# Patent

## Title
Dihalopropene compounds, processes for their preparation, compositions comprising them and their use as pesticides

## Abstract

Dihalopropene compounds, process for their preparation, compositions comprising them and their use as pesticides
What is described are dihalopropene compounds of the formula (I) 




in which R1 and R2 are halogen, Y is —O—, —S— or —NH—, X is —O—, —S(O)r— or —NR5— (where r=0, 1, 2 and R5 is hydrogen or C1-C8-alkyl), X′ is a direct C—C bond, —O—, —S(O)r— or —NR5— (where R5 is as defined above), R3 is hydrogen, halogen, nitro, cyano, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, C3-C10-cycloalkyl or has one of the meanings defined for A,

    A has the meaning given in the description (inter alia aryl, heterocyclyl), B is a divalent bridge having the meanings given in the description (inter alia alkylene) and
    R4 is a monovalent C6-C14-aryl radical or nitrogen-containing heteroaryl radical having at least one ring heteroatom which has the meanings given in the description.


These compounds can be used for preparing pesticides.

## Background
The invention relates to dihalopropene compounds, to a process for their preparation, to compositions comprising them and to their use for controlling animal pests, in particular arthropods, such as insects and acarids, and helminthes.
Owing to the enormous damage caused by insects, for example by feeding on useful plants, stored food, wood and textiles, or else by transferring diseases to man, domestic animals and useful plants, the use of insecticides or repellents remains indispensable. Insecticides are an important component of integrated pest control, and their contribution is decisive with respect to harvest yields and yield continuity all over the world.
The insecticidal and/or acaricidal action of compounds from the class of the dihalopropene compounds is known per se.
Compounds from this class of substances and their insecticidal and/or acaricidal action are described in EP-A-787,710, WO-A-96/11,909, WO-A-97/27,173 and WO-A-97/28,112.
However, since the ecological and economic demands made on modern insecticides are increasing continually, for example with respect to toxicity, selectivity, application rates, formation of residues and favorable manufacture, and there can furthermore be problems, for example with resistance, there is a constant need to develop novel insecticides which, at least in some areas, have advantages over those of the prior art.
It has been found that compounds of the formula (I) have a good activity spectrum against animal pests and at the same time good compatibility with plants and favorable toxicological properties with respect to mammals and aquatic animals.
Accordingly, the invention provides compounds of the formula (I) 




in which

    R1 and R2 independently of one another are halogen,
    Y is —O—, —S— or —NH—,
    X is —O—, —S(O)r— or —NR5—, where r=0, 1 or 2 and R5 is hydrogen or C1-C8-alkyl,
    X′ is a direct C—C bond, —O—, —S(O)r— or —NR5—, where r and R5 are as defined above,
    R3 is hydrogen, halogen, nitro, cyano, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy or C3-C10-cycloalkyl or has one of the meanings defined for A,
    A is one of the groups —OR6, —SR6, —NR7R8, —S(═O)R6, —S(═O)2R6, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —C(=Z)-O—N═C(NH2)—R6, —O—C(=Z)-R6, —O—C(=Z)-OR6, —O—C(=Z)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)-OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=)-SR6 or —NR9—C(=Z)-NR7R8, or
    A is C2-C8-alkenyl which is unsubstituted or substituted by one or more radicals, these radicals being halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, tri-(C1-C8-alkyl)silyl, aryl-(C1-C8)-dialkylsilyl, diaryl-(C1-C8)-alkylsilyl, triarylsilyl, —COOR6, —CO—NR7R8, C6-C14-aryl and/or heteroaryl having one to three ring heteroatoms, where these radicals for their part may be substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy and C1-C8-haloalkoxy; or
    A is C2-C8-alkynyl which is unsubstituted or substituted by one or more radicals, these radicals being halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, tri-(C1-C8-alkyl)silyl aryl-(C1-C8)-dialkylsilyl, diaryl-(C1-C8)-alkylsilyl, triarylsilyl, —COOR6, —CO—NR7R8, C6-C14-aryl and/or heteroaryl having one to three ring heteroatoms, where these radicals for their part may be substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy and C1-C8-haloalkoxy; or
    A is C6-C14-aryl which is unsubstituted or substituted by one or more radicals, these radicals being halogen, cyano, hydroxyl, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, C1-C8-alkylthio, C1-C8-haloalkylthio, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, C2-C8-alkyloxyalkylene, C2-C8-alkyl-thioalkylene, C3-C8-alkanoyloxyalkylene, C1-C8-aminoalkylene, phenyloxyalkylene, phenylthioalkylene, C3-C8-cycloalkyl, C6-C14-aryl, heteroaryl having one to three ring heteroatoms, —COOR6, —CO—NR7R8 and/or —S(O)r—R3, where r and R3 are as defined above, where the aryl and/or the heteroaryl radicals for their part may be substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy and C1-C8-haloalkoxy; or
    A is a heterocyclic radical having one to three ring heteroatoms and preferably two to eight ring carbon atoms which is unsubstituted or substituted by one or more radicals, these radicals being halogen, cyano, hydroxyl, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, C1-C8-alkylthio, C1-C8-haloalkylthio, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, C2-C8-alkyloxyalkylene, C2-C8-alkylthioalkylene, C3-C8-alkanoyloxyalkylene, C1-C8-aminoalkylene, phenyloxyalkylene, phenylthioalkylene, C3-C8-cycloalkyl, C6-C14-aryl, heteroaryl having one to three ring heteroatoms, —COOR6, —CO—NR7R8 and/or —S(O)r—R3, where r and R3 are as defined above, where the aryl and/or the heteroaryl radicals for their part may be substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, hydroxyl, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy and C1-C8-haloalkoxy; or
    A is C1-C8-alkyl which is substituted by one to six groups, its substituents being selected from the group consisting of hydroxyl, amino, N—(C1-C8-alkyl)amino, N,N-bis-(C1-C8-alkyl)amino, C1-C8-alkoxy, C1-C8-haloalkoxy, C1-C8-acyloxy and C1-C8-haloacyloxy, or where two substituents together may also form an alkylene chain which may contain one or more oxygen, nitrogen and/or sulfur atoms, for example an acetal, lactone or lactam ring system,
    Z is ═O, ═S, ═N—R33, ═N—O—R33 or ═N—NR33R34,
    R6, R7, R8, R9, R33 and R34 independently of one another are hydrogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl or heteroaryl having one to three ring heteroatoms which for their part may be substituted by halogen, hydroxyl, cyano, nitro, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl, halogen-substituted C6-C14-aryl, heteroaryl having one to three ring heteroatoms or halogen-substituted heteroaryl having one to three ring heteroatoms, amino, N—(C1-C8-alkyl)amino, N,N-bis-(C1-C8-alkyl)amino, tri-(C1-C8-alkyl)silyl, aryl-(C1-C8)-dialkylsilyl, diaryl-(C1-C8)-alkylsilyl, triarylsilyl, C1-C8-alkoxy and/or C1-C8-haloalkoxy,
    B is a divalent bridge and is alkylene having one to twelve carbon atoms, cycloalkylene having three to fourteen carbon atoms, alkylene-cycloalkylene having four to twenty-six carbon atoms, alkylene-cycloalkylene-alkylene having five to thirty-eight carbon atoms, where these bridges may have one to three ethylenically unsaturated bonds and/or may be interrupted by —O—, —S—, —C(═O)O— or —NR5— groups, where R5 is as defined above and where the bridge may be unsubstituted or substituted by one to ten substituents selected from the group consisting of C1-C3-alkyl, trifluoromethyl and trichloromethyl, and
    R4 is a monovalent C6-C14-aryl radical or nitrogen-containing heteroaryl radical having at least one, preferably one to three, ring heteroatom which is unsubstituted or substituted by one to four radicals selected from the group consisting of halogen, cyano, nitro, thiocyanato, isocyanato, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl, nitrogen-containing heteroaryl having one to three ring heteroatoms, where these substituents for their part may be substituted by radicals selected from the group consisting of halogen, cyano, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —C(=Z)-O—N═C(NH2)—R6, —O—C(=Z)-R6, —O—C(=Z)-OR6, —O—C(=Z)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)-OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=Z)-SR6, —NR9—C(=Z)-NR7R8, —OR6, —SR6, —S(═O)R6, —S(═O)2R6, NR7R8, where Z, R6, R7, R8 and R9 are as defined above.


The term “halogen” includes fluorine, chlorine, bromine and/or iodine. Preferred are fluorine, chlorine and/or bromine.
The term “(C1-C8)-alkyl” is to be understood as meaning an unbranched or branched aliphatic and saturated hydrocarbon radical having one to eight carbon atoms, such as, for example, the methyl, ethyl, propyl, isopropyl, 1-butyl, 2-butyl, isobutyl, tert-butyl, n-pentyl, 2-methylbutyl, 1,1-dimethylpropyl, n-hexyl, n-heptyl, n-octyl or 2-ethylhexyl radical. Preference is given to methyl.
“(C1-C8)-haloalkyl” is to be understood as meaning an alkyl group mentioned under the term “(C1-C8)-alkyl” in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably by chlorine or fluorine, such as the trifluoromethyl, the 1- or 2-fluoroethyl, the 2,2,2-trifluoroethyl, the chloromethyl, the fluoromethyl, the difluoromethyl or the 1,1,2,2-tetrafluoroethyl group.
“(C1-C8)-alkoxy” is to be understood as meaning alkoxy groups whose hydrocarbon radicals have the meanings given under the terms “(C1-C8)-alkyl”.
“(C1-C8)-haloalkoxy” is to be understood as meaning an alkoxy group mentioned under the term “(C1-C8)-alkoxy” in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably by chlorine or fluorine, such as the trifluoromethyloxy, the 1- or 2-fluoroethyloxy, the 2,2,2-tri-fluoroethyloxy, the chloromethyloxy, the fluoromethyloxy, the difluoromethyloxy or the 1,1,2,2-tetrafluoroethyloxy group.
“(C1-C8)-alkylthio” is to be understood as meaning alkylthio groups whose hydrocarbon radicals have the meanings given under the terms “(C1-C8)-alkyl”.
“(C1-C8)-haloalkylthio” is to be understood as meaning an alkylthio group mentioned under the term “(C1-C8)-alkylthio” in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably by chlorine or fluorine, such as the trifluoromethylthio, the 1- or 2-fluoroethylthio, the 2,2,2-trifluoroethylthio, the chloromethylthio, the fluoromethylthio, the difluoromethylthio or the 1,1,2,2-tetrafluoroethylthio group.
“(C3-C10)-cycloalkyl” is to be understood as meaning monocyclic and saturated alkyl radicals having three to ten ring carbon atoms. Examples are cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The term furthermore comprises bicyclic and saturated alkyl radicals, such as the norbornyl or bicyclo[2.2.2]octyl radical, or else fused and saturated systems, such as, for example, the decahydronaphthyl radical.
The term “tri-(C1-C8-alkyl)silyl” denotes a silicon atom which carries three identical or different alkyl radicals according to the above definition. Analogously, “aryl-(C1-C8)-dialkylsilyl” denotes a silicon atom which carries an aryl radical and two identical or different alkyl radicals according to the above definition, “diaryl-(C1-C8)-alkylsilyl” denotes a silicon atom which carries one alkyl radical and two identical or different aryl radicals according to the above definition, and “triarylsilyl” denotes a silicon atom which carries three identical or different aryl radicals according to the above definition.
Examples of radicals —COOR6 are the carboxyl groups or esters thereof with mono-valent aliphatic, cycloaliphatic, aromatic or heterocyclic alcohols according to the definitions given above for R6. Preferred are the carboxyl group, the methyl, ethyl or propyl esters, the cyclohexyl esters and the phenyl esters, where in the aliphatic, cycloaliphatic, aromatic or heterocyclic radicals one or more hydrogen atoms may be replaced by halogen, in particular by fluorine or chlorine. One example is the trifluoromethyl group.
Examples of radicals —CO—NR7R8 are the carboxamide groups whose nitrogen atom may be mono- or disubstituted by monovalent aliphatic, cycloaliphatic, aromatic or heterocyclic radicals according to the definitions given above for R7 and R8. Preference is given to the carboxamide group, the N-methyl-, N-ethyl- or N-propyl-carboxamide group and to the corresponding disubstituted derivatives, such as the N,N-dimethyl-, N,N-diethyl- or N,N-dipropylcarboxamide group and the corresponding asymmetrically substituted groups, where in the aliphatic, cycloaliphatic, aromatic or heterocyclic radicals one or two hydrogen atoms may be replaced by halogen, in particular by fluorine or chlorine. One example is the trifluoromethyl group.
The term “(C6-C14)-aryl” is to be understood as meaning a carbocyclic, i.e. constructed of carbon atoms, aromatic radical having 6 to 14, in particular 6 to 12, ring carbon atoms. Examples are monocyclic aromatic radicals, such as phenyl, polycyclic fused aromatic radicals, such as naphthyl or anthracyl, or polycyclic aromatic radicals which are attached via C—C bonds or bridges such as —O— or —S—, such as biphenylyl. Preference is given to phenyl.
The term “heterocyclic radical having one to three ring heteroatoms” denotes a cyclic radical which may be completely saturated, partially unsaturated or fully unsaturated or aromatic and which is interrupted by at least one to three identical or different heteroatoms, preferably from the group consisting of nitrogen, sulfur and oxygen, where, however, two oxygen atoms may not be directly adjacent and at least one carbon atom has to be present in the ring. Preferred are radicals having four, five, six or seven ring atoms, in particular five or six ring atoms.
The terms “C2-C8-alkenyl” or “C3-C8-alkenyl” and “C2-C8-alkynyl” or “C3-C8-alkynyl” denote a straight-chain or branched hydrocarbon radical having two to eight and three to eight carbon atoms, respectively, which hydrocarbon radical contains at least one multiple bond which may be located in any position of the unsaturated radical in question.
Accordingly, “(C2-C8)-alkenyl” denotes, for example, the vinyl, allyl, 2-methylpropenyl, 1- or 2-butenyl, pentenyl, 2-methylpentenyl, hexenyl, heptenyl or octenyl group.
Accordingly, “(C2-C8)-alkynyl” denotes, for example, the ethynyl, propargyl, 2-methylpropynyl, 2-butynyl, pentynyl, 2-methylpentynyl, hexynyl, heptynyl or octynyl group.
“(C2-C8)-haloalkenyl” and “(C2-C8)-haloalkynyl” are to be understood as meaning alkenyl and alkynyl groups, respectively, mentioned under the terms “(C2-C8)-alkenyl” and “(C2-C8)-alkynyl”, respectively, in which one or more hydrogen atoms are replaced by the same number of identical or different halogen atoms, preferably by chlorine or fluorine, such as the 1- or 2-fluoroethenyl or -ethynyl group or the 1- or 2-chloroethenyl or -ethynyl group.
“C2-C8-alkyloxyalkylene” is to be understood as meaning alkyl radicals having two to eight carbon atoms and containing one or more oxygen atoms in the alkyl chain. Examples are methoxymethylene, methoxyethylene, methoxypropylene, methoxybutylene, ethoxymethylene, ethoxyethylene, ethoxypropylene and ethoxybutylene.
“C2-C8-alkylthioalkylene” is to be understood as meaning alkyl radicals having two to eight carbon atoms and containing one or more sulfur atoms in the alkyl chain. Examples are methylthiomethylene, methylthioethylene, methylthiopropylene, methylthiobutylene, ethylthiomethylene, ethylthioethylene, ethylthiopropylene and ethylthiobutylene.
“C3-C8-alkanoyloxyalkylene” is to be understood as meaning alkyl radicals having three to eight carbon atoms and containing one or more carbonyloxy groups, preferably one carbonyloxy group, in the alkyl chain. Examples are methanoyloxymethylene, methanoyloxyethylene, methanoyloxypropylene, methanoyloxybutylene, ethanoyloxymethylene, ethanoyloxyethylene, ethanoyloxypropylene and ethanoyloxybutylene.
“C1-C8-aminoalkylene” is to be understood as meaning alkyl radicals having one to eight carbon atoms and containing one or more amino groups in the alkyl chain or as substituents on the alkyl chain. The amino groups for their part may be mono- or dialkylsubstituted. The amino groups may be terminal or located within the chain. Examples are aminomethylene, 2-aminoethylene, 3-aminopropylene, 4-aminobutylene, methylaminomethylene, 2-methylaminoethylene, 3-methylaminopropylene and 4-methylaminobutylene.
“Phenyloxyalkylene” is to be understood as meaning alkyl radicals substituted by one or more phenyloxy groups. One example is phenyloxymethylene.
“Phenylthioalkylene” is to be understood as meaning alkyl radicals substituted by one or more phenylthio groups. One example is phenylthiomethylene.
The term “C1-C8-alkyl substituted by one to six groups” denotes a C1-C8-alkyl radical in which one to six hydrogen atoms are substituted by hydroxyl groups, by unsubstituted amino groups, by amino groups which are substituted on the nitrogen by one or two C1-C8-alkyl groups, by C1-C8-alkoxy groups, by C1-C8-haloalkoxy groups, by C1-C8-acyloxy groups, by C1-C8-haloacyloxy groups or by combinations of these groups.
Here, the terms “C1-C8-alkyl groups”, “C1-C8-alkoxy groups” and “C1-C8-haloalkoxy groups” are as defined above.
“C1-C8-acyloxy groups” is to be understood as meaning monovalent radicals of saturated carboxylic acids having one to eight carbon atoms. Examples are the formyl, acetyl, propionyl, butyryl, 2-methylbutyryl, pivaloyl or octanoyl groups.
“C1-C8-haloacyloxy groups” is to be understood as meaning monovalent radicals of saturated carboxylic acids having one to eight carbon atoms in which one or more hydrogen atoms are substituted by halogen atoms. Examples are the chloroformyl, monochloroacetyl, dichloroacetyl, trichloroacetyl, monochloropropionyl, dichloropropionyl, trichloropropionyl, tetrachloropropionyl, pentachloropropionyl, monochlorobutyryl, dichlorobutyryl, trichlorobutyryl, tetrachlorobutyryl, pentachlorobutyryl, hexachlorobutyryl and heptachlorobutyryl groups and the corresponding brominated derivatives and brominated and chlorinated derivatives.
“(C4-C10)-cycloalkenyl” is to be understood as meaning monocyclic alkyl radicals which contain at least one multiple bond and four to ten ring carbon atoms. Examples are cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl and cyclodecenyl. These radicals furthermore include bicyclic alkyl radicals which contain at least one multiple bond, such as the norbornenyl or bicyclo[2.2.2]octenyl radical, or else fused systems which contain at least one multiple bond, such as, for example, the tetra-, hexa- or octahydronaphthyl radical.
“(C4-C10)-cycloalkynyl” denotes, for example, the cyclooctynyl, cyclononynyl or cyclodecynyl radical.
The term “divalent bridge” is to be understood as meaning divalent alkylene radicals having one to twelve carbon atoms, divalent cycloalkylene radicals having three to fourteen carbon atoms, and combinations thereof, such as alkylene-cycloalkylene having four to twenty-six carbon atoms, alkylene-cycloalkylene-alkylene having five to thirty-eight carbon atoms. These alkylene and/or cycloalkylene radicals may have one to three ethylenically unsaturated bonds, and/or they can be interrupted by one or more oxygen atoms, sulfur atoms, nitrogen atoms or groups containing oxygen atoms. The alkylene radicals can be straight-chain or branched.
These alkylene and/or cycloalkylene radicals may furthermore have one to ten substituents. These substituents are C1-C3-alkyl groups and/or trichloromethyl and/or trifluoromethyl. Examples of C1-C3-alkyl groups are methyl, ethyl, n-propyl and isopropyl. Preference is given to methyl, trichloromethyl and trifluoromethyl.
The term “nitrogen-containing heteroaryl radical having at least one, preferably one to three, ring heteroatoms” denotes a heteroaromatic radical which may be interrupted by at least one or a plurality of identical or different heteroatoms, in particular atoms selected from the group consisting of nitrogen, sulfur and oxygen, where at least one heteroatom has to be a nitrogen atom, but where two oxygen atoms may not be directly adjacent and where at least one carbon atom has to be present in the ring. These are preferably radicals having five or six ring atoms, of which one, two or three are nitrogen atoms.
Preference is given to compounds of the formula I in which R1 and R2 are each chlorine or bromine.
Preference is also given to compounds of the formula I in which Y is —O—.
Very particular preference is given to compounds of the formula I in which R1 and R2 are each chlorine and Y is —O—.
Preference is furthermore given to compounds of the formula I in which X is —O—, —S— or —NH— and X′ is a direct C—C bond, —O—, —S— or —NH—, in particular to compounds of the formula I in which X and X′ are each —O— or X is —O— and X′ is a direct C—C bond.
Preference is given to compounds of the formula I in which R3 is hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, methoxy, trifluoromethoxy, monochloromethoxy, dichloromethoxy, trichloromethoxy, nitro, cyano, cyclohexyl, phenyl or a monovalent radical derived from 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, pyrazine, pyrimidine, pyridazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,4,5-tetrazine, quinoline, isoquinoline, quinoxaline, quinazoline, cinnoline, 1,8-naphthyridine, 1,5-naphthyridine, 1,6-naphthyridine, 1,7-naphthyridine, phthalazine, pyridopyrimidine, purine, pteridine, 4H-quinolizine, piperidine, pyrrolidine, oxazoline, tetrahydrofuran, tetrahydropyran, isoxazolidine or thiazolidine.
Very particular preference is given to compounds of the formula I in which R3 is methyl, trifluoromethyl, cyano, chlorine or bromine.
Preference is given to compounds of the formula I in which Z is ═O, ═N—OH, ═N—OCH3 or ═N—CH2—CH═CH2.
Particularly preferred radicals A are the groups —C(═O)—CH3, —C(═N—OCH3)—CH3, —C(═N—OH)—CH3, —C(═O)—OCH3, —C(═O)—CH═CH—N(CH3)2, —C(═O)—NH—C2H5, —C(═O)—NH2, —C(═O)—N(CH3)2, —C(═O)—NH—CH2—CH2—OH, —C(═O)—NH—CH(CH3)—CH2—OH, —C(═O)—CHBr2, —C(═O)—N(CH3)—O—CH3, —C(═N—O—CH2—CH═CH2)—CH3, —C(═S)—NH2, —C(═O)—O—C6H5, —C(═O)—O—C3H7, —C(═O)-imidazolyl, —C(═O)-3-ethyl-1,2,4-oxadiazol-5-yl, —C(═O)-2Δ-oxazolin-2-yl, —C(═O)-1-methylpyrazol-3-yl, —C(═O)-ethyn-2-yl, —C(═O)-1-hydroxyethyn-2-yl, —C(═O)-1-trimethylsilylethyn-2-yl, —C(═O)-1-hexylethyn-2-yl, —C(═O)-1-(2-chlorophenyl)ethyn-2-yl, —C(═O)-1-methoxyethyn-2-yl and —C(═O)-ethen-2-yl.
Preference is given to compounds of the formula I in which A is C2-C8-alkenyl, C2-C8-alkynyl, phenyl, pyridyl or pyrimidyl which are unsubstituted or substituted by one or more halogen atoms, cyano groups, nitro groups, hydroxyl groups, C1-C3-alkoxy radicals or C1-C3-haloalkoxy radicals, C1-C3-alkoxy radicals, C1-C3-haloalkoxy radicals which for their part are unsubstituted or substituted by one or more halogen atoms, cyano groups, nitro groups, hydroxyl groups, C1-C3-alkoxy radicals or C1-C3 haloalkoxy radicals, or is —OR6, —SR6, —NR7R8, —S(═O)R6, —S(═O)2R6, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —O—C(=Z)-R6, —O—C(=)-OR6, —O—C(=)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)-OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=Z)-SR6 or —NR9—C(=Z)-NR7R8, where Z, R6, R7, R8 and R9 are as defined in Claim 1, or is C1-C8-alkyl which is substituted by one or more hydroxyl groups, C1-C3-alkoxy radicals, C1-C3-haloalkoxy radicals, C1-C3-acyloxy radicals or C1-C3-haloacyloxy radicals, or is a group of the formulae Q1-Q10




in which W is oxygen or sulfur, R10 to R18, R20 and R21, R23 to R31 are hydrogen, C1-C6-alkyl, C3-C7-cycloalkyl, C2-C6-alkenyl, C4-C7-cycloalkenyl, pyridyl or phenyl, where the C1-C6-alkyl, C3-C7-cycloalkyl, C2-C6-alkenyl and C4-C7-cycloalkenyl radicals are unsubstituted or mono- or polysubstituted, preferably mono-, di- or trisubstituted by halogen, cyano, —OR6, —SR6, —S(O)R6, —S(O)2R6 and/or —NR7R8, where the radicals R6, R7 and R8 are as defined above, and where phenyl and pyridyl are unsubstituted or mono- or polysubstituted, preferably mono-, di- or trisubstituted by halogen, cyano, nitro, —OR6, —SR6, —S(O)R6, —S(O)2R6, —NR7R8, C1-C4-alkyl, C1-C4-haloalkyl, C2-C4-alkenyl and/or C2-C4-haloalkyl.

Preference is given to compounds of the formula I in which B is a group of the formulae P1 to P6




in which R32 in each case independently of the others is hydrogen, C1-C3-alkyl or trifluoromethyl,

    Y′ in each case independently of the others is a direct C—C bond, —O—, —S— or —NH—,
    i is an integer from 1 to 6,
    j is an integer from 1 to 6,
    k is an integer from 0 to 2,
    l is an integer from 0 to 2,
    m is an integer from 0 to 2,
    o is an integer from 0 to 1 and
    p is an integer from 0 to 1.


Very particular preference is given to compounds of the formula I in which B is a group of the formula —CqH2q— and q is an integer from 2 to 4, in particular —(CH2)2—, —(CH2)3— and —(CH2)4—.
Preference is furthermore given to compounds of the formula I in which R4 is C6-C14-aryl which is unsubstituted or substituted by one or more, preferably by one to three radicals selected from the group consisting of halogen, cyano, nitro, thiocyanato, isocyanato, C1-C6-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C4-C8-cycloalkenyl and C2-C8-alkynyl, where one or more hydrogen atoms of the C1-C6-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C4-C8-cycloalkenyl and/or C2-C8-alkynyl radicals may be substituted by halogen and/or cyano.
Particular preference is given to compounds of the formula I in which R4 is selected from the group consisting of phenyl, pyridyl, pyrimidyl, pyrazynyl, pyrazolyl and naphthyl which are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —O—C(=Z)-R6, —O—C(=Z)-OR6, —O—C(=Z)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)-OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=Z)-SR6, —NR9—C(=Z)-NR7R8, —OR6, —SR6, —S(═O)R6 and —S(═O)2R6, where Z, R6, R7, R8 and R9 are as defined above.
Very particular preference is given to the formula I in which R4 is phenyl or pyridyl which carries one to three substituents from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and C1-C3-haloalkyl or of combinations of these substituents.
Very particularly preferred radicals R4 are trifluoromethylphenyl, chlorophenyl, nitrophenyl, nitropyridyl, trifluoromethylpyridyl, di(trifluoromethyl)pyridyl, chloropyridyl, dichloropyridyl, chlorotrifluoromethylpyridyl, trifluoromethylpyrimidyl, di(trifluoromethyl)pyrimidyl, methyltrifluoromethylpyrimidyl or trifluoromethylpyrazolyl.
Depending on the nature of the substituents defined above, the compounds of the formula (I) have acidic or basic properties and are capable of forming salts. If, for example, the compounds of the formula (I) carry groups such as hydroxyl, carboxyl or other groups which induce acidic properties, these compounds can be reacted with bases to form salts. Suitable bases are, for example, hydroxides, carbonates and bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore ammonia, primary, secondary and tertiary amines with (C1-C4) alkyl radicals and mono-, di- and trialkanolamines of (C1-C4)-alkanols. If, for example, the compounds of the formula (I) carry groups such as amino, alkylamino or other groups which induce basic properties, these compounds can be reacted with acids to form salts. Suitable acids are, for example, mineral acids, such as hydrochloric, sulfuric and phosphoric acid, organic acids, such as acetic acid or oxalic acid, and acidic salts, such as NaHSO4 and KHSO4. The salts obtainable in this manner likewise have insecticidal, acaricidal and miticidal properties.
The compounds of the formula (I) can have one or more asymmetrically substituted carbon atoms or stereoisomers on double bonds. Therefore, it is possible for enantiomers or diastereomers to be present. The invention embraces both the pure isomers and their mixtures. The mixtures of diastereomers can be separated into the isomers by customary methods, for example by selective crystallization from suitable solvents or by chromatography. Racemates can be separated into the enantiomers by customary methods.
The preparation of the compounds according to the invention is carried out by methods known per se from the literature, as described in standard works on organic synthesis, for example Houben-Weyl, Methoden der Organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart.
The synthesis routes described below employ reaction procedures and work-up and purification methods commonly encountered in the organic or chemical literature. Reactions generally take place in solution where, for example, alcoholic solvents such as methanol or ethanol; hydrocarbons, such as hexane, benzene or toluene; ethers, such as diethyl ether or tetrahydrofuran; chlorinated hydrocarbons, such as dichloromethane, chloroform or tetrachloroethane; amide-containing solvents, such as N,N-dimethylformamide; or sulfur-containing solvents, such as dimethyl sulfoxide or sulfolane, may be employed.
In individual cases, the reactions may also take place in suspension, emulsion or in solid phase.
Suitable reaction temperatures are in the range of from −200° C. to 250° C. However, in general, the reaction temperature is from −78° C. to 150° C.
For work-up, the reaction mixture is usually extracted with two or more solvents which are not miscible with one another. Alternatively, it is possible to use solid-phase extractions (H. G. Kicinski, Chemie in Labor and Biotechnik [Chemistry in the Laboratory and in Biological Engineering], 1996, 47(12), 542-8) or precipitation of the products in a suitable solvent or solvent mixture.
The crude products are usually purified by chromatographic processes, such as column chromatography or HPLC; by distillation or by crystallization from suitable solvents. However, other methods are not excluded.
The present invention also relates to processes for preparing compounds of the formula (I), which processes comprise the steps: 




    
    
        a) a reaction of the compounds of the formulae II and III to give the compound of the formula IV and
        b) a reaction of the compounds of the formulae IV and V to give the compound of the formula I,

where R1, R2, R3, R4, A, Y, X and X′ are as defined above and Q and Q′ are leaving groups.

    
    


To prepare compounds of the formula (I) in which

    R1, R2, R3, R4, R5 and A have the meanings given for formula (I) and in which Y, X and X′ are each O, it is possible, for example, to proceed according to schemes 1 and 2 below.


A general procedure for preparing dihalopropene ether compounds is shown in scheme 1. Analogously, dihalopropene thioethers or amines can be prepared using corresponding thioether and amine starting materials, respectively. 




A large number of the compounds claimed herein is accessible via a building block of type 4 in scheme 1 as common intermediate. 4 is generally synthesized from compounds 1 which are commercially available or have been described in the literature. Initially, the methyl ether in 1 is cleaved by reaction with Lewis acids, such as, for example, boron tribromide, or with strong Brönsted acids, such as, for example, hydrobromic acid. The resulting compound 2 is alkylated with 5. This can take place under carefully controlled reaction conditions (for example at low temperatures and substoichiometric amounts of 5), so that the building block 4 is formed in one step. Alternatively, the alkylation may also initially yield 3, which is then converted further into 4 using a weak Lewis acid, such as, for example, magnesium dibromide/diethyl ether complex.
The phenols 4 can, as shown in scheme 2, be reacted in an alkylation reaction with a building block of type 11 or in a condensation reaction with a building block of type 12 to give the compounds 9. 




In the case of an alkylation reaction, the presence of a base may be required, suitable bases being organic bases, such as, for example, triethylamine or dimethylaminopyridine, or else inorganic bases, such as, for example, calcium carbonate. To carry out a condensation, the presence of a dehydrating agent or a dehydrating combination of reagents is required.
The reaction is carried out under Mitsunobu conditions, i.e. by reacting the OH derivative with an alcohol in the presence of an azodicarboxylic diester and a phosphine. By way of example, diethyl azodicarboxylate in combination with triphenylphosphine may be mentioned here.
The preparation of building blocks 11 and 12 follows the procedures described in the literature (for example WO-A-96/11,909). However, it is also possible to initially convert the phenols 4 into the corresponding thiophenols 6. Suitable for this purpose is, for example, a Kwart-Newman rearrangement via a suitable N,N-dialkylthio-carbamoyl derivative of 4 (see K. -D. Gundermann, K. Hümke in Houben-Weyl, “Methoden der Organischen Chemie”, Georg-Thieme-Verlag, 4th Edition, 1985, Volume E11, “Organische Schwefelverbindungen Teil I” [Organic Sulfur Compounds Part I], pages 54-55). Further conversion into the claimed compounds 8 is carried out analogously to the conversion of 4 into 9.
It is furthermore possible to convert the phenolic group in 4 into a leaving group suitable for transition-metal-catalyzed reactions (for example a trifluoromethane-sulfonate group), which is subsequently substituted, according to processes known from the literature, by an amine of type 13 (see, for example, John P. Wolfe et al., J. Org. Chem. 2000, 65(4), 1158-1174).
Suitable transition metal catalysts are, in particular, palladium complexes. This procedure affords the claimed compounds 10.
The claimed compounds in which group A in formula I is an alkynyl or alkenyl group according to structural formulae 19 and 20 are—as shown in scheme 3—obtainable from the monobenzoylated hydroquinones 14, which are known from the literature. 




The monobenzoylated hydroquinones 14 are initially selectively brominated or iodinated in the ortho-position to the free phenol group, by action of a suitable reagent. An iodination can be effected, inter alia, with the aid of a mixture of chloramine T and sodium iodide, giving structures 15. 15 is reacted in an alkylation or condensation with building blocks 11 or 12 (analogously to the conversion of 4 into 9), giving the compounds 16. The benzoyl group in 16 is removed hydrolytically in a basic reaction medium. Basic reaction conditions can be established using, in particular, inorganic bases, such as, for example, sodium hydroxide or potassium carbonate. The resulting phenols 17 are alkylated using a building block 5 and any base. Final introduction of an alkynyl group, giving the claimed compounds 19, or an alkenyl group, giving the claimed compounds 20, is carried out by reaction with suitable alkynes 21 and suitable alkenes 22, respectively, a transition metal catalyst and any base. Suitable transition metal catalysts are, in particular, palladium complexes or mixtures of palladium complexes and inorganic copper compounds.
The claimed compounds or intermediates in which group A of formula I or of structures 4, 6 or 7 is an acetyl group or an alkoxycarbonyl group can be used as starting materials for further modifications of group A using standard reactions of organic chemistry. This is shown in an exemplary manner in scheme 4. 




It is possible, for example, to alkylate and/or brominate a compound of structure 23 in the α-position to the carbonyl group. The literature mentions a number of suitable alkylation processes, of which the alkylation of metallated hydrazones according to Chem. Ber. 1978, 111, 1337-1361 may be mentioned by way of example. A bromination can be effected by reaction with bromine or a large number of possible brominating agents, in most cases in an inert solvent. The resulting bromoketones can be reacted with primary thioamides, affording thiazoles of the formula 25. The reaction of compounds of the formula 23 with hydroxylamines or salts thereof gives oximes which can be modified further in the α-position, as desired, for example by alkylation, furnishing structures of type 26. Reaction of the acyl group in 23 with suitable amide acetals such as, for example, N,N-dimethylformamide O,O-dimethyl acetal affords an enaminoketone as intermediate, further reaction of which with any hydrazines leads to structures of type 27.
Compounds of structure 28 can be reacted with any amidoximes, giving 1,2,4-oxadiazoles of formula 28. This reaction can take place in one step using a strong base, in most cases a protic solvent, or in two steps via the corresponding open-chain O-acylamidoximes as intermediate. Transesterification of 28 with any alcohols according to a standard method as described, for example, in Org. Syn. Coll. Vol. 1955, 3,146, affords the corresponding esters 30. According to the process described in Org. Coll. Vol. 1955, 3, 516, 536 or any equivalent process, the ester in compounds 28 can be converted into a primary amide. With the aid of a suitable thiolating agent, such as, for example, Lawesson's reagent (Tetrahedron 1985, 41, 5061), the corresponding thioamides are obtained, further reaction of which with any α-haloketones or α-haloaldehydes gives the thiazoles of type 31. Hydrolysis of the ester function in 28 under basic or acidic protic conditions gives the corresponding acids, which are degraded, for example in a Curtius rearrangement. Suitable for this purpose is, inter alia, action of diphenylphosphoryl azide (DPPA), as described in J. Am. Chem. Soc. 1972, 94, 6203. If this rearrangement is carried out in the presence of a suitable alcohol R3—OH, the carbamates 32 are obtained. In the presence of a primary or secondary amine, the products are the corresponding ureas.
Collections of compounds of the formula (I) which can be synthesized by the abovementioned scheme may also be prepared in a parallel manner, and this may be effected manually or in a semiautomated or fully automated manner. In this case, it is possible, for example, to automate the procedure of the reaction, work-up or purification of the products or of the intermediates. In total, this is to be understood as meaning a procedure as is described, for example, by S. H. DeWitt in “Annual Reports in Combinatorial Chemistry and Molecular Diversity: Automated Synthesis”, Volume 1, Verlag Escom 1997, pages 69 to 77.
A series of commercially available apparatuses as are offered by, for example, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM98SE, England or H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleiβheim, Germany may be used for the parallel procedure of the reaction and work-up. For the parallel purification of compounds of the formula (I), or of intermediates obtained during the preparation, use may be made, inter alia, of chromatography apparatuses, for example those from ISCO, Inc., 4700 Superior Street, Lincoln, Nebr. 68504, USA.
The apparatuses mentioned lead to a modular procedure in which the individual process steps are automated, but manual operations must be performed between the process steps. This can be prevented by employing semi-integrated or fully integrated automation systems where the automation modules in question are operated by, for example, robots. Such automation systems can be obtained, for example, from Zymark Corporation, Zymark Center, Hopkinton, Mass. 01748, USA.
In addition to the methods described here, compounds of the formula (I) may be prepared in part or fully by solid-phase-supported methods. For this purpose, individual intermediate steps or all intermediate steps of the synthesis or of a synthesis adapted to suit the procedure in question are bound to a synthetic resin. Solid-phase-supported synthesis methods are described extensively in the specialist literature, for example Barry A. Bunin in “The Combinatorial Index”, Academic Press, 1998.
The use of solid-phase-supported synthesis methods permits a series of protocols which are known from the literature and which, in turn, can be performed manually or in an automated manner. For example, the “tea-bag method” (Houghten, U.S. Pat. No. 4,631,211; Houghten et al., Proc. Natl. Acad. Sci, 1985, 82, 5131-5135), in which products from IRORI, 11149 North Torrey Pines Road, La Jolla, Calif. 92037, USA are employed, may be semiautomated. The automation of solid-phase-supported parallel syntheses is performed successfully, for example, by apparatuses from Argonaut Technologies, Inc., 887 Industrial Road, San Carlos, Calif. 94070, USA or MultiSynTech GmbH, Wullener Feld 4, 58454 Witten, Germany.
The preparation by the processes described herein yields compounds of the formula (I) in the form of substance collections which are termed libraries.
The present invention also relates to libraries which comprise at least two compounds of the formula (I).
The compounds of the formula (I) are suitable for controlling animal pests, in particular insects, arachnids, helminthes and mollusks, very especially preferably for controlling insects and arachnids which are encountered in agriculture, in livestock breeding, in forests, in the protection of stored goods and materials, and in the hygiene sector, and have good plant tolerance and favorable toxicity to warm-blooded species. They are active against normally sensitive and resistant species and against all or individual developmental stages. The abovementioned pests include:
From the order of the Acarina, for example, 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, for example, Oniscus aselus, Armadium vulgare, Porcellio scaber. 
From the order of the Diplopoda, for example, Blaniulus guttulatus. 
From the order of the Chilopoda, for example, Geophilus carpophagus, Scutigera spp.
From the order of the Symphyla, for example, Scutigerella immaculata. 
From the order of the Thysanura, for example, 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 maderae, Blattella germanica, Acheta domesticus, Gryllotalpa spp., Locusta migratoria migratorioides, Melanoplus differentialis, Schistocerca gregaria. 
From the order of the Isoptera, for example, Reticulitermes spp.
From the order of the Anoplura, for example, Phylloera vastatrix, Pemphigus spp., Pediculus humanus corporis, Haematopinus spp., Linognathus spp.
From the order of the Mallophaga, for example, Trichodectes pp., Damalinea spp.
From the order of the Thysanoptera, for example, Hercinothrips femoralis, Thrips tabaci. 
From the order of the Heteroptera, for example, Eurygaster spp., Dysdercus intermedius, Piesma quadrata, Cimex lectularius, Rhodnius prolixus, Triatoma spp.
From the order of the Homoptera, for example, Aleurodes brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Doralis fabae, Doralis pomi, Eriosoma lanigerum, Hyalopterus arundinis, Macrosiphum avenae, Myzus spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp., Euscelus bilobatus, Nephotettix cincticeps, Lecanium corni, Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens, Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp., Psylla spp.
From the order of the Lepidoptera, for example, Pectinophora gossypiella, Bupalus piniarius, Cheimatobia brumata, Lithocolletis blancardella, Hyponomeuta padelia, Plutella maculipennis, Malacosoma neustria, Euproctis chrysorrhoea, Lymantria spp., Bucculatrix thurberiella, Phyllocnistis citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias insulana, Heliothis spp., Laphygma exigua, Mamestra brassicae, Panolis flammea, Prodenia litura, Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella, Galleria mellonella, Cacoecia podana, Capua reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona magnanima, Tortrix viridana. 
From the order of the Coleoptera, for example, 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, Anthonomus spp., Sitophilus spp., Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrynchus assimilis, Hypera postica, Dermestes spp., Trogoderma, Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus, Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium spp., Tenebrio molitor, Agriotes spp., Conoderus spp., Melolontha melolontha, Amphimallon solstitialis, Costelytra zealandica. 
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Monomorium pharaonis, Vespa spp.
From the order of the Diptera, for example, 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, for example, Xenopsylla cheopsis, Ceratophyllus spp.
From the order of the Arachnida, for example, Scorpio maurus, Latrodectus mactans. 
From the class of the helminths, for example, Haemonchus, Trichostrongulus, Ostertagia, Cooperia, Chabertia, Strongyloides, Oesophagostomum, Hyostrongulus, Ancylostoma, Ascaris and Heterakis and also Fasciola. 
From the class of the Gastropoda, for example, Deroceras spp., Arion spp., Lymnaea spp., Galba spp., Succinea spp., Biomphalaria spp., Bulinus spp., Oncomelania spp.
From the class of the Bivalva, for example, Dreissena spp.
The plant-parasitic nematodes which can be controlled in accordance with the invention include, for example, the root-parasitic soil-dwelling nematodes such as, for example, those of the genera Meloidogyne (root knot nematodes, such as Meloidogyne incognita, Meloidogyne hapla and Meloidogyne javanica), Heterodera and Globodera (cyst-forming nematodes, such as Globodera rostochiensis, Globodera pallida, Heterodera trifolii) and of the genera Radopholus, such as Radopholus similis, Pratylenchus such as Pratylenchus neglectus, Pratylenchus penetrans and Pratylenchus curvitatus; 
Tylenchulus such as Tylenchulus semipenetrans, Tylenchorhynchus, such as Tylenchorhynchus dubius and Tylenchorhynchus claytoni, Rotylenchus such as Rotylenchus robustus, Heliocotylenchus such as Haliocotylenchus multicinctus, Belonoaimus such as Belonoaimus longicaudatus, Longidorus such as Longidorus elongatus, Trichodorus such as Trichodorus primitivus and Xiphinema such as Xiphinema index. 
Other nematode genera which can be controlled using the compounds according to the invention are Ditylenchus (stem parasites, such as Ditylenchus dipsaci and Ditylenchus destructor), Aphelenchoides (foliar nematodes, such as Aphelenchoides ritzemabosi) and Anguina (seed nematodes, such as Anguina tritici).
The invention also relates to compositions, for example crop protection compositions, preferably insecticidal, acaricidal, ixodicidal, nematicidal, molluscicidal or fungicidal, especially preferably insecticidal and acaricidal, compositions which comprise one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
To prepare the compositions according to the invention, the active substance and the other additives are combined and brought into a suitable use form.
The invention also relates to compositions, in particular insecticidal and acaricidal compositions, which comprise the compounds of the formula (I) in addition to suitable formulation auxiliaries.
In general, the compositions according to the invention comprise 1 to 95% by weight of the active substances of the formula (I). They can be formulated in various ways, depending on the biological and/or chemical-physical parameters which prevail. The following are examples of possible formulations:
Wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil- or water-based dispersions (SC), suspo-emulsions (SE), dusts (DP), seed-dressing products, granules in the form of microgranules, spray granules, coated granules and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits.
These individual types of formulations are known in principle and are described, for example, in: Winnacker-Küchler, “Chemische Technologie” [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Edition 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 auxiliaries, i.e. carrier materials and/or surface-active substances such as inert materials, surfactants, solvents and other additives, are also known and described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Ed., Darland Books, Caldwell N.J.; H. v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, “Solvents Guide”, 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, “Detergents and Emulsifiers Annual”, MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface Active Agents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt, “Grenzflächenaktive Äthylenoxidaddukte” [Surface-active ethylene oxide adducts], Wiss. Verlagsgesell., Stuttgart 1967; Winnacker-Küchler, “Chemische Technologie”, Volume 7, C. Hanser Verlag Munich, 4th Edition 1986.
Based on these formulations, it is also possible to prepare combinations with other pesticidally active materials, fertilizers and/or growth regulators, for example in the form of a ready-mix formulation or a tank mix. Wettable powders are preparations which are uniformly dispersible in water which, besides the active substance, also comprise wetters, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or alkylphenolsulfonates and dispersants, for example sodium lignosulfonate or sodium 2,2′-dinaphthylmethane-6,6′-disulfonate, in addition to a diluent or inert material.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers. As emulsifiers, the following can be used, for example: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
Dusts are obtained, for example, by grinding the active substance with finely divided solid materials, for example talc or natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earth. Granules can be prepared either by atomizing the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carrier materials such as sand or kaolinites, or of granulated inert material, by means of adhesives, for example polyvinyl alcohol or sodium polyacrylate, or else mineral oils. Suitable active substances can also be granulated in the manner which is customary for the preparation of fertilizer granules, if desired as a mixture with fertilizers.
The active substance concentration in wettable powders is usually approximately 10 to 90% by weight, the remainder to 100% by weight is composed of customary formulation constituents. In the case of emulsifiable concentrates, the active substance concentration may be approximately 5 to 80% by weight. Formulations in the form of dusts usually comprise 5 to 20% by weight of active substance, sprayable solutions approximately 2 to 20% by weight. In the case of granules, the active substance content depends partly on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers and the like are being used.
Besides, the abovementioned active substance formulations comprise, if appropriate, the tackifiers, wetters, dispersants, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.
For use, the concentrates, which are present in commercially available form, are, if desired, diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules, using water. Preparations in the form of dusts and granules and sprayable solutions are usually not diluted any further with other inert substances prior to use.
The application rate required varies with the external conditions such as, inter alia, temperature and humidity. It may vary within wide limits, for example between 0.0005 and 10.0 kg/ha or more of active substance, but it is preferably between 0.001 and 5 kg/ha of active compound.
The active substances according to the invention, in their commercially available formulations and in the use forms prepared from these formulations, may be present in mixtures with other active substances such as insecticides, attractants, sterilants, acaricides, nematicides, fungicides, growth regulatory substances or herbicides.
The pesticides include, for example, phosphoric esters, carbamates, carboxylic esters, formamidines, tin compounds and materials produced by microorganisms.
Preferred components in mixtures are:

    1. from the group of the phosphorus compounds acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, bromophos, bromophos-ethyl, cadusafos (F-67825), chlorethoxyphos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, demeton, demeton-S-methyl, demeton-S-methyl sulfone, dialifos, diazinon, dichlorvos, dicrotophos, dimethoate, disulfoton, EPN, ethion, ethoprophos, etrimfos, famphur, fenamiphos, fenitriothion, fensulfothion, fenthion, fonofos, formothion, fosthiazate (ASC-66824), heptenophos, isazophos, isothioate, isoxathion, malathion, methacrifos, methamidophos, methidathion, salithion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosfolan, phospho-carb (BAS-301), phosmet, phosphamidon, phoxim, pirimiphos, pirimiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion;
    2. from the group of the carbamates alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenylbutyryl (methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino)-N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate;
    3. from the group of the carboxylic esters acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-dimethyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentylisomer), bioresmethrin, bifenthrin, (RS)-1-cyano-1-(6-phenoxy-2-pyridyl)methyl (1RS)-trans-3-(4-tert-butylphenyl)-2,2-dimethylcyclopropanecarboxylate (NCI 85193), cycloprothrin, cyfluthrin, cyhalothrin, cythithrin, cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, fenfluthrin, fenpropathrin, fenvalerate, flucythrinate, flumethrin, fluvalinate (D isomer), imiprothrin (S-41311), lambda-cyhalothrin, permethrin, phenothrin ((R) isomer), prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin (TD-2344), tralomethrin, transfluthrin, zeta-cypermethrin (F-56701);
    4. from the group of the amidines amitraz, chlordimeform;
    5. from the group of the tin compounds cyhexatin, fenbutatin oxide;
    6. others abamectin, ABG-9008, acetamiprid, Anagrapha falcitera, AKD-1022, AKD-3059, ANS-118, Bacillus thuringiensis, Beauveria bassianea, bensultap, bifenazate (D-2341), binapacryl, BJL-932, bromopropylate, BTG-504, BTG-505, buprofezin, camphechlor, cartap, chlorobenzilate, chlorfenapyr, chlorfluazuron, 2-(4-chlorophenyl)-4,5-diphenylthiophene (UBI-T 930), chlorfentezine, chromafenozide (ANS-118), CG-216, CG-217, CG-234, A-184699, 2-naphthylmethyl cyclopropane-carboxylate (Ro12-0470), cyromazin, diacloden (thiamethoxam), diafenthiuron, ethyl N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzocarboximidate, DDT, dicofol, diflubenzuron, N-(2,3-dihydro-3-methyl-1,3-thiazol-2-ylidene)-2,4-xylidine, dinobuton, dinocap, diofenolan, DPX-062, emamectin benzoate (MK-244), endosulfan, ethiprole (sulfethiprole), ethofenprox, etoxazole (YI-5301), fenazaquin, fenoxycarb, fipronil, fluazuron, flumite (flufenzine, SZI-121), flonicamid (IKI-220), 2-fluoro-5-(4-(4-fenoxyphenyl)-4-methyl-1-pentyl)diphenylether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halfenozide (RH-0345), halofenprox (MTI-732), hexaflumuron (DE—473), hexythiazox, HOI-9004, hydramethylnon (AC 217300), lufenuron, imidacloprid, indoxacarb (DPX-MP062), kanemite (AKD-2023), M-020, MTI-446, ivermectin, M-020, methoxyfenozide (Intrepid, RH-2485), milbemectin, NC-196, neemgard, nitenpyram (TI-304), 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), pyriproxyfen (S-71639), NC-196, NC-1111, NNI-9768, novaluron (MCW-275), OK-9701, OK-9601, OK-9602, propargite, pymethrozine, pyridaben, pyridalyl (S-1812), pyrimidifen (SU-8801), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, SI-8601, silafluofen, silomadine (CG-177), spinosad, SU-9118, spirodiclofen (BAI-2740), spiromesifen, tebufenozide, tebufenpyrad (MK-239), teflubenzuron, tetradifon, tetrasul, thiacloprid, thiocyclam, TI-435, tolfenpyrad (OMI-88), triazamate (RH-7988), triflumuron, verbutin, vertalec (Mykotal), YI-5301.


The abovementioned components for combinations are known active substances, many of which are described in Ch. R Worthing, S. B. Walker, The Pesticide Manual, 11th Edition, British Crop Protection Council, Farnham 1997.
The active substance content of the use forms prepared from the commercially available formulations may range from 0.00000001 up to 95% by weight of active substance, preferably between 0.00001 and 1% by weight.
Application is effected in a customary manner adapted to suit the use forms.
Therefore in further aspects of the invention there are provided the use of the compounds of the formula (I) or salts thereof for controlling animal pests; and a method for controlling animal pests, comprising the step of directly or indirectly applying to the pest a compound of the formula (I) or a salt thereof.
The active substances according to the invention are also suitable for controlling endoparasites and ectoparasites in the human and veterinary medicine sector and/or in the field of animal keeping. The active substances according to the invention are applied here in a known manner, such as by oral administration in the form of, for example, tablets, capsules, drinks or granules, by dermal application in the form of, for example, dipping, spraying, pouring on and spotting on, and dusting, and by parenteral administration in the form of, for example, an injection.
Accordingly, the compounds of the formula (I) according to the invention can also be employed particularly advantageously for the treatment of warm-blooded species, especially in livestock keeping (for example cattle, sheep, pigs and poultry such as chickens, geese and the like). In a preferred embodiment of the invention, the compounds, if appropriate in suitable formulations, are administered orally to the animals, if appropriate together with the drinking water or feed. Since excretion in the feces is efficient, the development of insects in the animals' feces can be prevented very easily in this manner. The dosages and formulations which are suitable in each case depend, in particular, on the species and the developmental stage of the productive livestock and also on the risk of infestation and can be determined readily and established by customary methods. For example, the compounds can be employed in cattle at dosages of 0.01 to 1 mg/kg of bodyweight.
In addition to their lethal effect on pests, the compounds of the formula (I) or their salts also have a pronounced repellant effect.
A repellant for the purpose of the description is a substance or substance mixture which has a warding-off or fending-off effect on other life organisms, in particular harmful pests and nuisance pests. The term also encompasses effects such as the antifeeding effect, where the intake of feed is disturbed or prevented (antifeedant effect), suppression of oviposition, or an effect on the development of the population.
The invention therefore also provides the use of compounds of the formula (I) or their salts for achieving the abovementioned effects, in particular in the case of the pests stated in the biological examples.
The invention also provides a method for fending off, or warding off, harmful organisms, where one or more compounds of the formula (I) or their salts are applied to the site from which the harmful organisms are to be fended off or warded off.
In the case of a plant, application may mean, for example, a treatment of the plant, but also of the seed.
As regards the effect on populations, it is interesting to note that effects can also be observed in succession during the development of a population, where summation may take place. In such a case, the individual effect itself may only have an efficacy of markedly less than 100% but in total an efficacy of 100% is still achieved in the end.
Moreover, the compounds of the formula (I) or their salts are distinguished by the fact that the composition is usually applied earlier than in the case of a direct control, if the abovementioned effects are to be exploited. The effect frequently lasts over a long period, so that a duration of action of over 2 months is achieved.
The effects are observed in insects, arachnids and the other abovementioned pests.
In addition to the abovementioned application methods, the active compounds of the formula (I) according to the invention have excellent systemic action. Accordingly, the active compounds can also be introduced into the plants via parts of the plant, both below ground and above ground (root, stem, leaf), if the active compounds are applied, in liquid or solid form in the direct vicinity of the plant (for example granules in soil application, application in flooded rice paddies).
Furthermore, the active compounds according to the invention are particularly useful for the treatment of vegetative and generative plant propagation material, such as, for example, of seeds, for example of cereals, vegetables, cotton, rice, sugar beet and other crops and ornamental plants, of bulbs, seedlings and tubers of other crops and ornamental plants which are propagated vegetatively. The treatment can be carried out before sowing or before planting (for example by special seed coating techniques, by dressing in liquid or solid form or as a seed box treatment), during sowing or planting or after sowing or planting by special application techniques (for example furrow treatment). The amount of active compound used can vary within a relatively large range, depending on the application. In general, the application rates are between 1 g and 10 kg of active compound per hectare of soil surface.
The compounds of the formula (I) can also be employed for controlling harmful plants in crops of known genetically engineered plants or genetically engineered plants yet to be developed. As a rule, the transgenic plants are distinguished by especially advantageous properties, for example by resistances to particular crop protection agents, resistances to plant diseases or pathogens of plant diseases, such as particular insects or microorganisms such as fungi, bacteria or viruses. Other particular properties concern, for example, the harvested material with regard to quantity, quality, storage properties, composition and specific constituents. Thus, transgenic plants are known where the starch content is increased, or the starch quality is altered, or where the harvested material has a different fatty acid composition.
The use in economically important transgenic crops of useful plants and ornamentals is preferred, for example of cereals such as wheat, barley, rye, oats, millet, rice, cassava and maize or else crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types of vegetables.
When used in transgenic crops, in particular those which have resistances to insects, effects are frequently observed, in addition to the effects against harmful organisms to be observed in other crops, which are specific for application in the transgenic crop in question, for example an altered or specifically widened spectrum of pests which can be controlled, or altered application rates which may be employed for application.
Therefore in further aspects of the invention there are provided the use of the compounds of formula (I) for controlling harmful organisms in transgenic crop plants; and a method for controlling harmful organisms in transgenic crop plants comprising the step of directly or indirectly applying to the pest a compound of the formula (I).
The use of the compounds according to the invention embraces, in addition to direct application onto the pests, any other application in which compounds of the formula (I) act on the pests. Such indirect applications can, for example, be the use of compounds which, for example in the soil, the plant or the pest, decompose into compounds of the formula (I) and/or are degraded into compounds of the formula (I). The examples below serve to illustrate the invention.


A. CHEMICAL EXAMPLES
Example A
3-Acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethyl-pyrid-2-yloxy)propyloxy]benzene (No. 27)
Step 1: 3-acetyl-1-chloro-2,5-dihydroxybenzene
8.7 g of 3-acetyl-1-chloro-2-hydroxy-5-methoxybenzene were taken up in 150 ml of hydrobromic acid (48% strength in water). 1.69 g of red phosphorus were added, and the mixture was then stirred at 85° C. for 15 hours. After cooling, the reaction mixture was poured into about 1 liter of ice-cold water and extracted with ethyl acetate. The crude product obtained after drying and concentration of the ethyl acetate phase was purified by column chromatography. Yield: 2.9 g (36%)
1H-NMR (CDCl3): δ=2.61 (s, 3H); 4.73 (s, 1H); 7.18 (m, 2H), 12.33 (s, 1H).
Step 2: 3-acetyl-2,5-bis-(3,3-dichloroprop-2-enyloxy)-1-chlorobenzene
2.9 g of 3-acetyl-1-chloro-2,5-dihydroxybenzene were dissolved in 29 ml of acetone, and 3.39 g of 1,1,3-trichloropropene, 4.3 g of potassium carbonate and 0.7 g of sodium iodide were added. The mixture was heated under reflux for 5 hours (monitored by TLC). The reaction mixture was then allowed to cool and concentrated using a rotary evaporator, and the resulting crude product was subjected to chromatographic purification. Yield: 6.1 g (99%)
1H-NMR (CDCl3): δ=2.60 (s, 3H); 4.58 (d, 2H); 4.62 (d, 2H); 6.12 (t, 1H); 6.21 (t,1H); 7.01 (d, 1H); 7.09 (d, 1H).
Step 3: 3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-hydroxybenzene
6.1 g of 3-acetyl-2,5-bis-(3,3-dichloroprop-2-enyloxy)-1-chlorobenzene were dissolved in 160 ml of toluene. 7.79 g of magnesium dibromide/diethyl ether complex, dissolved in 25 ml of diethyl ether, were added to this solution, and the mixture was then stirred at 85° C. for 6 hours. After the reaction had ended according to TLC, the mixture was allowed to cool, about 300 ml of water were added and the organic phase was separated off. The aqueous phase was re-extracted twice with ethyl acetate, and the combined organic phases were then washed with saturated sodium chloride solution. After drying and concentration of the organic phase, the crude product was purified chromatographically. Yield: 2.86 g (64%)
1H-NMR (CDCl3): δ=2.62 (s, 3H); 4.62 (d, 2H); 6.13 (t, 1H); 7.17 (d, 1H), 7.22 (d, 1H); 12.40 (s, 1H).
Step 4: 3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene
Under an atmosphere of protective gas, 1.2 g of 3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-hydroxybenzene, 0.9 g of 3-(5-trifluoromethylpyrid-2-yloxy)propan-1-ol and 1.12 g of triphenylphosphine were dissolved in 35 ml of dry tetrahydrofuran (THF). With ice-bath cooling, 0.74 g of diethyl azodicarboxylate was added dropwise. After about 30 minutes, the ice-bath was removed, and the mixture was stirred at room temperature for 15 hours. The mixture was then concentrated under reduced pressure and the residue was taken up in a mixture of ethyl acetate and water. After shaking, the organic phase was isolated, dried and concentrated under reduced pressure. The crude product was purified chromatographically. Yield: 1.52 g (74%)
1H-NMR (CDCl3): δ=2.27 (m, 2H); 2.6 (s, 3H); 4.08 (t, 2H); 4.60 (m, 4H); 6.12 (t, 1H); 6.81 (d, 1H); 6.99 (d, 1H); 7.08 (d, 1H); 7.77 (dd, 1H); 8.42 (br. s, 1H).
Example B
1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(3-ethyl-1,2,4-oxadiazol-5-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene (No. 356)
Step 1: 3-chloro-2,5-dihydroxybenzoic acid
9.95 g of methyl 3-chloro-2-hydroxy-5-methoxybenzoate were taken up in 300 ml of hydrobromic acid (48% strength in water). 1.79 g of red phosphorus were added, and the mixture was then stirred at 85° C. for 15 hours. After cooling, the reaction mixture was poured into about 1 liter of ice-cold water and extracted with ethyl acetate. The crude product obtained after drying and concentration of the ethyl acetate phase was used for the next step without further purification.
Step 2: methyl 3-chloro-2,5-dihydroxybenzoate
8.65 g of the crude product of the previous step were dissolved in 12 ml of anhydrous methanol, and 0.5 ml of concentrated sulfuric acid was added. The mixture was heated under reflux for 6 hours. After cooling, the reaction mixture was concentrated under reduced pressure, diluted with tert-butyl methyl ether to about 200 ml and washed with water and saturated sodium bicarbonate solution. The ether phase was dried and concentrated and the crude product was purified chromatographically. Yield: 4.85 g (52% over 2 steps)
1H-NMR (CDCl3): δ=3.97 (s, 3H); 4.61 (br. s, 1H); 7.15 (d, 1H); 7.22 (d, 1H); 10.83 (s, 1H).
Step 3: methyl 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-hydroxybenzoate
1.67 g of methyl 3-chloro-2,5-dihydroxybenzoate, 2 g of 1,1,3-trichloropropene, 2.27 g of potassium carbonate and 0.37 g of sodium iodide were dissolved in 17 ml acetone, and the mixture was stirred at 50° C. for 16 hours. After cooling, the mixture was concentrated under reduced pressure and the crude product was taken up in ethyl acetate and washed with water. Drying and concentration of the ethyl acetate phase gave a crude product which was dissolved in 65 ml of toluene. 2.95 g of magnesium dibromide/diethyl ether complex, dissolved in 10 ml of diethyl ether, were added using a pipette, and the mixture was heated at 80° C.-85° C. for 20 hours. The mixture was allowed to cool, about 300 ml of water were added and the organic phase was separated off. The aqueous phase was re-extracted twice with ethyl acetate, and the combined organic phases were then washed with saturated sodium chloride solution. After drying and concentration of the organic phase, the crude product was purified chromatographically. Yield: 2.01 g (79%)
1H-NMR (CDCl3): δ=3.99 (s, 3H); 4.60 (d, 2H); 6.12 (t, 1H); 7.20 (d, 1H), 7.25 (d, 1H); 10.95 (s, 1H).
Step 4: methyl 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzoate (No. 39)
Under an atmosphere of protective gas, 1.85 g of methyl 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-hydroxybenzoate, 1.3 g of 3-(5-trifluoromethylpyrid-2-yloxy)-propan-1-ol and 1.64 g of triphenylphosphine were dissolved in 50 ml of dry tetrahydrofuran (THF). With ice-bath cooling, 1.09 g of diethyl azodicarboxylate were added dropwise. After about 30 minutes, the ice-bath was removed, and the mixture was stirred at room temperature for 15 hours. The mixture was then concentrated under reduced pressure and the residue was taken up in a mixture of ethyl acetate and water. After shaking, the organic phase was isolated, dried and concentrated under reduced pressure. The crude product was purified chromatographically. Yield: 1.79 g (59%)
1H-NMR (CDCl3): δ=2.30 (m, 2H); 3.86 (s, 3H); 4.16 (t, 2H); 4.62 (m, 4H); 6.13 (t, 1H); 6.80 (d, 1H); 7.10 (d, 1H); 7.21 (d, 1H); 7.77 (dd, 1H); 8.42 (br. s, 1H).
Step 5: 1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(3-ethyl-1,2,4-oxadiazol-5-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene
0.05 g of methyl 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzoate and 0.028 g of propionamidoxime were dissolved in 1 ml of anhydrous ethanol. A solution of 0.008 g of sodium in 0.5 ml of ethanol was added to this solution. The mixture was stirred at 40° C. for 2 hours and at room temperature for 20 hours. The mixture was then concentrated, and diethyl ether and water were added. After shaking, the ether phase was isolated, dried and concentrated under reduced pressure, and the crude product was purified chromatographically. Yield: 0.017 g (32%)
1H-NMR (CDCl3): δ=1.40 (t, 3H); 2.38 (m, 2H); 2.82 (q, 2H); 4.19 (t, 2H); 4.66 (m, 4H); 6.15 (t, 1H); 6.80 (d, 1H); 7.17 (d, 1H); 7.47 (d, 1H); 7.76 (dd, 1H); 8.43 (br. s, 1H).
Example C
3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[4-(5-trifluoromethylpyrid-2-yloxy)butyloxy]benzene (No. 59)
Under an atmosphere of protective gas, 0.1 g of 3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-hydroxybenzene, 0.08 g of 4-(5-trifluoromethylpyrid-2-yloxy)butan-1-ol and 0.093 g triphenylphosphine were dissolved in 2 ml of dry tetrahydrofuran (THF). With ice-bath cooling, 56 μl of diethyl azodicarboxylate were added dropwise. After about 30 minutes, the ice-bath was removed, and the mixture was stirred at room temperature for 15 hours. The mixture was then concentrated under reduced pressure and the residue was taken up in a mixture of ethyl acetate and water. After shaking, the organic phase was isolated, dried and concentrated under reduced pressure. The crude product was purified chromatographically. Yield: 0.051 g (35%)
1H-NMR (CDCl3): δ=1.96 (m, 4H); 2.6 (s, 3H); 4.02 (m, 2H); 4.41 (m, 2H); 4.59 (d, 2H); 6.12 (t, 1H); 6.80 (d, 1H); 7.00 (d, 1H); 7.08 (d, 1H); 7.78 (dd, 1H); 8.42 (br. s, 1H).
Example D
1-chloro-3-(2-chlorophenylethynyl)-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene (No. 226)
Step 1: 5-benzoyloxy-3-chloro-2-hydroxy-1-iodobenzene
3 g of 5-benzoyloxy-1-chloro-2-hydroxybenzene were dissolved in 35 ml of DMF. 2.17 g of sodium iodide and 3.29 g of chloramin T were added. After one hour of stirring at room temperature, about 500 ml of water were added to the mixture, which was then extracted with ethyl acetate. The organic phase was washed with 5% strength sodium thiosulfate solution, dried and concentrated using a rotary evaporator. The resulting product was clean enough for the next reaction. Yield: 3.81 g (84%)
1H-NMR (CDCl3): δ=4.70 (br. s, 1H); 7.30 (d, 1H); 7.54 (m, 3H); 7.63 (m, 1H); 8.17 (d, 2H).
Step 2: 5-benzoyloxy-3-chloro-1-iodo-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]-benzene
Under an atmosphere of protective gas, 3.5 g of 5-benzoyloxy-3-chloro-2-hydroxy-1-iodobenzene, 2.07 g of 3-(5-trifluoromethylpyrid-2-yloxy)propan-1-ol and 2.57 g of triphenylphosphine were dissolved in 100 ml of dry tetrahydrofuran (THF). With ice-bath cooling, 1.71 g of diethyl azodicarboxylate were added dropwise. After about 30 minutes, the ice-bath was removed, and the mixture was stirred at room temperature for 15 hours. The mixture was then concentrated under reduced pressure and the residue was taken up in a mixture of ethyl acetate and water. After shaking, the organic phase was isolated, dried and concentrated under reduced pressure. The crude product was purified chromatographically. Yield: 3.12 g (58%)
1H-NMR (CDCl3): δ=2.38 (quint., 2H); 4.19 (t, 2H); 4.65 (t, 2H); 6.82 (d, 1H); 7.31 (d, 1H); 7.53 (m, 2H); 7.58 (d, 1H); 7.65 (m, 1H); 7.78 (dd, 1H); 8.16 (d, 1H); 8.43 (br. s, 1H).
Step 3: 3-chloro-5-hydroxy-1-iodo-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]-benzene
3.12 g of 5-benzoyloxy-3-chloro-1-iodo-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene were dissolved in 16 ml of tetrahydrofuran and 7.8 ml of methanol, and 3.9 ml of 2N aqueous sodium hydroxide solution were added. After 30 minutes of stirring at room temperature. 3.9 ml of 2N hydrochloric acid were added, and the reaction mixture was concentrated under reduced pressure. Saturated sodium chloride solution and ethyl acetate were added to the residue, and the mixture was shaken. The ethyl acetate phase was isolated, dried and concentrated. The resulting crude product was purified chromatographically. Yield: 2.03 g (80%)
1H-NMR (CDCl3): δ=2.34 (quint., 2H); 4.09 (t, 2H); 4.62 (t, 2H); 5.13 (s, 1H); 6.82 (d, 1H); 6.88 (d, 1H); 7.17 (d, 1H); 7.78 (dd, 1H); 8.43 (br. s, 1H).
Step 4: 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-1-iodo-2-[3-(5-trifluoromethylpyrid-2--yloxy)propyloxy]benzene
2.23 g of 3-chloro-5-hydroxy-1-iodo-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]-benzene were dissolved in 22 ml of acetone, and 0.79 g of 1,1,3-trichloropropene, 1.3 g of potassium carbonate and 0.27 g of sodium iodide were added. The mixture was stirred at room temperature for 20 hours (monitored by TLC). The reaction mixture was then concentrated using a rotary evaporator, and the resulting crude product was subjected to chromatographic purification. Yield: 2.62 g (95%)
1H-NMR (CDCl3): δ=2.35 (quint., 2H); 4.12 (t, 2H); 4.58 (d, 2H); 4.62 (t, 2H); 6.10 (t, 1H); 6.81 (d, 1H); 6.92 (d, 1H); 7.20 (d, 1H); 7.78 (dd, 1H); 8.43 (br. s, 1H).
Step 5: 1-chloro-3-(2-chlorophenylethynyl)-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene
Under an atmosphere of protective gas, 0.1 g of 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-1-iodo-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene, 0.03 g of 1-chloro-2-ethynylbenzene and 0.003 g of copper(I) iodide were dissolved in 1 ml of triethylamine. 0.005 g of bis(triphenylphosphine)palladium(II) chloride was added, and the mixture was stirred at 70° C. for 1 hour. The mixture was then allowed to cool and concentrated under reduced pressure, and the resulting residue was subjected to chromatographic purification. Yield: 0.085 g (84%)
1H-NMR (CDCl3): δ=2.35 (quint., 2H); 4.31 (t, 2H); 4.61 (m, 4H); 6.14 (t, 1H); 6.73 (d, 1H); 6.95 (m, 2H); 7.2-7.3 (m, 2H); 7.40 (m, 1H); 7.55 (m, 1H); 7.70 (dd, 1H); 8.36 (br. s, 1H).
Example E
1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(2Δ-oxazolin-2-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene (No. 738)
Step 1: 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)-propyloxy]benzoic acid
1 g of methyl 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzoate was dissolved in 20 ml of tetrahydrofuran and 10 ml of methanol, and 2.6 ml of 2N aqueous sodium hydroxide solution were added. After one hour of stirring at room temperature, 2.6 ml of 2N hydrochloric acid were added, and the reaction mixture was concentrated under reduced pressure. Saturated sodium chloride solution and ethyl acetate were added to the residue, and the mixture was shaken. The ethyl acetate phase was isolated, dried and concentrated. The resulting crude product was purified chromatographically. Yield: 0.91 g (94%)
1H-NMR (CDCl3): δ=2.39 (m, 2H); 4.32 (t, 2H); 4.62 (m, 4H); 6.16 (t, 1H); 6.83 (d, 1H); 7.18 (d, 1H); 7.52 (d, 1H); 7.78 (dd, 1H); 8.42 (br. s, 1H).
Step 2: N-(2-hydroxyethyl)-3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzamide (No. 33)
0.2 g of 3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)-propyloxy]benzoic acid and 0.065 g of carbonyldiimidazole were allowed to react at room temperature in 4 ml of anhydrous toluene for 1.5 hours. 0.027 g of 2-amino-ethanol was then added, and the mixture was stirred at room temperature for another hour. The reaction mixture was concentrated under reduced pressure and purified by column chromatography. Yield: 0.159 g (73%)
1H-NMR (CDCl3): δ=2.36 (m, 2H); 3.23 (br. s, 1H); 3.60 (m, 2H); 3.82 (m, 2H); 4.13 (t, 2H); 4.60 (t, 4H); 4.63 (d, 2H); 6.15 (t, 1H); 6.82 (d, 1H); 7.06 (d, 1H); 7.28 (d, 1H); 7.79 (dd, 1H); 8.20 (br. m, 1H); 8.42 (br. s, 1H).
Step 3: 1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(2Δ-oxazolin-2-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene
0.099 g of N-(2-hydroxyethyl)-3-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzamide was dissolved in 1 ml of anhydrous toluene, and 0.065 g of (methoxycarbonylsulfamoyl)triethylammonium N-betaine was added. The mixture was stirred at 50° C. for 1.5 hours. The reaction mixture was then allowed to cool, ethyl acetate and water were added and the mixture was shaken. The ethyl acetate phase was isolated, dried and concentrated under reduced pressure. The crude product was purified chromatographically. Yield: 0.018 g (20%)
1H-NMR (CDCl3): δ=2.28 (m, 2H); 4.04 (t, 2H); 4.15 (t, 2H); 4.40 (t, 2H); 4.60 (m, 4H); 6.14 (t, 1H); 6.80 (d, 1H); 7.03 (d, 1H); 7.20 (d, 1H); 7.76 (dd, 1H); 8.42 (br. s, 1H).
Example F
1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(1-methylpyrazol-3-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene (No. 950)
0.3 g of 3-acetyl-1-chloro-5-(3,3-dichloroprop-2-enyloxy)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene and 128 μl of N,N-dimethylformamide dimethyl acetal were stirred at 95° C. for 5 hours. The reaction mixture was then concentrated under high vacuum (<1 mbar) and the residue was dissolved in 4 ml of ethanol. 0.015 g of methylhydrazine was added, and the mixture was heated under reflux for 2 hours. After cooling, the mixture was concentrated and the resulting crude product was purified chromatographically. Yield: 0.212 g (66%)
1H-NMR (CDCl3): δ=1.98 (m, 2H); 3.73 (t, 2H); 3.77 (s, 3H); 4.34 (t, 2H); 4.62 (d, 2H); 6.15 (t, 1H); 6.27 (m, 1H); 6.73 (d, 1H); 6.76 (d, 1H); 7.01 (d, 1H); 7.42 (m, 1H); 7.78 (dd, 1H); 8.41 (br. s, 1H).
The product was contaminated with less than 10% of the regioisomeric structure 1-chloro-5-(3,3-dichloroprop-2-enyloxy)-3-(1-methylpyrazol-5-yl)-2-[3-(5-trifluoromethylpyrid-2-yloxy)propyloxy]benzene.
The compounds listed in Tables 1 to 11 below can be prepared in an analogous manner. Here, Me is methyl, Et is ethyl, Ph is phenyl, Py is pyridine and m.p. means melting point.








 TABLE 1





Number
Skeleton







1







2







3







4







5







6







7







8







9







10







11







12







13







14







15







16







17







18







19







20







21







22







23







24







25







26







27







28







29







30







31







32







33







34







35







36







37







38







39







40







41







42







43







44







45







46







47







48







49







50







51







52







53







54







55







56





















 TABLE 2























No.
Skeleton
X
R
m.p.














1
1
O
CH2CF3



2
1
O
Et


3
1
O
Me


4
2
O
CH2CF3


5
2
O
Et


6
2
O
Me
oil


7
2
O
OMe
oil


8
3
O
CH2CF3


9
3
O
Et


10
3
O
Me


11
4
O
CH2CF3


12
4
O
Et


13
4
O
Me


14
5
O





68° C.


15
5
O





oil


16
5
O





oil


17
5
O





oil


18
5
O





oil


19
5
O





oil


20
5
O
1-imidazolyl
oil


21
5
O
CH═CH—NMe2
syrup


22
5
O
CH2CF3


23
5
O
CH2CH2CH3


24
5
O
CHBr2
oil


25
5
O
Et
oil


26
5
O
H
oil


27
5
O
Me
oil


28
5
N—OH
Me
66° C.


29
5
N—OMe
Me
oil


30
5
O
NH2
91° C.


31
5
S
NH2
110° C.


32
5
O
NHCH(Me)CH2OH
106° C.


33
5
O
NHCH2CH2OH
78° C.


34
5
O
NHEt
73° C.


35
5
O
NHMe—OMe
oil


36
5
O
NMe2
oil


37
5
O
O—CH(Me)2
glass-like


38
5
O
O—CH2CH2CH3
oil


39
5
O
OMe
oil


40
5
O
O-phenyl
oil


41
6
O
CH2CF3


42
6
O
Et


43
6
O
Me
oil


44
6
N—OH
Me
129° C.


45
6
N—OMe
Me
oil


46
6
O
Me


47
7
O
CH2CF3


48
7
O
Et


49
7
O
Me


50
8
O





oil


51
8
O





oil


52
8
O





oil


53
8
O





oil


54
8
O





oil


55
8
O





oil


56
8
O
CH2CF3


57
8
O
Et


58
8
O
H


59
8
O
Me
oil


60
8
O
OMe
oil


61
9
O
CH2CF3


62
9
O
Et


63
9
O
Me


64
10
O
CH2CF3


65
10
O
Et


66
10
O
Me


67
11
O
CH2CF3


68
11
O
Et


69
11
O
Me


70
11
O
OMe
32° C.-35° C.


71
12
O
CH2CF3


72
12
O
Et


73
12
O
Me
82° C.


74
13
O
CH2CF3


75
13
O
Et


76
13
O
Me
110° C.


77
14
O
CH2CF3


78
14
O
Et


79
14
O
Me


80
15
O
CH2CF3


81
15
O
Et


82
15
O
Me
oil


83
15
N—OH
Me
oil


84
15
N—OMe
Me
oil


85
15
N—OCH2CH═CH2
Me
oil


86
15
O
OMe
oil


87
16
O
CH2CF3


88
16
O
Et


89
16
O
Me
oil


90
16
N—OH
Me
oil


91
16
N—OMe
Me
oil


92
16
N—OCH2CH═CH2
Me
oil


93
16
O
OMe
oil


94
17
O
CH2CF3


95
17
O
Et


96
17
O
Me


97
17
O
OMe
oil


98
18
O
CH2CF3


99
18
O
Et


100
18
O
Me


101
19
O
CH2CF3


102
19
O
Et


103
19
O
Me


104
20
O
CH2CF3


105
20
O
Et


106
20
O
Me


107
21
O
Me


108
22
O
CH2CF3


109
22
O
Et


110
22
O
H


111
22
O
Me


112
23
O
CH2CF3


113
23
O
Et


114
23
O
Me


115
24
O
CH2CF3


116
24
O
Et


117
24
O
Me


118
25
O
CH2CF3


119
25
O
Et


120
25
O
H


121
25
O
Me


122
26
O
CH2CF3


123
26
O
Et


124
26
O
Me


125
27
O
CH2CF3


126
27
O
Et


127
27
O
Me


128
28
O
CH2CF3


129
28
O
Et


130
28
O
Me


131
29
O
CH2CF3


132
29
O
Et


133
29
O
Me


134
30
O
CH2CF3


135
30
O
Et


136
30
O
Me


137
31
O
CH2CF3


138
31
O
Et


139
31
O
Me


140
32
O
CH2CF3


141
32
O
Et


142
32
O
Me


143
33
O
CH2CF3


144
33
O
Et


145
33
O
Me


146
34
O
CH2CF3


147
34
O
Et


148
34
O
Me


149
35
O
CH2CF3


150
35
O
Et


151
35
O
Me


152
36
O
CH2CF3


153
36
O
Et


154
36
O
Me


155
37
O
CH2CF3


156
37
O
Et


157
37
O
Me


158
38
O
CH2CF3


159
38
O
Et


160
38
O
Me


161
39
O
CH2CF3


162
39
O
Et


163
39
O
Me


164
40
O
CH2CF3


165
40
O
Et


166
40
O
Me


167
41
O
CH2CF3


168
41
O
Et


169
41
O
Me


170
42
O
CH2CF3


171
42
O
Et


172
42
O
Me


173
43
O
CH2CF3


174
43
O
Et


175
43
O
Me


176
44
O
CH2CF3


177
44
O
Et


178
44
O
Me


179
45
O
CH2CF3


180
45
O
Et


181
45
O
Me


182
46
O
CH2CF3


183
46
O
Et


184
46
O
Me


185
47
O
CH2CF3


186
47
O
Et


187
47
O
Me


188
48
O
CH2CF3


189
48
O
Et


190
48
O
H


191
48
O
Me


192
49
O
CH2CF3


193
49
O
Et


194
49
O
Me


195
50
O
CH2CF3


196
50
O
Ft


197
50
O
Me


198
51
O
CH2CF3


199
51
O
Et


200
51
O
H


201
51
O
Me


202
52
O
CH2CF3


203
52
O
Et


204
52
O
Me


205
53
O
CH2CF3


206
53
O
Et


207
53
O
Me


208
54
O
CH2CF3


209
54
O
Ft


210
54
O
Me


211
55
O
CH2CF3


212
55
O
Ft


213
55
O
Me


214
56
O
CH2CF3


215
56
O
Ft


216
56
O
Me


1236
5
O
OCH2CF3


1237
5
O
O(3-(OCF2CF2H)—Ph


1238
5
O
O(4-F—Ph)


1239
5
O
O(3-F—Ph)


1240
5
O
O(3-CF3—Ph)


1241
5
O
SCH2CF3


1242
5
O
O(4-OCF3—Ph)


1243
5
O
SPh


1244
5
O
S(3-F—Ph)


1245
5
O
S(4-CF3—Ph)


1246
5
O
NHNH(2,6-Cl2—4-CF3—Ph)


1247
5
O
O(C2H4(2,6-Cl2—4-CF3—Ph)


1248
5
N
NH(2,6-Cl2—4-CF3—Ph))
















 TABLE 3
























No.
Skeleton
R
m.p.
















217
1
H




218
1
Me



219
2
H



220
2
Me



221
3
H



222
3
Me



223
4
H



224
4
Me



225
5
1-hexyl
oil



226
5
2-chlorophenyl
oil



227
5
CH2OH
89° C.



228
5
CH2OMe
oil



229
5
H
oil



230
5
Me



231
5
SiMe3
oil



232
6
H



233
6
Me



234
7
H



235
7
Me



236
8
H



237
8
Me



238
9
H



239
9
Me



240
10
H



241
10
Me



242
11
H



243
11
Me



244
12
H



245
12
Me



246
13
H



247
13
Me



248
14
H



249
14
Me



250
15
H



251
15
Me



252
16
H



253
16
Me



254
17
H



255
17
Me



256
18
H



257
18
Me



258
19
H



259
19
Me



260
20
H



261
20
Me



262
22
H



263
22
Me



264
23
H



265
23
Me



266
24
H



267
24
Me



268
25
H



269
25
Me



270
26
H



271
26
Me



272
27
H



273
27
Me



274
28
H



275
28
Me



276
29
H



277
29
Me



278
30
H



279
30
Me



280
31
H



281
31
Me



282
32
H



283
32
Me



284
33
H



285
33
Me



286
34
H



287
34
Me



288
35
H



289
35
Me



290
36
H



291
36
Me



292
37
H



293
37
Me



294
38
H



295
38
Me



296
39
H



297
39
Me



298
40
H



299
40
Me



300
41
H



301
41
Me



302
42
H



303
42
Me



304
43
H



305
43
Me



306
44
H



307
44
Me



308
45
H



309
45
Me



310
46
H



311
46
Me



312
47
H



313
47
Me



314
48
H



315
48
Me



316
49
H



317
49
Me



318
50
H



319
50
Me



320
51
H



321
51
Me



322
52
H



323
52
Me



324
53
H



325
53
Me



326
54
H



327
54
Me



328
55
H



329
55
Me



330
56
H



331
56
Me

















TABLE 4
























No.
Skeleton
R
m.p.
















332
1
CH2SMe




333
1
Et



334
1
Me



335
2
CH2SMe



336
2
Et



337
2
Me



338
3
CH2SMe



339
3
Et



340
3
Me



341
4
CH2SMe



342
4
Et



343
4
Me



344
5
CH(Me)2



345
5
CH2CF3



346
5
CH2CH2CH2OMe



347
5
CH2CH2CH3
oil



348
5
CH2CH2OEt
oil



349
5
CH2CO2Me



350
5
CH2N(Me)2



351
5
CH2SMe
oil



352
5
CH2SPh



353
5
CHMe2
oil



354
5
cyclohexyl
oil



355
5
cyclopentyl
oil



356
5
Et
oil



357
5
Me
oil



358
6
CH2SMe



359
6
Et



360
6
Me



361
7
CH(Me)2



362
7
CH2CF3



363
7
CH2CH2CH2OMe



364
7
CH2CO2Me



365
7
CH2N(Me)2



366
7
CH2SMe



367
7
CH2SPh



368
7
Et



369
7
Me



370
8
CH(Me)2



371
8
CH2CF3



372
8
CH2CH2CH2OMe



373
8
CH2CH2CH3
oil



374
8
CH2CH2OEt
oil



375
8
CH2CH3
oil



376
8
CH2CO2Me



377
8
CH2N(Me)2



378
8
CH2SMe



379
8
CH2SPh



380
8
CHMe2
oil



381
8
cyclohexyl
oil



382
8
cyclopentyl
oil



383
8
Me



384
9
CH2SMe



385
9
Et



386
9
Me



387
10
CH2SMe



388
10
Et



389
10
Me



390
11
CH2SMe



391
11
Et



392
11
Me



393
12
CH2SMe



394
12
Et



395
12
Me



396
13
CH2SMe



397
13
Et



398
13
Me



399
14
CH2SMe



400
14
Et



401
14
Me



402
15
CH2SMe



403
15
Et



404
15
Me



405
16
CH2SMe



406
16
Et



407
16
Me



408
17
CH2SMe



409
17
Et



410
17
Me



411
18
CH2SMe



412
18
Et



413
18
Me



414
19
CH2SMe



415
19
Et



416
19
Me



417
20
CH2SMe



418
20
Et



419
20
Me



420
21
CH2SMe



421
21
Et



422
21
Me



423
22
CH(Me)2



424
22
CH2CF3



425
22
CH2CH2CH2OMe



426
22
CH2CO2Me



427
22
CH2N(Me)2



428
22
CH2SMe



429
22
CH2SPh



430
22
Et



431
22
Me



432
23
CH2SMe



433
23
Et



434
23
Me



435
24
CH2SMe



436
24
Et



437
24
Me



438
25
CH(Me)2



439
25
CH2CF3



440
25
CH2CH2CH2OMe



441
25
CH2CO2Me



442
25
CH2N(Me)2



443
25
CH2SMe



444
25
CH2SPh



445
25
Et



446
25
Me



447
26
CH(Me)2



448
26
CH2CF3



449
26
CH2CH2CH2OMe



450
26
CH2CO2Me



451
26
CH2N(Me)2



452
26
CH2SMe



453
26
CH2SPh



454
26
Et



455
26
Me



456
27
CH2SMe



457
27
Et



458
27
Me



459
28
CH2SMe



460
28
Et



461
28
Me



462
29
CH2SMe



463
29
Et



464
29
Me



465
30
CH2SMe



466
30
Et



467
30
Me



468
31
CH2SMe



469
31
Et



470
31
Me



471
32
CH2SMe



472
32
Et



473
32
Me



474
33
CH2SMe



475
33
Et



476
33
Me



477
34
CH2SMe



478
34
Et



479
34
Me



480
35
CH(Me)2



481
35
CH2CF3



482
35
CH2CH2CH2OMe



483
35
CH2CO2Me



484
35
CH2N(Me)2



485
35
CH2SMe



486
35
CH2SPh



487
35
Et



488
35
Me



489
36
CH2SMe



490
36
Et



491
36
Me



492
37
CH2SMe



493
37
Et



494
37
Me



495
38
CH(Me)2



496
38
CH2CF3



497
38
CH2CH2CH2OMe



498
38
CH2CO2Me



499
38
CH2N(Me)2



500
38
CH2SMe



501
38
CH2SPh



502
38
Et



503
38
Me



504
39
CH2SMe



505
39
Et



506
39
Me



507
40
CH(Me)2



508
40
CH2CF3



509
40
CH2CH2CH2OMe



510
40
CH2CO2Me



511
40
CH2N(Me)2



512
40
CH2SMe



513
40
CH2SPh



514
40
Et



515
40
Me



516
41
CH2SMe



517
41
Et



518
41
Me



519
42
CH2SMe



520
42
Et



521
42
Me



522
43
CH2SMe



523
43
Et



524
43
Me



525
44
CH2SMe



526
44
Et



527
44
Me



528
45
CH2SMe



529
45
Et



530
45
Me



531
46
CH2SMe



532
46
Et



533
46
Me



534
47
CH2SMe



535
47
Et



536
47
Me



537
48
CH(Me)2



538
48
CH2CF3



539
48
CH2CH2CH2OMe



540
48
CH2CO2Me



541
48
CH2N(Me)2



542
48
CH2SMe



543
48
CH2SPh



544
48
Et



545
48
Me



546
49
CH2SMe



547
49
Et



548
49
Me



549
50
CH2SMe



550
50
Et



551
50
Me



552
51
CH(Me)2



553
51
CH2CF3



554
51
CH2CH2CH2OMe



555
51
CH2CO2Me



556
51
CH2N(Me)2



557
51
CH2SMe



558
51
CH2SPh



559
51
Et



560
51
Me



561
52
CH2SMe



562
52
Et



563
52
Me



564
53
CH2SMe



565
53
Et



566
53
Me



567
54
CH2SMe



568
54
Et



569
54
Me



570
55
CH2SMe



571
55
Et



572
55
Me



573
56
CH2SMe



574
56
Et



575
56
Me

















TABLE 5


























No.
Skeleton
R1
R2
R3
m.p.


















576
1
H
Me
H




577
1
H
Me
Me



578
2
H
CH2CF3
Me



579
2
H
CO2Et
H



580
2
H
CO2Me
H



581
2
H
Et
Me



582
2
H
H
H



583
2
H
Me
H



584
2
H
Me
Me



585
3
H
Me
H



586
3
H
Me
Me



587
4
H
Me
H



588
4
H
Me
Me



589
5
H
Br
Br



590
5
H
CH2CF3
Me



591
5
H
Cl
Cl



592
5
H
CO2Et
H
oil



593
5
H
CO2Me
H
oil



594
5
H
Et
Me



595
5
H
H
H
oil



596
5
H
Me
H
oil



597
5
H
Me
Me



598
5
Me
CF3
H



599
6
H
Me
H



600
6
H
Me
Me



601
7
H
Br
Br



602
7
H
Cl
Cl



603
7
H
Me
H



604
7
H
Me
Me



605
7
Me
CF3
H



606
8
H
Br
Br



607
8
H
C1
Cl



608
8
H
Me
H



609
8
H
Me
Me



610
8
Me
CF3
H



611
9
H
Me
H



612
9
H
Me
Me



613
10
H
Me
H



614
10
H
Me
Me



615
11
H
Me
H



616
11
H
Me
Me



617
12
H
Me
H



618
12
H
Me
Me



619
13
H
Me
H



620
13
H
Me
Me



621
14
H
Me
H



622
14
H
Me
Me



623
15
H
Me
H



624
15
H
Me
Me



625
16
H
Me
H



626
16
H
Me
Me



627
17
H
Me
H



628
17
H
Me
Me



629
18
H
Me
H



630
18
H
Me
Me



631
19
H
Me
H



632
19
H
Me
Me



633
20
H
Me
H



634
20
H
Me
Me



635
21
H
Me
H



636
21
H
Me
Me



637
22
H
Br
Br



638
22
H
Cl
Cl



639
22
H
Me
H



640
22
H
Me
Me



641
22
Me
CF3
H



642
23
H
Me
H



643
23
H
Me
Me



644
24
H
Me
H



645
24
H
Me
Me



646
25
H
Br
Br



647
25
H
Cl
Cl



648
25
H
Me
H



649
25
H
Me
Me



650
25
Me
CF3
H



651
26
H
Br
Br



652
26
H
Cl
Cl



653
26
H
Me
H



654
26
H
Me
Me



655
26
Me
CF3
H



656
27
H
Me
H



657
27
H
Me
Me



658
28
H
Me
H



659
28
H
Me
Me



660
29
H
Me
H



661
29
H
Me
Me



662
30
H
Me
H



663
30
H
Me
Me



664
31
H
Me
H



665
31
H
Me
Me



666
32
H
Me
H



667
32
H
Me
Me



668
33
H
Me
H



669
33
H
Me
Me



670
34
H
Me
H



671
34
H
Me
Me



672
35
H
Br
Br



673
35
H
Cl
Cl



674
35
H
Me
H



675
35
H
Me
Me



676
35
Me
CF3
H



677
36
H
Me
H



678
36
H
Me
Me



679
37
H
Me
H



680
37
H
Me
Me



681
38
H
Br
Br



682
38
H
Cl
Cl



683
38
H
Me
H



684
38
H
Me
Me



685
38
Me
CF3
H



686
39
H
Me
H



687
39
H
Me
Me



688
40
H
Br
Br



689
40
H
Cl
Cl



690
40
H
Me
H



691
40
H
Me
Me



692
40
Me
CF3
H



693
41
H
Me
H



694
41
H
Me
Me



695
42
H
Me
H



696
42
H
Me
Me



697
43
H
Me
H



698
43
H
Me
Me



699
44
H
Me
H



700
44
H
Me
Me



701
45
H
Me
H



702
45
H
Me
Me



703
46
H
Me
H



704
46
H
Me
Me



705
47
H
Me
H



706
47
H
Me
Me



707
48
H
Br
Br



708
48
H
Cl
Cl



709
48
H
Me
H



710
48
H
Me
Me



711
48
Me
CF3
H



712
49
H
Me
H



713
49
H
Me
Me



714
50
H
Me
H



715
50
H
Me
Me



716
51
H
Br
Br



717
51
H
Cl
Cl



718
51
H
Me
H



719
51
H
Me
Me



720
51
Me
CF3
H



721
52
H
Me
H



722
52
H
Me
Me



723
53
H
Me
H



724
53
H
Me
Me



725
54
H
Me
H



726
54
H
Me
Me



727
55
H
Me
H



728
55
H
Me
Me



729
56
H
Me
H



730
56
H
Me
Me



1249 
5
H
CF3
H

















TABLE 6

























No.
Skeleton
R1
R2
R3
R4
m.p.
















731
1
H
H
H
H



732
1
H
H
Me
H


733
1
Me
H
H
H


734
3
H
H
H
H


735
3
H
H
Me
H


736
3
Me
H
H
H


737
5





H
Me
H


738
5
H
H
H
H
oil


739
5
H
H
Me
H
oil


740
5
H
H
3-pyridyl
H


741
5
Me
H
H
H


742
7
H
H
Me
H


743
7
H
H
Me
Me


744
7
Me
H
H
H


745
8





H
Me
H


746
8
H
H
H
H


747
8
H
H
Me
H


748
8
H
H
3-pyridyl
H


749
8
Me
H
H
H


750
14
H
H
H
H


751
14
H
H
Me
H


752
14
Me
H
H
H


753
16
H
H
H
H


754
18
H
H
Me
H


755
22





H
Me
H


756
22
H
H
Me
H


757
22
H
H
Me
Me


758
22
H
H
3-pyridyl
H


759
22
Me
H
H
H


760
25





H
Me
H


761
25
H
H
Me
H


762
25
H
H
Me
Me


763
25
H
H
3-pyridyl
H


764
25
Me
H
H
H


765
26
H
H
Me
H


766
26
H
H
Me
Me


767
26
Me
H
H
H


768
33
Me
H
H
H


769
35





H
Me
H


770
35
H
H
Me
H


771
35
H
H
Me
Me


772
35
H
H
3-pyridyl
H


773
35
Me
H
H
H


774
38





H
Me
H


775
38
H
H
Me
H


776
38
H
H
Me
Me


777
38
H
H
3-pyridyl
H


778
38
Me
H
H
H


779
40
H
H
Me
H


780
40
H
H
Me
Me


781
40
Me
H
H
H


782
48





H
Me
H


783
48
H
H
Me
H


784
48
H
H
Me
Me


785
48
H
H
3-pyridyl
H


786
48
Me
H
H
H


787
51





H
Me
H


788
51
H
H
Me
H


789
51
H
H
Me
Me


790
51
H
H
3-pyridyl
H


791
51
Me
H
H
H
















TABLE 7























No.
Skeleton
R1
R2
m.p.














792
5
H
CF3



793
5
H
CH2CH2OMe


794
5
H
Me
oil


795
5
Me







796
5
Me
cyclopropyl


797
5
Me
Me
105°  C.


798
7
H
CF3


799
7
H
CH2CH2OMe


800
7
H
Me


801
7
Me







802
7
Me
cyclopropyl


803
7
Me
Me


804
8
H
CF3


805
8
H
CH2CH2OMe


806
8
H
Me


807
8
Me







808
8
Me
cyclopropyl


809
8
Me
Me


810
22
H
CF3


811
22
H
CH2CH2OMe


812
22
H
Me


813
22
Me







814
22
Me
cyclopropyl


815
22
Me
Me


816
25
H
CF3


817
25
H
CH2CH2OMe


818
25
H
Me


819
25
Me







820
25
Me
cyclopropyl


821
25
Me
Me


822
26
H
CF3


823
26
H
CH2CH2OMe


824
26
H
Me


825
26
Me







826
26
Me
cyclopropyl


827
26
Me
Me


828
35
H
CF3


829
35
H
CH2CH2OMe


830
35
H
Me


831
35
Me







832
35
Me
cyclopropyl


833
35
Me
Me


834
38
H
CF3


835
38
H
CH2CH2OMe


836
38
H
Me


837
38
Me







838
38
Me
cyclopropyl


839
38
Me
Me


840
40
H
CF3


841
40
H
CH2CH2OMe


842
40
H
Me


843
40
Me







844
40
Me
cyclopropyl


845
40
Me
Me


846
48
H
CF3


847
48
H
CH2CH2OMe


848
48
H
Me


849
48
Me







850
48
Me
cyclopropyl


851
48
Me
Me


852
51
H
CF3


853
51
H
CH2CH2OMe


854
51
H
Me


855
51
Me







856
51
Me
cyclopropyl


857
51
Me
Me
















TABLE 8

























No.
Skeleton
R1
R2
m.p.

















858
1
Me
H




859
2
Me
H



860
3
Me
H



861
4
Me
H



862
5
CF3
H



863
5
CH═CH2
Me



864
5
H
H
oil



865
5
Me
H
oil



866
6
Me
H



867
7
CF3
H



868
7
CH═CH2
Me



869
7
H
H



870
7
Me
H



871
8
CF3
H



872
8
CH═CH2
Me



873
8
H
H



874
8
Me
H



875
9
Me
H



876
10
Me
H



877
11
Me
H



878
12
Me
H



879
13
Me
H



880
14
Me
H



881
15
Me
H



882
16
Me
H



883
17
Me
H



884
18
Me
H



885
19
Me
H



886
20
Me
H



887
21
Me
H



888
22
CF3
H



889
22
CH═CH2
Me



890
22
H
H



891
22
Me
H



892
23
Me
H



893
24
Me
H



894
25
CF3
H



895
25
CH═CH2
Me



896
25
H
H



897
25
Me
H



898
26
CF3
H



899
26
CH═CH2
Me



900
26
H
H



901
26
Me
H



902
27
Me
H



903
28
Me
H



904
29
Me
H



905
30
Me
H



906
31
Me
H



907
32
Me
H



908
33
Me
H



909
34
Me
H



910
35
CF3
H



911
35
CH═CH2
Me



912
35
H
H



913
35
Me
H



914
36
Me
H



915
37
Me
H



916
38
CF3
H



917
38
CH═CH2
Me



918
38
H
H



919
38
Me
H



920
39
Me
H



921
40
CF3
H



922
40
CH═CH2
Me



923
40
H
H



924
40
Me
H



925
41
Me
H



926
42
Me
H



927
43
Me
H



928
44
Me
H



929
45
Me
H



930
46
Me
H



931
47
Me
H



932
48
CF3
H



933
48
CH═CH2
Me



934
48
H
H



935
48
Me
H



936
49
Me
H



937
50
Me
H



938
51
CF3
H



939
51
CH═CH2
Me



940
51
H
H



941
51
Me
H



942
52
Me
H



943
53
Me
H



944
54
Me
H



945
55
Me
H



946
56
Me
H

















TABLE 9
























No.
Skeleton
R1
R2
R3
m.p.















947
5





Me
Me


948
5
CH(Me)2
H
Me


949
5
H
H
H
oil


950
5
Me
H
H
oil


951
7





Me
Me


952
7
CH(Me)2
H
Me


953
7
H
H
H


954
7
Me
H
H


955
8





Me
Me


956
8
CH(Me)2
H
Me


957
8
H
H
H


958
8
Me
H
H


959
22





Me
Me


960
22
CH(Me)2
H
Me


961
22
H
H
H


962
22
Me
H
H


963
25





Me
Me


964
25
CH(Me)2
H
Me


965
25
H
H
H


966
25
Me
H
H


967
26





Me
Me


968
26
CH(Me)2
H
Me


969
26
H
H
H


970
26
Me
H
H


971
35





Me
Me


972
35
CH(Me)2
H
Me


973
35
H
H
H


974
35
Me
H
H


975
38





Me
Me


976
38
CH(Me)2
H
Me


977
38
H
H
H


978
38
Me
H
H


979
40





Me
Me


980
40
CH(Me)2
H
Me


981
40
H
H
H


982
40
Me
H
H


983
48





Me
Me


984
48
CH(Me)2
H
Me


985
48
H
H
H


986
48
Me
H
H


987
51





Me
Me


988
51
CH(Me)2
H
Me


989
51
H
H
H


990
51
Me
H
H
















TABLE 10

























No.
Skeleton
R1
R2
m.p.















991
1
H
C(═O)NMe2



992
1
H
C(═O)OMe


993
2
H
C(═O)NMe2


994
2
H
C(═O)OMe


995
3
H
C(═O)NMe2


996
3
H
C(═O)OMe


997
4
H
C(═O)NMe2


998
4
H
C(═O)OMe


999
5
H
C(═O)Me


1000
5
H
C(═O)NMe2
111° C.


1001
5
H
C(═O)OMe
oil


1002
5
Me
C(═O)H


1003
6
H
C(═O)NMe2


1004
6
H
C(═O)OMe


1005
7
H
C(═O)Me


1006
7
H
C(═O)NMe2


1007
7
H
C(═O)OMe


1008
7
Me
C(═O)Et


1009
8
H
C(═O)Me


1010
8
H
C(═O)NMe2


1011
8
H
C(═O)OMe


1012
8
Me
C(═O)Me


1013
9
H
C(═O)NMe2


1014
9
H
C(═O)OMe


1015
10
H
C(═O)NMe2


1016
10
H
C(═O)OMe


1017
11
H
C(═O)NMe2


1018
11
H
C(═O)OMe


1019
12
H
C(═O)NMe2


1020
12
H
C(═O)OMe


1021
13
H
C(═O)NMe2


1022
13
H
C(═O)OMe


1023
14
H
C(═O)NMe2


1024
14
H
C(═O)OMe


1025
15
H
C(═O)NMe2


1026
15
H
C(═O)OMe


1027
16
H
C(═O)NMe2


1028
16
H
C(═O)OMe


1029
17
H
C(═O)NMe2


1030
17
H
C(═O)OMe


1031
18
H
C(═O)NMe2


1032
18
H
C(═O)OMe


1033
19
H
C(═O)NMe2


1034
19
H
C(═O)OMe


1035
20
H
C(═O)NMe2


1036
20
H
C(═O)OMe


1037
21
H
C(═O)NMe2


1038
21
H
C(═O)OMe


1039
22
H
C(═O)Et


1040
22
H
C(═O)NMe2


1041
22
H
C(═O)OMe


1042
22
Me
C(═O)CH2CH2CH3


1043
23
H
C(═O)NMe2


1044
23
H
C(═O)OMe


1045
24
H
C(═O)NMe2


1046
24
H
C(═O)OMe


1047
25
Et
C(═O)F3


1048
25
H
C(═O)Me


1049
25
H
C(═O)NMe2


1050
25
H
C(═O)OMe


1051
26
Et
C(═O)CF3


1052
26
H
C(═O)Et


1053
26
H
C(═O)NMe2


1054
26
H
C(═O)OMe


1055
27
H
C(═O)NMe2


1056
27
H
C(═O)OMe


1057
28
H
C(═O)NMe2


1058
28
H
C(═O)OMe


1059
29
H
C(═O)NMe2


1060
29
H
C(═O)OMe


1061
30
H
C(═O)NMe2


1062
30
H
C(═O)OMe


1063
31
H
C(═O)NMe2


1064
31
H
C(═O)OMe


1065
32
H
C(═O)NMe2


1066
32
H
C(═O)OMe


1067
33
H
C(═O)NMe2


1068
33
H
C(═O)OMe


1069
34
H
C(═O)NMe2


1070
34
H
C(═O)OMe


1071
35
Et
C(═O)CF3


1072
35
H
C(═O)Me


1073
35
H
C(═O)NMe2


1074
35
H
C(═O)OMe


1075
36
H
C(═O)NMe2


1076
36
H
C(═O)OMe


1077
37
H
C(═O)NMe2


1078
37
H
C(═O)OMe


1079
38
Et
C(═O)CF3


1080
38
H
C(═O)Me


1081
38
H
C(═O)NMe2


1082
38
H
C(═O)OMe


1083
39
H
C(═O)NMe2


1084
39
H
C(═O)OMe


1085
40
Et
C(═O)CF3


1086
40
H
C(═O)CH(Me2)


1087
40
H
C(═O)NMe2


1088
40
H
C(═O)OMe


1089
41
H
C(═O)NMe2


1090
41
H
C(═O)OMe


1091
42
H
C(═O)NMe2


1092
42
H
C(═O)OMe


1093
43
H
C(═O)NMe2


1094
43
H
C(═O)OMe


1095
44
H
C(═O)NMe2


1096
44
H
C(═O)OMe


1097
45
H
C(═O)NMe2


1098
45
H
C(═O)OMe


1099
46
H
C(═O)NMe2


1100
46
H
C(═O)OMe


1101
47
H
C(═O)NMe2


1102
47
H
C(═O)OMe


1103
48
Et
C(═O)CF3


1104
48
H
C(═O)Me


1105
48
H
C(═O)NMe2


1106
48
H
C(═O)OMe


1107
49
H
C(═O)NMe2


1108
49
H
C(═O)OMe


1109
50
H
C(═O)NMe2


1110
50
H
C(═O)OMe


1111
51
Et
C(═O)CF3


1112
51
H
C(═O)Me


1113
51
H
C(═O)NMe2


1114
51
H
C(═O)OMe


1115
52
H
C(═O)NMe2


1116
52
H
C(═O)OMe


1117
53
H
C(═O)NMe2


1118
53
H
C(═O)OMe


1119
54
H
C(═O)NMe2


1120
54
H
C(═O)OMe


1121
55
H
C(═O)NMe2


1122
55
H
C(═O)OMe


1123
56
H
C(═O)NMe2


1124
56
H
C(═O)OMe
















TABLE 11
























No.
Skeleton
X
R1
R2
m.p.















1125
5
NMe
Me
Me


1126
5
O
H
Me
oil


1127
5
O
H
H
oil


1128
5
O
H
Et
oil


1129
5
O
C(═O)Me
H
oil











1130
5
O
—CH2CH(OMe)CH2O—
oil


1131
5
O
—CH(Me)CH(Me)O—
oil


1132
5
O
—CH(Et)CH2O—
oil


1133
5
O
—CH(CH2SEt)CH2O—
oil


1134
5
O
—CH2CH2O—


1135
5
S
—CH2CH2CH2S—
oil


1136
7
O
—CH2CH(OMe)CH2O—












1137
7
O
H
Me


1138
7
O
H
Et











1139
7
O
—CH(Me)CH(Me)O—


1140
7
O
—CH(Et)CH2O—


1141
7
S
—CH2CH2CH2S—












1142
8
NMe
Me
Me


1143
8
O
H
Me
oil











1144
8
O
—CH2CH(OMe)CH2O—












1145
8
O
H
Me


1146
8
O
H
Et


1147
8
O
H
H


1148
8
O
C(═O)Me
H











1149
8
O
—CH2CH2O—


1150
8
O
—CH(Me)CH(Me)O—


1151
8
O
—CH(Et)CH2O—


1152
8
S
—CH2CH2CH2S—


1153
22
O
—CH2CH(OMe)CH2O—












1154
22
O
H
Me


1155
22
O
H
Et











1156
22
O
—CH(Me)CH(Me)O—


1157
22
O
—CH(Et)CH2O—


1158
22
S
—CH2CH2CH2S-


1159
25
O
—CH2CH(OMe)CH2O—












1160
25
O
H
Me


1161
25
O
H
Et











1162
25
O
—CH(Me)CH(Me)O—


1163
25
O
—CH(Et)CH2O—


1164
25
S
—CH2CH2CH2S—


1165
26
O
—CH2CH(OMe)CH2O—












1166
26
O
H
Me


1167
26
O
H
Et











1168
26
O
—CH(Me)CH(Me)O—


1169
26
O
—CH(Et)CH2O—


1170
26
S
—CH2CH2CH2S—












1171
35
NMe
Me
Me











1172
35
O
—CH2CH(OMe)CH2O—












1173
35
O
H
Me


1174
35
O
H
Et


1175
35
O
H
H


1176
35
O
C(═O)Me
H











1177
35
O
—CH2CH2O—


1178
35
O
—CH(Me)CH(Me)O—


1179
35
O
—CH(Et)CH2O—


1180
35
S
—CH2CH2CH2S—












1181
38
NMe
Me
Me











1182
38
O
—CH2CH(OMe)CH2—












1183
38
O
H
Me


1184
38
O
H
Et


1185
38
O
H
H


1186
38
O
C(═O)Me
H











1187
38
O
—CH2CH2O—


1188
38
O
—CH(Me)CH(Me)O—


1189
38
O
—CH(Et)CH2O—


1190
38
S
—CH2CH2CH2S—


1191
40
O
—CH2CH(OMe)CH2O—












1192
40
O
H
Me


1193
40
O
H
Et











1194
40
O
—CH(Me)CH(Me)O—


1195
40
O
—CH(Et)CH2O—


1196
40
S
—CH2CH2CH2S—


1197
48
O
—CH2CH(0Me)CH2O—












1198
48
O
H
Me


1199
48
O
H
Et











1200
48
O
—CH(Me)CH(Me)O—


1201
48
O
—CH(Et)CH2O—


1202
48
S
—CH2CH2CH2S—


1203
51
O
—CH2CH(OMe)CH2O—












1204
51
O
H
Me


1205
51
O
H
Et











1206
51
O
—CH(Me)CH(Me)O—


1207
51
O
—CH(Et)CH2O—


1208
51
S
—CH2CH2CH2S—


1209
5
O
CO(2,4,6-Cl3—Ph)
H


1210
5
O
CO(3-CF3—Ph)
H


1211
5
O
CO(2-OCF3—Ph)
H


1212
5
O
CO(2-F-4-Cl—Ph)
H


1213
5
O
CO(2,6-F2—Ph)
H


1214
5
O
CO(2,6-Cl2—Ph)
H


1215
5
O
CO(2,6-Cl2-4-CF3—Ph)
H


1216
5
O
CO(2,3-Cl2—Ph)
H


1217
5
O
CO(3-CF3-5-NO2Ph)
H


1218
5
S
CH2CF3
H


1219
5
O
4-OCF3—Ph
H


1220
5
O
3-(OCF2CF2H)—Ph
H


1221
5
O
4-F—Ph
H


1222
5
O
3-CF3—Ph
H


1223
5
O
3-F—Ph
H


1224
5
O
OCH2CF3
H


1225
5
S
4-CF3—Ph
H


1226
5
S
4-F—Ph
H


1227
5
S
Ph
H


1228
5
O
SO2Me
H


1229
5
SO
CH2CF3
H


1230
5
SO2
CH2CF3
H


1231
5
O
CH2CHCCl2
H


1232
5
O
C2H4O(4-CF3Py-2-yl)
H


1233
5
SO
C2H4O(4-CF3Py-2-yI)
H


1234
5
SO2
C2H4O(4-CF3Py-2-yl)
H


1235
5
S
C2H4O(4-CF3Py-2-yI)
H









B. FORMULATION EXAMPLES


    a) A dust is obtained by mixing 10 parts by weight of active substance and 90 parts by weight of talc as inert material and comminuting the mixture in a hammer mill.
    b) A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of active substance, 65 parts by weight of kaolin-containing quartz as inert material, 10 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyltaurinate as wetter and dispersant and grinding the mixture in a pinned-disk mill.
    c) A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active substance with 7 parts by weight of a sulfosuccinic monoester, 2 parts by weight of a sodium lignosulfonate and 51 parts by weight of water and grinding the mixture in a ball mill to a fineness of below 5 microns.
    d) An emulsifiable concentrate can be prepared from 15 parts by weight of active substance, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier.
    e) Granules can be prepared from 2 to 15 parts by weight of active substance and an inert granule carrier material such as attapulgite, pumice granules and/or quartz sand. It is expedient to use a suspension of the wettable powder of Example b) with a solids content of 30%, which is sprayed onto the surface of attapulgite granules, and these are dried and mixed intimately. The wettable powder amounts to approx. 5% by weight and the inert carrier material to approx. 95% by weight of the finished granules.


C. BIOLOGICAL EXAMPLES
In Examples A to L below, compounds are considered to be active when, at a concentration of 500 ppm or less, their action on the harmful organisms is 50% or more.
Example A
Cut stems of bean plants (Phaseolus vulgaris) carrying one leaf were transferred into brown glass bottles filled with tap water and subsequently populated with approximately 100 spider mites (Tetranychus urticae). The plant leaf and the spider mites were then dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined. After the solution had run off, plants and animals were stored in a climatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 6 days of storage, the effect of the preparation on all stages of the spider mites was determined. The following examples were active: Nos. 43, 45, 97, 1132.
Example B
Germinated field bean seeds (Vicia faba) with radicles were transferred into brown glass bottles filled with tap water and subsequently populated with approximately 100 black bean aphids (Aphis fabae). Plants and aphids were then dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined. After the solution had run off, plants and animals were stored in an acclimatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 3 and 6 days of storage, the effect of the preparation on the aphids (mortality) was determined. The following examples were active: Nos. 33, 36, 357, 1126.
Example C
A Petri dish whose bottom was covered with filter paper and which contained about 5 ml of culture medium was prepared. Pieces of filter paper with about 30, one-day-old eggs of the American tobacco budworm (Heliothis virescens) were dipped for 5 seconds into an aqueous solution of the formulated preparation to be examined and subsequently placed in a Petri dish. A further 200 μl of the aqueous solution were spread over the culture medium. The Petri dish was closed and then stored at about 25° C. in a climatized chamber. After 6 days of storage, the effect of the preparation on the eggs and any larvae which may have hatched from these (mortality) was determined. The following examples were active: Nos. 6, 27, 28, 29, 31, 35, 39, 43, 45, 59, 97, 226, 227, 228, 229, 351, 356, 357, 592, 593, 595, 949, 1001, 1126, 1129, 1132.
Example D
A Petri dish whose bottom was covered with filter paper and which contained about 5 ml of culture medium was prepared. Five L2 larvae of the Egyptian cotton leaf worm (Spodoptera littoralis) were counted into small beakers. 200 μl of an aqueous solution of the formulated preparation to be examined were pipetted into the beaker. The treated larvae were then poured into the Petri dish, and a further 200 μl of the aqueous solution were distributed over the culture medium. The Petri dish was closed and then stored at about 25° C. in a climatized chamber. After 6 days of storage, the effect of the preparation on the larvae (mortality) was determined. The following examples were active: Nos. 27, 28, 29, 39, 43, 45, 59.
Example E
A Petri dish, half of whose bottom was covered with filter paper and which contained a germinated maize corn on a moist cotton pad, was prepared. About 50, 4-5 day-old eggs of the corn rootworm (Diabrotica undecimpunctata) were transferred onto the filter paper. Three drops of 200 μl of an aqueous solution of the formulated preparation to be examined were pipetted onto the eggs, and the rest was pipetted onto the maize corn. The Petri dish was closed and then stored at about 25° C. in a climatized chamber. After 6 days of storage, the effect of the preparation on the eggs and any larvae which may have hatched from these (mortality) was determined. The following examples were active: No. 7.
Example F
Part A of the examination (contact action): in a glass vessel, an aqueous solution of the formulated preparation to be examined was added to about 5000 freshly hatched active (mobile) larvae (2nd development stage) of the root gall nematode (Meloidogyne incognita) (final volume 20 ml). After 6 days of permanent exposure of the nematode larvae, the percentage of the individual larvae immobilized by the action of the preparation was determined in comparison to the untreated controls (nematicidal contact action in percent).
Part B of the examination (soil drench action): to this end, the entire solution from part A of the examination (active compound and pre-treated nematode larvae) was poured into a pot, filled with 60 ml of soil, into which three 9-day-old cucumber plants (Cucumis sativus) had been planted. This drench application reduced the active compound content based on the soil volume to one third of the active compound content in part A of the examination. After 2 weeks in a greenhouse at about 26° C. (watering: twice a day), the root balls of the cucumber plants were carefully washed out of the soil mixture contaminated with nematodes. The number of root galls per plant was counted and compared to the infection of untreated control plants. The reduction of the infection in percent as a criterion for the assessment of the activity was calculated using Abbott's formula (nematicidal soil drench action). The following examples were active: Nos. 6, 7, 29, 32, 34, 44, 356.
Example G
Germinated field bean seeds (Vicia faba) with radicles were transferred into brown glass bottles filled with tap water. Four milliliters of an aqueous solution of the formulated preparation to be examined were pipetted into the brown glass bottle. The field bean was then heavily infested with approximately 100 black bean aphids (Aphis fabae). Plants and animals were then stored in a climatized chamber (16 hours of light/day, 25° C., 40-60% relative atmospheric humidity). After 3 and 6 days of storage, the root-systemic effect of the preparation on the aphids (mortality) was determined. The following examples were active: No. 1126.
Example H
A Petri dish whose bottom was covered with filter paper and which contained about 5 ml of culture medium was prepared. Five L2 larvae of the sugar beet armyworm (Spodoptera exigua) were counted into a small beaker. 200 μl of an aqueous solution of the formulated preparation to be examined were pipetted into the beaker. The treated larvae were then poured into the Petri dish and a further 200 μl of the aqueous solution were distributed over the culture medium. The Petri dish was closed and then stored at 25° C. in a climatized chamber. After 6 days of storage, the effect of the preparation on the larvae (mortality) was determined. The following examples were active: Nos. 31, 97, 226, 227, 228, 229, 351, 356, 357, 592, 593, 595, 949, 1001, 1126, 1129, 1132.
Example I
Cotton plants were sprayed with an aqueous solution of the formulated preparation to be examined. After drying, leaves were cut off, placed into a Petri dish and populated with 5 L2 larvae of the sugar beet armyworm (Spodoptera exigua). After 4 days of storage at about 23° C., the effect of the preparation on the larvae (mortality) was determined. The following examples were active: Nos. 27, 28, 45, 59.
Example J
Culture medium was mixed with an aqueous solution of the formulated preparation to be examined and populated with 10 L1 larvae of the codling moth (Carpocapsa pomonella). After 14 days of storage at about 23° C., the effect of the preparation on the larvae (mortality) was determined. The following examples were active: Nos. 28, 59.
Example K
Cotton leaves were placed into a Petri dish, populated with in each case 5 L1, L2, L3 and L4 larvae of the American tobacco budworm (Heliothis virescens) and sprayed with an aqueous solution of the formulated preparation to be examined. After 4 days of storage at about 25° C., the effect of the preparation on the larvae (mortality) was determined. The following examples were active: No. 27
Example L
A cabbage leaf was sprayed with an aqueous solution of the formulated preparation to be examined. After drying, the treated leaf was populated with larvae of the diamondback moth (Plutella xylostella). After 4 days of storage at about 25° C., the effect of the preparation on the larvae (mortality) was determined. The following examples were active: Nos. 27, 28, 45.

## Claims

1. A compound of the formula (I) 




or a salt thereof, in which
R1 and R2 independently of one another are halogen, 
Y is —O—, —S— or —NH—, 
X is —O—, —S(O)r— or —NR5—, where r=0, 1 or 2 and R5 is hydrogen or C1-C8-alkyl, 
X′ is a direct bond, —O—, —S(O)r— or —NR5—, where r and R5 are as defined above, 
R3 is hydrogen, halogen, nitro, cyano, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy or C3-C10-cycloalkyl, 
A is one of the groups —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, or —C(=Z)-O—N═C(NH2)—R6, 
Z is O, S, N—R33, N—O—R33 or N—NR33R34, 
R6, R7, and R8, R33 and R34 independently of one another are hydrogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl or heteroaryl having one to three ring heteroatoms which for their part may be substituted by halogen, hydroxyl, cyano, nitro, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl, halogen-substituted C6-C14-aryl, heteroaryl having one to three ring heteroatoms or halogen-substituted heteroaryl having one to three ring heteroatoms, amino, N—(C1-C8-alkyl)amino, N,N-bis-(C1-C8-alkyl)amino, tri-(C1-C8-alkyl)silyl, aryl-(C1-C8)-dialkylsilyl, diaryl-(C1-C8)-alkylsilyl, triarylsilyl, C1-C8-alkoxy and/or C1-C8-haloalkoxy, 
B is a divalent bridge and is alkylene having one to twelve carbon atoms, cycloalkylene having three to fourteen carbon atoms, alkylene-cycloalkylene having four to twenty-six carbon atoms, alkylene-cycloalkylene-alkylene having five to thirty-eight carbon atoms, where these bridges may have one to three ethylenically unsaturated bonds and/or may be interrupted by —O—, —S—, —C(═O)O— or —NR5— groups, where R5 is as defined above and where the bridge may be unsubstituted or substituted by one to ten substituents selected from the group consisting of C1-C3-alkyl, trifluoromethyl and trichloromethyl, and 
R4 is a monovalent C6-C14-aryl radical or nitrogen-containing heteroaryl radical having at least one ring heteroatom which is unsubstituted or substituted by one to four radicals selected from the group consisting of halogen, cyano, nitro, thiocyanato, isocyanato, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, C6-C14-aryl, nitrogen-containing heteroaryl having one to three ring heteroatoms, where these substituents for their part may be substituted by radicals selected from the group consisting of halogen, cyano, nitro, C1-C8-alkyl, C1-C8-haloalkyl, C1-C8-alkoxy, C1-C8-haloalkoxy, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —C(=Z)-O—N═C(NH2)—R6, —O—C(=Z)-R6, —O—C(=Z)-OR6, —O—C(=Z)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)-OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=Z)-SR6, —NR9—C(=Z)-NR7R8, —OR6, —SR6, —S(═O)R6, —S(═O)2R6, —NR7R8, where Z, R6, R7, and R8 are as defined above and R9 is independently any group defined above for R6.

2. A compound of the formula (I) as claimed in claim 1 wherein R1 and R2 are each chlorine or bromine.

3. A compound of the formula (I) as claimed in claim 1 wherein Y is —O—.

4. A compound of the formula (I) as claimed in claim 1 wherein R1 and R2 are each chlorine and Y is —O—.

5. A compound of the formula (I) as claimed in claim 1 wherein X is —O—, —S— or —NH— and X′ is a direct bond, —O—, —S— or —NH—.

6. A compound of the formula (I) as claimed in claim 5 wherein X and X′ are each —O— or X is —O— and X′ is a direct bond.

7. A compound of the formula (I) as claimed in claim 1 wherein R3 is hydrogen, fluorine, chlorine, bromine, methyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, methoxy, trifluoromethoxy, monochloromethoxy, dichloromethoxy, trichloromethoxy, nitro, cyano, or cyclohexyl.

8. A compound of the formula (I) as claimed in claim 1 wherein R3 is methyl, trifluoromethyl, cyano, chlorine or bromine.

9. A compound of the formula (I) as claimed in claim 1 wherein Z is O, N—OH, N—OCH3 or N—CH2—CH═CH2.

10. A compound of the formula (I) as claimed in claim 1 wherein A is a group of the formula —C(═O)—CH3, —C(═N—OCH3)—CH3, —C(═N—OH)—CH3, —C(═O)—OCH3, —C(═O)—CH═CH—N(CH3)2, —C(═O)—NH—C2H5, —C(═O)—NH2, —C(═O)—N(CH3)2, —C(═O)—NH—CH2—CH2—OH, —C(═O)—NH—CH(CH3)—CH2—OH, —C(═O)—CHBr2, —C(═O)—N(CH3)—O—CH3, —C(═N—O—CH2—CH═CH2)—CH3, —C(═S)—NH2, —C(═O)—O—C6H5, —C(═O)—O—C3H7, —C(═O)-imidazolyl, —C(═O)-3-ethyl-1,2,4-oxadiazol-5-yl, —C(═O)-2-Δ-oxazolin-2-yl, —C(═O)-1-methylpyrazol-3-yl, —C(═O)-ethyn-2-yl, —C(═O)-1-hydroxyethyn-2-yl, —C(═O)-1-trimethylsilylethyn-2-yl, —C(═O)-1-hexylethyn-2-yl, —C(═O)-1-(2-chlorophenyl)ethyn-2-yl, —C(═O)-1-methoxyethyn-2-yl or —C(═O)-ethen-2-yl.

11. A compound of the formula (I) as claimed in claim 1 wherein A is —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, or —C(=Z)-NR7R8, where Z, R6, R7, and R8 are as defined in claim 1.

12. A compound of the formula (I) as claimed in claim 1 wherein B is a group of the formulae P1 to P6




in which R32 in each case independently of the others is hydrogen, C1-C3-alkyl or trifluoromethyl,
Y′ in each case independently of the others is a direct C—C bond, —O—, —S— or —NH—, 
i is an integer from 1 to 6, 
j is an integer from 1 to 6, 
k is an integer from 0 to 2, 
l is an integer from 0 to 2, 
m is an integer from 0 to 2, 
o is an integer from 0 to 1 and 
p is an integer from 0 to 1.

13. A compound of the formula (I) as claimed in claim 1 wherein B is a group of the formula —CqH2q- and q is an integer from 2 to 4.

14. A compound of the formula (I) as claimed in claim 1 wherein R4 is C6-C14-aryl which is unsubstituted or substituted by one to three radicals selected from the group consisting of halogen, cyano, nitro, thiocyanato, isocyanato, C1-C6-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C4-C8-cycloalkenyl and C2-C8-alkynyl, where one or more hydrogen atoms of the C1-C6-alkyl, C3-C8-cycloalkyl, C2-C8-alkenyl, C4-C8-cycloalkenyl and/or C2-C8-alkynyl radicals may be substituted by halogen and/or cyano.

15. A compound of the formula (I) as claimed in claim 1 wherein R4 is selected from the group consisting of phenyl, pyridyl, pyrimidyl, pyrazynyl, pyrazolyl and naphthyl which are unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, cyano, nitro, C1-C3-alkyl, C1-C3-haloalkyl, C1-C3-alkoxy, C1-C3-haloalkoxy, —C(=Z)-R6, —C(=Z)-OR6, —C(=Z)-SR6, —C(=Z)-NR7R8, —O—C(=Z)-R6, —O—C(=Z)-OR6, —O—C(=Z)-SR6, —O—C(=Z)-NR7R8, —S—C(=Z)-R6, —S—C(=Z)OR6, —S—C(=Z)-SR6, —S—C(=Z)-NR7R8, —NR9—C(=Z)-R6, —NR9—C(=Z)-OR6, —NR9—C(=Z)-SR6, —NR9—C(=Z)-NR7R8, —OR6, —SR6, —S(═O)R6 and —S(═O)2R6, where Z, R6, R7, R8 and R9 are as defined in claim 1.

16. A compound of the formula (I) as claimed in claim 1 wherein R4 is phenyl or pyridyl which carries one to three substituents from the group consisting of halogen, cyano, nitro, C1-C3-alkyl and C1-C3-haloalkyl or of combinations of these substituents.

17. A compound of the formula (I) as claimed in claim 1 wherein R4 is trifluoromethylphenyl, chlorophenyl, nitrophenyl, nitropyridyl, trifluoromethylpyridyl, di(trifluoromethyl)pyridyl, chloropyridyl, dichloropyridyl, chlorotrifluoromethylpyridyl, trifluoromethylpyrimidyl, di(trifluoromethyl)pyrimidyl, methyltrifluoromethylpyrimidyl or trifluoromethylpyrazolyl.

18. A process for preparing compounds of the formula (I) as claimed in claim 1, which process comprises the following steps: 



a) reacting the compounds of the formulae II and III to give the compound of the formula IV and 
b) reacting the compounds of the formulae IV and V to give the compound of the formula I, 

where R1, R2, R3, R4, A, Y, X and X′ are as defined in claim 1 and Q and Q′ are leaving groups.

19. A composition having insecticidal, acaricidal, ixodicidal, nematicidal, molluscicidal and/or fungicidal action, which comprises a pesticidally effective amount of one or more compounds of the formula (I) or salts thereof as claimed in claim 1 and one or more formulation auxiliaries therefor.

20. A composition as claimed in claim 19 comprising a mixture of carriers and/or surfactants.

21. A method for controlling animal pests comprising the step of directly or indirectly applying to the pest a pesticidally effective amount of a compound of the formula (I) or a salt thereof as claimed in claim 1.

22. A method for controlling harmful organisms in transgenic crop plants comprising the step of directly or indirectly applying to the pest a pesticidally effective amount of a compound of the formula (I) as claimed in claim 1.

23. A veterinary medicament comprising a pesticidally effective amount of a compound of the formula (I) as claimed in claim 1 and one or more veterinarily acceptable formulation auxiliaries therefor.

24. A medicament against endo- and ectoparasites comprising an endo- or ectoparasiticidally effective amount of a compound of the formula (I) as claimed in claim 1 and one or more veterinarily acceptable formulation auxiliaries therefor.

25. A compound as claimed in claim 1, having the formula: 













wherein A is as defined in claim 1.

26. A compound as claimed in claim 1, having the formula: 







wherein A is as defined in claim 1.

27. A compound as claimed in claim 1, having the formula: 







wherein A is as defined in claim 1.

28. A compound as claimed in claim 1, wherein A is


—C(═X′′)R 


wherein
X′′ is O and R is 




X′′ is O and R is 




X′′ is O and R is 




X′′ is O and R is 




X′′ is O and R is 




X′′ is O and R is 




X′′ is O and R is 1-imidazolyl; 
X′′ is O and R is CH═CH—NMe2; 
X′′ is O and R is CH2CF3; 
X′′ is O and R is CH2CH2CH3; 
X′′ is O and R is CHBr2; 
X′′ is O and R is Et; 
X′′ is O and R is H; 
X′′ is O and R is Me; 
X′′ is N—OH and R is Me; 
X′′ is N—OMe and R is Me; 
X′′ is O and R is NH2; 
X′′ is S and R is NH2; 
X′′ is O and R is NHCH(Me)CH2OH; 
X′′ is O and R is NHCH2CH2OH; 
X′′ is O and R is NHEt; 
X′′ is O and R is NHMe-OMe; 
X′′ is O and R is NMe2; 
X′′ is O and R is O—CH(Me)2; 
X′′ is O and R is O—CH2CH2CH3; 
X′′ is O and R is OMe; or 
X′′ is O and R is O-phenyl.

29. A compound as claimed in claim 28, wherein X′′ is O and R is Me, X′′ is N—OH and R is Me, X′′ is N—OMe and R is Me or X′′ is O and R is O-Me.

30. The compound having the formula:

31. The compound according to claim 30, having the formula:

32. The compound according to claim 31, having the formula:

33. The compound according to claim 32, which has the formula:

34. A compound as claimed in claim 1, wherein R6, R7, and R8, independently of one another are hydrogen, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl, C4-C10-cycloalkynyl, phenyl, imidazolyl, oxadiazolyl, Δ2-oxazolinyl or pyrazolyl, wherein each of phenyl, imidazolyl, oxadiazolyl, Δ2-oxazolinyl and pyrazolyl is optionally substituted by halogen, hydroxyl, cyano, nitro, C1-C8-alkyl, C2-C8-alkenyl, C2-C8-alkynyl, C3-C10-cycloalkyl, C4-C10-cycloalkenyl or C4-C10-cycloalkynyl.

35. A compound as claimed in claim 13, wherein B is —(CH2)2—, —(CH2)3— or —(CH2)4—.