Example 8: Root systemic effect on the common spider mite

Field bean plants (Vicia faba) potted in the root area

Root balls were covered with foil, an aqueous preparation of the respective active ingredient was evenly distributed (25 ppm active ingredient concentration based on the volume of the soil). After two days, the plants were infected with common spider mites (Tetranychus urticae, full population). After a further 7 days of cultivation of the plants in the greenhouse, the

Spider mite mortality (full population) checked. 100% mortality was found in the following sample numbers:

360, 399, 804, 807, 813.

Example 9: Stem systemic effect on the common spider mite

Three stems of field bean plants (Vicia faba) with heavy infestation by the common spider mite (Tetranychus urticae, full population) were provided with a 300 mg cotton bandage. 2 ml of an aqueous preparation which contained 500 ppm of the respective active ingredient were added to this. After cultivating the plants treated in this way in the greenhouse for 7 days, the mortality of the spider mites (full population) on the leaves was checked.

100% mortality was found in the following sample number:

813.

Example 10: Cockroach (Blaberus craniifer)

Cockroach larvae (L4), Blaberus craniifer, were dissolved in methanol

Active ingredients injected. 100% mortality was found in the following sample numbers detected:

 382, 431, 438, 536, 546, 803, 804, 813, 819, 841, 843, 855.

Example 11:

Larvae (L4) of the tobacco owl, Manduca sexta, were dissolved in acetone

Active ingredients injected. 100% mortality was found in the following sample numbers:

 382, 431, 438, 536, 546, 803, 804, 813, 819, 841, 843.

Example 12: Housefly

The bottom and lid of a Petri dish are coated on the inside with 3 ml of an aqueous dilution of a wettable powder concentrate, which contained 250 ppm of the respective active ingredient.

After the coating had dried on, 24-hour-old houseflies (Musca domestica) were placed in the Petri dishes and these were closed with the treated lid. After 3 hours at room temperature (20 ° C) the mortality of the flies was checked. 100% kill was found in the following sample numbers:

 359, 360, 361, 362, 382, 392, 399, 405, 412, 416, 424, 438, 530, 536,

539, 546, 549, 803, 813, 815, 819, 841.

Example 13: Diabrotica undecimpunctata

Round filter paper was each with 1 ml of the aqueous dilution

Spray powder concentrate, which contained 250 ppm of the respective active ingredient, treated and stored open until dry. After that it was Filter paper placed in the bottom of a petri dish and drizzled with 1 ml of water (distilled) each. Then 10 larvae (L3) from Diabrotica

Place undecimpunctata on the filter paper, close the Petri dish and keep at 28 ° C in the dark for 48 h. The mortality of the larvae was then determined. 100% kill was found in the following sample numbers: 267, 359, 360, 382, 388, 392, 412, 438, 538, 540, 545, 549, 813, 818, 819, 825, 841, 843, 1049, 1050, 1069 .

Example 14: Spodoptera litoralis

Larvae (L3) of the butterfly species Spodoptera litoralis were placed in petri dishes containing about 5 ml of an artificial feed diet and with an aqueous dilution of a wettable powder suspension of the test specimen

Compounds sprayed in an application rate corresponding to 600 l / ha. The petri dishes were then sealed and kept at room temperature for 5 days. The mortality of the animals used was then determined. The compounds in the table examples provided 100% activity

382 and 438.

Example 15: Ovicidal activity (Manduca sexta)

Petri dishes were covered with Japanese filter paper on the inside of the bottom and 20 pieces of 1 day old Manduca sexta eggs were placed on the paper.

Then about 1 ml of an artificial insect feed diet was added to the middle of the Petri dish and the inside of the base was sprayed with eggs and feed diet with an aqueous wettable powder suspension of the test products corresponding to 600 l / ha. After closing the petri dish and storing for 5 days at room temperature, the mortality of the eggs was determined. The compounds in the table examples provided 100% activity 360, 392, 412, 431, 533, 536, 539, 546, 549, 803, 815, 819, 843, 853, 1049.

Example 16: Nilaparvata lugens

Rice seed was germinated under moist conditions and approx.

10 cm high powered. 3 rice plants each were planted in glass tubes which were filled with wet cotton wool and the leaves of the rice plants were immersed in an aqueous dilution of a wettable powder concentrate which contained 250 ppm of the respective active ingredient. After the covering had dried on, the plants were placed with the tube on the bottom of a dish, 10 animals of the brown-backed rice leafhopper (Nilaparvata lugens, L3) were placed in each dish, the dish was closed and stored at 25 ° C. The cicada mortality was checked after 3 days. 100% killing was achieved with the compounds of the table examples

 382, 388, 399, 412, 424, 431, 438, 530, 538, 804, 813, 843, 855, 1050.

Ixodicidal effect

Example 17:

In vitro test on tropical cattle ticks (Boophilus microplus)

The effectiveness of the

Detect compounds according to the invention against ticks:

To prepare a suitable preparation of active compound, the active compounds were dissolved in 10% (w / v) in a mixture consisting of dimethylformamide (85 g), nonylphenol polyglycol ether (3 g) and oxyethylated castor oil (7 g), and the emulsion concentrates thus obtained were dissolved in water diluted a test concentration of 500 ppm. Ten fully sucked females of the tropical tick, Boophilus microplus, were immersed in these active ingredient dilutions for five minutes. The ticks were then dried on filter paper and then attached to the back on an adhesive film for the purpose of laying eggs. The ticks were stored in a warming cabinet at 28 ° C and a humidity of 90%.

As a control, female ticks were only immersed in water. The inhibition of oviposition was used two weeks after treatment to evaluate the effectiveness.

In this test, the compounds according to example numbers 382, 392, 412, 431, 438, 530, 533, 536, 539, 546, 809, 819, 841, 843, 1049 each have a 100% concentration in an active ingredient concentration of 500 ppm Inhibition of egg laying.

C. Manufacturing Examples

Example A (Table Example 817)

5-chloro-4- (3,3-diethyl-1,5-dioxa-spiro [5.5] undec-9-yloxy) -6-ethyl-pyrimidine

2.0 g (8.8 mmol) were added to a suspension of 0.80 g (13.2 mmol) sodium hydride (80%) in 20 ml dry THF under a nitrogen atmosphere.

3,3-Diethyl-1, 5-dioxa-spiro [5.5] undecan-9-ol added and until

complete deprotonation heated under reflux for 2 hours. The reaction solution was then allowed to cool to about 35 ° C., and 1.60 g (8.9 mmol) of 4,5-dichloro-6-ethylpyrimidine, dissolved in 3 ml of dry THF, were rapidly added and the reaction mixture was refluxed to completion Implementation (approx. 2 hours,

DC control). After the reaction mixture had cooled to room temperature, 3 ml of isopropanol were added to destroy excess sodium hydride, stirred for a further 15 minutes and poured onto a mixture of 100 ml of ether and saturated aqueous ammonium chloride solution. The aqueous phase was extracted thoroughly with ether, the combined organic phases over

Dried magnesium sulfate and then concentrated in vacuo. After chromatography on silica gel (petroleum ether / ethyl acetate 3: 2), 2.0 g (60.3% of theory) of a colorless oil were obtained.

Synthesis of the alcohol component

3,3-diethyl-1,5-dioxa-spiro [5.5] undecan-9-ol

820 mg (21.5 mmol) sodium borohydride were added to a solution of 13 g (57.4 mmol) 3,3-diethyl-1, 5-dioxa-spiro [5.5] undecan-9-one in 200 ml ethanol and 1 Stirred for one hour at room temperature. To complete the reaction, the mixture was heated at 40 ° C. for a further 15 hours. To destroy

Excess sodium borohydride was added to about 5 ml of acetone to the reaction solution and stirring was continued for a further 30 min at 40 ° C. The reaction solution was then concentrated in vacuo, taken up in ether and with

Washed ammonium chloride solution and water. The organic phase was carefully dried over magnesium sulfate and then evaporated to dryness. 11.8 g (90.0%) of the desired cyclohexanol were obtained. The crude product was implemented without further purification.

3,3-diethyl-1,5-dioxa-spiro.5.5] undecan-9-one

30 g (0.27 mmol) of cyclohexane-1,4-dione, 35.4 g (0.27 mol) of 2,2-diethyl-propane-1,3-diol and 360 mg of para-toluenesulfonic acid were dissolved in 200 ml of toluene at the

Water separator heated. After cooling to room temperature and separating off the water of reaction, the organic phase was washed with a semi-saturated sodium hydrogen carbonate solution and dried over magnesium sulfate. Evaporation of the solvent gave 65 g Crude product which was purified by flash chromatography (ethyl acetate / petroleum ether = 1: 4). The first fraction contained the 1,4-diketal (10 g) formed as a by-product. The main fraction contained 28.5 g (47%) yellow oil.

Example B (table example 804)

4- (3,3-Dimethyl-1,5-dioxa-spiro [5.5] undec-9-ylamino) -5-methoxy-6-methoxymethyl-pyrimidine

3.8 g (0.02 mol) of 4-chloro-5-methoxy-6-methoxymethyl-pyrimidine (Collection Czechoslov. Chem. Commun. 33 (1968), 2266), 5.0 g (0.025 mol)

3,3-dimethyl-1,5-dioxa-spiro [5.5.undec-9-ylamine and 2.5 g (0.025 mol) triethylamine were heated to 90 ° without solvent for 3 h. After cooling to room temperature, the mixture was taken up in water / methylene chloride and the organic phase was dried and concentrated. Chromatography (silica gel, ethyl acetate) gave 2.8 g (39.8% of theory) of a colorless oil which gradually solidified.

Mp 112-114 ° C

Preparation of the amine component

3,3-dimethyl-1,5-dioxa-spiro.5.5] undec-9-ylamine

A solution of 20.0 g (0.1 mol) of 3,3-dimethyl-1,5-dioxa-spiro [5.5] undecan-9-one in 250 ml of methanol, which contains 38 g of ammonia, was in the presence of 3 g Raney nickel hydrogenated at 100 ° C and 100 bar hydrogen pressure. The catalyst was filtered off and the solvent was removed in vacuo. The crude product was cleaned on a thin film evaporator

(140 ° C / 0.8 bar). 16 g (80% of theory) of distillate were obtained, which solidified on standing. 50-51 ° C

Example C (table example 530)

5-chloro-4- (2-ethoxymethyl-1,4-dioxa-spiro [4.5] dec-8-ylamino) -6-ethyl-pyrimidine

3.0 g (10 mmol) of 4- (5-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone ethylene ketal and 10 ml of 3-ethoxypropane-1,2-diol were mixed with 100 mg of p-toluenesulfonic acid -Hydrate in 10 ml of toluene heated under reflux for 8 h. The reaction mixture was stirred with dilute sodium hydroxide solution and water, the organic phase was dried and the solvent was removed in vacuo. The

Crude product was purified by chromatography on silica gel (eluent

Petroleum ether / ethyl acetate 3: 2) cleaned. 2.0 g (56.3% of theory) of colorless oil (mixture of diastereomers) were obtained.

Preparation of 4- (5-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone ethylene ketal (starting material)

53.1 g (0.3 mol) of 4,5-dichloro-6-ethylpyrimidine, 47.1 g (0.3 mol) of 4-amino-cyclohexanone ethylene ketal (made from cyclohexane-1,4-dione-monoethylene ketal by reductive amination with

 Ammonia / hydrogen / Raney nickel, 100 ° C / 100 bar, yield 90%) and 52 g triethylamine are heated to 90 ° without solvent for 6 h. For working up, the mixture was stirred with water, the organic phase was dried and concentrated in vacuo. After distillation on a thin film evaporator (135 ° / 0.5 bar), 57.8 g (65% of theory) of colorless product remained, which solidified on standing.

Mp .: 102-103 ° C. Example D (table examples 430, 431)

5-chloro-6-ethyl-4- (2-phenyl-1,4-dioxa-spiro [4.5] dec-8-ylamino) pyrimidine

3.8 g (15 mmol) of 4- (4-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone, 2.8 g (20 mmol) of phenylethylene glycol and 500 mg of p-toluenesulfonic acid hydrate were added to 200 ml of toluene heated at the water separator. After disconnecting the

Water of reaction was stirred twice with dilute sodium hydroxide solution and once with water. The organic phase was dried and concentrated. The crude product was chromatographed on silica gel (petroleum ether / ethyl acetate 1: 1). 0.78 g (13.9% of theory) of a diastereomer (colorless crystals, mp. 105-106 ° C.) with relatively weak biological activity were initially obtained and after 1.5 g (26.7% of theory .) Mixed fraction 1.2 g (21.4% of theory). of the other

Diastereomers (colorless oil) with strong biological activity.

Preparation of 4- (4-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone

(Starting material)

70 g (0.235 mol) of 4- (5-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone ethylene ketal (starting material for example C) were mixed in a mixture of 250 ml of tetrahydrofuran and 250 ml of 2N hydrochloric acid for 8 hours at 50 ° C stirred. For working up, the mixture was diluted with 250 ml of toluene and the organic phase was stirred out with sodium carbonate solution and water. After the solvent mixture had been stripped off, 53.4 g (90% of theory) of product remained, which can be reacted without further purification.

M.p. 108-1 10 ° C

Example E (Table Examples 504, 505) 5-chloro-6-ethyl-4- (2-hydroxymethyl-1,4-dioxa-spiro [4.5] dec-8-ylamino) pyrimidine 10.2 g (0.04 mol) of 4- (5-chloro-6-ethyl-pyrimidin-4-ylamino) cyclohexanone ethylene ketal (Example C, starting material), 7.4 g (0.08 mol) of glycerol and 0.5 g of toluenesulfonic acid hydrate were mixed with 100 ml of toluene until the end of

Water development at the water separator heated. After cooling down

Room temperature was stirred twice with dilute sodium hydroxide solution and the organic phase was dried and concentrated. To purify and separate the isomers, the crude product was chromatographed on silica gel (ethyl acetate as the eluent). 3.0 g (22.9% of theory) of pure were initially obtained

Isomers A (colorless crystals, mp: 109-1 10 ° C), then 1.8 (13.7% of theory) of a mixture of isomers and finally 1.8 g (13.7% of theory) of Isomers B (colorless crystals, m.p .: 97-98 ° C).

Example F (table example 659)

5-chloro-6-ethyl-4- [2-methyl-pyridine-5-oxymethyl) -1, 4-dioxa-spiro [4.5] dec-8-ylamino] pyrimidine

1.1 g (0.01 mol) of 3-hydroxy-6-methylpyrimidine, 3.3 g (0.01 mol) of 5-chloro-6-ethyl-4- (2-hydroxy-methyl-1, 4-dioxa -spiro [4.5] dec-8-ylamino) pyrimidine (Example E) and 2.6 g (0.01 mol) of triphenylphosphine were placed in 75 ml of tetrahydrofuran and a solution of 1.8 g (0.01 mol )

Diethyl azodicarboxylate added dropwise in 10 ml of tetrahydrofuran. The mixture was stirred for 4 hours at room temperature, concentrated and the residue was stirred with diisopropyl ether. Solid triphenylphosphine oxide and

Hydrazinedicarboxylic acid diethyl ester, the filtrate was concentrated and

chromatographed the residue on silica gel (eluent: ethyl acetate). 2.6 g (62% of theory) of colorless oil (mixture of isomers) were obtained.

Example G

5-chloro-6-ethyl-4- (2-methylsulfonyloxymethyl-1,3-dioxa-spiro [4.5] dec-8-ylamino) pyrimidine 1.8 g (5.5 mol) of 5-chloro-6-ethyl-4- (2-hydroxymethyl-1,4-dioxa-spiro [4,5] dec-8-ylamino) pyrimidine (Example E, mixture of isomers ), were dissolved in 20 ml of pyridine and a solution of 0.7 g (6.1 mmol) of methanesulfonyl chloride was added dropwise at 0.degree. After standing overnight, it was poured onto ice, brought to pH 3-4 with concentrated hydrochloric acid, stirred with dichloromethane and the

dried organic phase and concentrated. 1.9 g (85% of theory) of a colorless solid (mixture of isomers) were obtained.

Example H (table example 569)

5-chloro-6-ethyl-4- [2- (4-methoxyphenoxymethyl) -1, 4-dioxa-spiro [4.5] dec-8-ylamino] pyrimidine

To a suspension of 0.28 g (9.4 mmol) 80% sodium hydride

(Dispersion in oil) in 25 ml of dimethylformamide, 1.17 g (94 mmol) of 4-hydroxyanisole were added in portions and the mixture was stirred until the evolution of hydrogen had ended, and a solution of 1.90 g (47 mmol) of 5-chloro-6 was then added dropwise -ethyl-4- (2-methylsulfonyloxymethyl-1,3-dioxa-spiro [4,5] dec-8-ylamino] pyrimidine

(Example G) in a little dimethylformamide and stirred for 6 hours at 100 ° C. After the solvent had been stripped off, the mixture was taken up in water / dichloromethane, stirred with dilute sodium hydroxide solution and with water, and the organic phase was dried and concentrated. The crude product was chromatographed on silica gel (eluent ethyl acetate / methanol 9: 1). 1.3 g (68.6% of theory) of a colorless oil (mixture of isomers) were obtained.

Example I (table examples 266, 267)

5-chloro-6-ethyl-4- (2-n-pentyl-1-oxa-spiro [2,5] oct-6-ylamino) pyrimidine

A solution was slowly added dropwise at 0 ° C. to a solution of 6.4 g (0.02 mol) of 5-chloro-6-ethyl-4- (4-hexylidene-cyclohexylamino) pyridimine (WO 95 07894) in 25 ml of dichloromethane Solution of 4.0 g (0.02 mol) m-chloroperbenzoic acid (85 %) in 25 ml dichloromethane. The mixture was stirred at room temperature for 4 h. After standing overnight, the mixture was stirred with aqueous sodium bicarbonate solution and the organic phase was dried and concentrated. The crude product was chromatographed on silica gel (petroleum ether / ethyl acetate 4: 1). First 1.8 g (26.6% of theory) of the isomer with the larger R _f value (0.62) was eluted (colorless crystals, mp: 41-42 ° C.), then a further 1.2 g (18.2% of theory) isomer mixture 0.22 g (3.3% of theory) of the isomer with the smaller R _f value (0.53) as a colorless oil.

In the following tables are others according to the present invention

Establishable connections listed. Insofar as diastereomers are possible, the isomers first eluted with A, the last eluted isomers with B and non-separated mixtures with G in the tables in the chromatography on silica gel with ethyl acetate, petroleum ether / ethyl acetate or ethyl acetate / methanol mixtures.

Claims

Claims:

1. compound of formula I,

in which

R ^{1 represents} hydrogen, halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₃ -C ₅ ) cycloalkyl or (C ₃ -C ₅ ) halocycloalkyl;

R ² and R ^{3 are} identical or different and are each hydrogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) -Halogenalkenyl, (C ₂ -C ₄ ) - alkynyl, (C ₂ -C ₄ ) -haloalkynyl, tri- (C ₁ -C ₄ ) -alkylsilyl- (C ₂ -C ₄ ) -alkynyl, (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) haloalkoxy, (C ₁ -C ₄ ) alkoxy- (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkoxy- (C ₁ -C alkyl _4), (C ₁ -C ₄₎ alkoxy- (C ₁ -C ₄₎ -haloalkyl, (C _l -C ₄₎ -haloalkoxy (C ₁ -C ₄₎ haloalkyl, halogen, hydroxy, ( C ₁ -C ₄ ) hydroxyalkyl, (C ₁ -C ₄ ) alkanoyl, (C ₁ -C ₄ ) alkanoyl (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkanoyl, ( C ₃ -C ₅ ) cycloalkyl, (C ₃ -C ₅ ) halocycloalkyl, cyano, (C ₁ -C ₄ ) cyanoalkyl, nitro, (C ₁ -C ₄ ) nitroalkyl, thiocyano. (C ₁ -C ₄ ) thiocyanoalkyl, (C ₁ -C ₄ ) alkoxycarbonyl, (C ₁ -C ₄ ) alkoxycarbonyl- (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkoxycarbonyl, (C ₁ -C ₄ ) alkylthio, (C ₁ -C ₄ ) alkylthio- (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkylthio, (C ₁ -C ₄ ) alkylsulfinyl, (C ₁ -C ₄ ) haloalkylsulfinyl, (C ₁ -C ₄ ) alkylsulfonyl or (C ₁ -C ₄ ) haloalkylsulfonyl; or

R ² and R ³ 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 CH ₂ , or, if it is a 6-ring, one or two instead of one or two CH units May contain nitrogen atoms and which is optionally substituted by 1, 2 or 3 identical or different radicals and these radicals (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, halogen, (C ₁ -C ₄ ) -Alkoxy or (C ₁ -C ₄ ) - haloalkoxy, or

R ² and R ³ together with the carbon atoms to which they are attached form a saturated 5-, 6- or 7-membered isocyclic ring which can contain oxygen and / or sulfur instead of one or two CH ₂ groups and which is optionally substituted by 1, 2 or 3 (C ₁ -C ₄ ) alkyl groups;

 A represents CH or N;

X represents NH, oxygen or S (O) _q , with q = 0, 1 or 2;

E represents a direct bond or a straight-chain or branched (C ₁ -C ₄ ) alkanediyl group;

Y and Z are the same or different and each independently CH ₂ ,

Is oxygen or a group S (O) _x where x = 0, 1 or 2;

W is a group (CH ₂ ) _n , where n is an integer from 1 to 4, or

W in the event that Y and / or Z are CH ₂ , a direct bond

 can mean between Y and Z;

wherein in the grouping -YWZ- one or more hydrogen atoms, as shown in formula I and described below, by

and are optionally replaced by R ⁵ ;

a and b are the same or different and, independently of one another, the numbers 0,

1, 2 or 3, where a and b do not simultaneously mean 0;

R ⁴ and R ^{5 are the} same or different and each independently

Are halogen, alkyl, haloalkyl, alkoxy, haloalkoxy or alkylthio;

r and s are the same or different and are independently 0, 1 or 2;

U is a single bond, oxygen, a group S (O) _y , with y = 0, 1 or 2 or a group NR ⁷ , where R ^{7 is} hydrogen, (C ₁ -C ₄ ) -alkyl or

Is (C ₁ -C ₄ ) alkoxy;

V for a single bond, carbonyl, or a grouping of the Formula or is where Q is oxygen, sulfur or

(C ₁ -C ₄ ) alkylimino, T is oxygen, sulfur or a group NR ^{7 '} and T' (C ₁ -C ₄ ) alkoxy, (C ₁ -C ₄ ) alkylthio or NR ^{7 '} R ^{7 "} , and wherein R ^{7 '} and R ^{7 "are} identical or different and have the meanings given above for R ⁷ ; or

 U and V together represent a double bond; and

a) R ⁶ denotes alkyl, alkenyl, alkynyl, optionally substituted aryl, optionally substituted heterocyclyl or cyano, or, in the event that U and V together stand for a direct single bond,

b) R ^{6 is} as defined above or is halogen, hydroxy, carboxy, nitro or a group SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ and R ⁹ (C ₁ -C ₄ ) alkyl and R ¹⁰ alkyl or optionally substituted aryl mean, or, in the event that U and V together represent a double bond,

c) R ^{6 represents} alkylidene or alkyloximino;

and the alkyl, alkenyl, alkynyl, alkylidene or alkyloximino radicals mentioned under R ⁶ , R ⁸ , R ⁹ and R ¹⁰ under a), b) or c) may have at least one of the following features:

i. one or more non-adjacent CH ₂ groups are replaced by CO and / or heteroatom units;

 ii. 3 to 12 atoms of these residues form an up to 12-membered

Cycle;

 iii. the hydrocarbon residues are with or without the specified

Variations, optionally with one or more identical or different radicals from the series 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, Cycloatkanoyloxy, cycloalkylalkanoyloxy, aroyloxy, arylalkanoyloxy, heterocycloylalkanoyloxy, alkylsulfonyloxy, arylsulfonyloxy, hydroxy, cyano, thiocyano or nitro substituted, the cycloaliphatic, aromatic or heterocyclic ring systems in the case of the above also unsubstituted or unsubstituted by the same as in the above may be provided with the same or different substituents up to the maximum number;

and furthermore, in the event that R ⁵ and R ^{6 are} alkyl radicals, these can be cyclically or spirocyclically linked;

 or their salts.

2. Compound of formula I according to claim 1, in which

R ⁴ and R ^{5 are} halogen, (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₁ -C ₄ ) alkoxy,

(C ₁ -C ₄₎ -haloalkoxy or (C ₁ -C ₄₎ alkylthio; and

a) R ⁶ (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₂ -C ₂₀ ) alkynyl, if appropriate

 substituted aryl, optionally substituted heterocyclyl, or cyano, or, in the event that U and V together represent a single bond,

b) R ^{6 is} as defined above or halogen, hydroxyl, carboxy, nitro or a group SiR ⁸ R ⁹ R ¹⁰ , where R ⁸ and R ⁹ (C ₁ -C ₄ ) alkyl and R ¹⁰ (C ₁ -C ₂₀ ) alkyl or optionally substituted aryl, or in the event that U and V together represent a double bond, c) R ^{6 is} (C ₁ -C ₂₀ ) alkylidene or (C ₁ -C ₂₀ ) alkyloximino;

and the alkyl groups mentioned for R ⁶ , R ⁸ , R ⁹ and R ¹⁰ under a), b) and c),

Alkenyl, alkynyl, alkylidene or alkyloximino radicals, optionally having at least one of the following features:

i. one or more non-adjacent CH ₂ groups are replaced by CO and / or heteroatom units;

 ii. 3 to 8 atoms these residues form an up to 8-membered cycle; iii. the hydrocarbon residues are with or without the specified

Variations, optionally with one or more identical or different radicals from the series halogen, aryl, aryloxy, arylthio, (C ₃ -C ₈ ) cycloalkoxy, (C ₃ -C ₈ ) cycloalkylthio, heterocyclyl,

Heterocyclyloxy, heterocyclylthio, (C ₁ -C ₁₂ ) alkanoyl, (C ₃ -C ₈ ) cycloalkanoyl, (C ₂ -C ₁₂ ) haloalkanoyl, aroyl, aryl (C ₁ -C ₄ ) alkanoyl, (C ₃ -C ₈ ) -cycloalkyl- (C ₁ -C ₄ ) -alkanoyl, heterocyclyl- (C ₁ -C ₄ ) -alkanoyl, (C ₁ -C ₁₂ ) -alkoxycarbonyl, (C ₁ -C ₁₂ ) -haloalkoxycarbonyl, (C ₃ -C ₈ ) cycloalkoxycarbonyl, (C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) alkoxycarbonyl-, aryl- (C ₁ -C ₄ ) alkoxycarbonyl, heterocyclyl- (C ₁ -C ₄ ) alkoxycarbonyl,

Aryloxycarbonyl, heterocyclyloxycarbonyl, (C ₁ -C ₁₂ ) alkanoyloxy,

(C ₂ -C ₁₂ ) haloalkanoylalkoxy, (C ₃ -C ₈ ) cycloalkanoyloxy, (C ₃ -C ₈ ) cycloalkyl- (C ₁ -C ₄ ) alkanoyloxy, aroyloxy, aryl- (C ₁ -C ₄ ) -alkanoyloxy, heterocyclyl- (C ₁ -C ₄ ) -alkanoyloxy, (C ₁ -C ₁₂ ) -alkylsulfonyloxy,

 Arylsulfonyloxy, hydroxy, cyano, thiocyano or nitro substituted, the cycloaliphatic, aromatic or heterocyclic ring systems among those just mentioned

Substituents may be unsubstituted or may be provided with up to three, in the case of halogen, up to the maximum number of identical or different substituents, and furthermore, if R ⁵ and R ^{6 are} alkyl radicals, these may be cyclically or spirocyclically linked, and the remaining radicals and variables are as defined in claim 1, or their salts.

3. A compound of formula I according to claim 1 or 2, in which

R ^{1 represents} hydrogen, chlorine or fluorine;

R ² (C ₁ -C ₄ ) alkyl, (C ₁ -C ₄ ) haloalkyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl,

Trimethylsilylethynyl, (C ₂ -C ₄ ) haloalkenyl, cyclopropyl,

 Is halocyclopropyl, methoxymethyl or cyano;

R ^{3 is} hydrogen, halogen, methyl, ethyl, (C ₂ -C ₄ ) alkenyl, (C ₂ -C ₄ ) alkynyl,

Trimethylsilylethynyl, (C ₂ -C ₄ ) haloalkenyl, methoxy, ethoxy, cyano or (C ₁ -C ₄ ) alkoxycarbonyl; or

R ² and R ³ together with the carbon atoms to which they are attached form an optionally substituted unsaturated 5- or 6-membered Form ring, which in the case of the 5-ring instead of a CH ₂ unit

May contain sulfur atom, or

R ² and R ³ , together with the carbon atoms to which they are attached, form a saturated 5- or 6-membered ring which instead of one

CH ₂ unit may contain a sulfur or an oxygen atom;

A represents CH or N;

X represents NH or oxygen;

E stands for a direct bond;

Y and Z are identical or different and each represent CH ₂ , oxygen or sulfur and the group -YWZ- is substituted as described above;

a and b each represent the number 2,

R ⁴ and R ^{5 are the} same or different and each represents (C ₁ -C ₄ ) alkyl, trifluoromethyl or (C ₁ -C ₄ ) alkoxy;

and the remaining radicals and variables are as defined in claim 1;

or their salts.

4. A compound of formula I according to any one of claims 1 to 3, in which

R ^{1 represents} hydrogen or fluorine;

R ^{2 is} methyl, ethyl, propyl, isopropyl, (C ₁ -C ₂ ) fluoroalkyl, ethynyl,

 Trimethylsilylethynyl, cyclopropyl or methoxymethyl;

R ^{3 is} halogen, methyl, ethyl, ethynyl, trimethylsilylethynyl, methoxy, ethoxy or cyano, or

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline or quinoline system, which may be substituted by fluorine in the carbocyclic part, or

R ² and R ³ together with the carbon atoms to which they are attached form a saturated 6-membered ring which can contain an oxygen or sulfur atom instead of a CH ₂ group;

Y and Z are identical or different and each represent CH ₂ or oxygen and and the group -YWZ- is substituted as described above; r = 0; R ^{5 represents} methyl or trifluoromethyl;

 U represents a direct bond or oxygen;

 V represents a direct bond; or

 U and V together represent a double bond; and the remaining radicals and variables are as defined in claim 1;

 or their salts.

5. A compound of formula I according to any one of claims 1 to 4, in which

R ^{1 represents} hydrogen;

R ^{2 is} ethyl, propyl, isopropyl, 1-fluoroethyl, ethynyl, trimethylsilylethynyl,

 Trifluoromethyl or methoxymethyl means

R ^{3 represents} fluorine, chlorine, bromine, ethynyl, trimethylsilylethynyl or methoxy; or if A is nitrogen,

 or if A is nitrogen,

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline system, which may be substituted with a fluorine atom, or

R ² and R ³ together with the ring system to which they are attached, the

 Form 5,6,7,8-tetrahydroquinazoline system;

A represents CH or N;

X represents NH or oxygen;

E stands for a direct bond;

Y and Z are the same or different and each represents CH ₂ or oxygen; W is a group (CH ₂ ) _n , where n is 2 or 3, or

W in the event that Y and / or Z are CH ₂ , a direct bond

 can mean between Y and Z;

wherein in the grouping -YWZ- one or more hydrogen atoms, as shown in formula I and described above, by and are optionally replaced by R ⁵ ;

a and b represent the number 2;

r = 0;

s = 0, 1 or 2; R ^{5 represents} methyl;

 U denotes a single bond or oxygen,

 Y represents a single bond; or

 and the remaining radicals are as defined in claim 1;

 or their salts.

6. A compound of formula I according to any one of claims 1 to 5, in which in particular those in which

Y represents CH ₂ ;

Z means CH ₂ or oxygen, and in this case

 W represents a direct bond between Y and Z;

or Y and Z are oxygen, and in this case

W represents a group (CH ₂ ) _n and n represents 2 or 3;

 U and V together represent a single bond;

 and the remaining radicals and variables are as defined in claim 1; or their salts.

7. A compound of formula I according to any one of claims 1 to 6, in which R ^{1 is} hydrogen;

R ^{2 represents} ethyl or methoxymethyl;

R ^{3 is} fluorine, chlorine, bromine or methoxy, or

R ² and R ³ together with the ring system to which they are attached, the

 Form quinazoline or the 5,6,7,8-tetrahydroquinazoline system;

A represents CH or N;

X represents NH or oxygen;

a and b are each 2, and r and s are each 0;

E stands for a direct bond;

Y CH ₂ and

Z represents CH ₂ or oxygen,

 U and V together stand for a direct single bond;

 and in this case

W means a direct bond between Y and Z, or Y and Z each represent oxygen, and for this case

W represents an optionally substituted group as described above (CH ₂ ) _n and n represents the numbers 2 or 3;

r and s are each = 0;

R ⁶ (C ₁ -C ₂₀ ) alkyl, (C ₂ -C ₂₀ ) alkenyl, (C ₂ -C ₂₀ ) alkynyl, optionally

substituted aryl or optionally substituted heterocyclyl, and in the alkyl, alkenyl or alkynyl radicals mentioned one or more non-adjacent CH ₂ groups can be replaced by oxygen or sulfur, and in addition 3 to 6 atoms of these alkyl, alkenyl or or alkynyl radicals, with or without the above variations, can form a cycle and these alkyl, alkenyl or alkynyl radicals, with or without the above variations including the cyclic formation, optionally with one, in the case of halogen, up to the maximum number of radicals can be substituted from the series halogen, aryl, aryloxy, arylthio, heterocyclyl, heterocyclyloxy, heterocyclylthio or hydroxy; and the remaining radicals and variables are as defined in claim 1;

or their salts.

8. A compound of formula I according to any one of claims 1 to 7, in which

R ^{2 is} methoxymethyl and R ^{3 is} methoxy, or

R ^{2 is} ethyl and R ^{3 is} chlorine or bromine;

 X represents NH;

 A represents nitrogen;

 Y and Z are oxygen;

W represents an optionally substituted group (CH ₂ ) _n as described above and n represents the number 2;

R ⁶ denotes (C ₁ -C ₂₀ ) alkyl, aryl or heterocyclyl, all of which are optionally substituted, and where one or more non-adjacent CH ₂ groups in the alkyl radical mentioned can be replaced by oxygen or sulfur, and above in addition 3 to 6 atoms, with or without the above substitution, can form a cycle; and the remaining radicals and variables are as defined in claim 1;

or their salts.

9. A process for the preparation of compounds of formula I according to any one of claims 1 to 8, characterized in that

a) a compound of formula II

wherein A, R ¹ , R ² and R ^{3 have} the meanings given under formula I and L represents a leaving group, with a compound of formula III

in which a, b, r, s, E, U, V, W, X, Y, Z, R ⁴ , R ⁵ and R ^{6 have} the meanings given under formula I; b) for the preparation of compounds of the formula I in which Y and Z are oxygen and W is a group (CH ₂ ) _n with n = 2, 3, 4, one is Compound of the general formula IV,

wherein a, b, r, A, X, E, R ¹ , R ² , R ³ and R ^{4 are} those given for formula I.

Have meanings in the presence of an acidic catalyst with a diol of the general formula V,

wherein U, V, R ⁵ , R ⁶ and s have the meanings given above and n denotes the numbers 2, 3 or 4; c) for the preparation of compounds of the formula I in which Y and Z are oxygen and W is a group (CH ₂ ) _n with n = 2, 3, 4, a compound of the formula I ' for the R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , a, b, r, s, A, X and E those for the formula I.

have the meanings indicated, n = 2, 3 or 4 and s are preferably = 0, in the presence of an acidic catalyst with a diol of the general formula V defined above under b) with transketalization; and the compounds of the formula I obtained in this way or otherwise, optionally on the heterocycle; and / or further derivatized in the side chain R ⁶ ; and optionally converting the compounds of formula I thus obtained 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 effective amount of at least one compound according to one of claims 1 to 8 together with the additives or auxiliaries customary for this application.

12. Insecticides, acaricides, ixodicides or nematicides according to

Claim 10, containing an effective amount of at least one compound according to one of claims 1 to 8 together with the additives or auxiliaries customary for this application.

13. Plant protection products containing a fungicidal, insecticidal, acaricidal, ixodicidal or nematicidal effective amount of at least one compound according to one of claims 1 to 8 and at least one further active ingredient, preferably from the series of fungicides, insecticides, attractants, sterilants, acaricides,

Nematicides and herbicides together with the auxiliaries and additives customary for this application.

14. Means for use in wood protection or as a preservative in sealing compounds, in paints, in cooling lubricants for metalworking or in drilling and cutting oils, containing an effective amount of at least one compound according to one of claims 1 to 8 together with the usual auxiliary for these applications - and additives.

15. A compound according to any one of claims 1 to 8 or agent according to claim 10, for use as a veterinary medicinal product, preferably in the

Control of endo- or ectoparasites.

16. A process for the preparation of an agent according to any one of claims 10 to 15, characterized in that the active ingredient and the other additives are added together and brought into a suitable form of use.

17. Use of a compound according to one of claims 1 to 8 or agent according to one of claims 10, 1 1, 13 and 14 as a fungicide.

18. Use of a compound of formula I according to one of claims 1 to 8 or an agent according to one of claims 10, 1 1 and 14 as

Wood preservatives or as preservatives in sealants, in

Paints, in cooling lubricants for metalworking or in drilling and cutting oils.

19. A method of combating phytopathogenic fungi, characterized in that one of these or the plants infested by them, A fungicidally effective amount of a compound according to one of claims 1 to 8 or an agent according to one of claims 10, 11 and 13 is applied to surfaces or substrates or on seeds.

20. A method for controlling insect pests, acarina, mollusks and nematodes, in which an effective amount of a compound according to any one of claims 1 to 8 or an agent according to any one of claims 10 is applied to these or the plants, surfaces or substrates which they infest. 12 and 13 applied.

21. Use of compounds according to one of claims 1 to 8 or an agent according to one of claims 10, 12 and 13 for controlling insect pests, acarina, mollusks and nematodes.

22. Seed, treated or coated with an effective amount of a compound according to any one of claims 1 to 8 or an agent according to any one of claims 10, 1 1 and 13.