# Patent

## Title
Substituted propargylamines

## Abstract

The present invention relates to the use of substituted aryl- and heteroarylpropargylamines of the formula (I)




where

    a) R1 is heteroaryl or aryl, unsubstituted or mono- or polysubstituted by identical or different radicals,
    b) A is a group CR4R5 or C═O, where
    
        R4 is hydrogen, halogen or alkyl;
        R5 is hydrogen, halogen or a substituted or unsubstituted hydrocarbon radical;
    
    
    c) R2 and R3 together with the nitrogen atom to which they are attached form N-heteroaryl or N-heterocyclyl, unsubstituted or mono- or polysubstituted by identical or different radicals,

if appropriate also as N-oxide or salt, as pesticide against arthropods and helminths for protecting plants and animals.

## Background
This application claims priority under 35 U.S.C. §§ 119 and/or 365 to Patent Application No. 101 41 339.4 filed in Germany on Aug. 23, 2001 and Patent Application No. 102 17 697.3 filed in Germany on Apr. 20, 2002; the entire contents of which are hereby incorporated by reference.
The invention relates to the use of substituted aryl- and heteroarylpropargylamines as pesticides, in particular against harmful arthropods and helminths.
In EP-A-0 041 324, 1-[3-(3,5-bistrifluoromethylphenyl)-2-propynyl]-4-tert-butylpiperidine is described as rodenticide. Similar compounds in which the tertiary butyl radical is substituted are described in DE-A-3 504 412. Further compounds of this type in which the butyl radical is replaced by other alkyl radicals are described in 1987 BCPC mono. No. 37 Stored Products Pest Control, p. 125. In addition, there are further publications in which compounds are mentioned in which aryl radicals are attached via propargyl to nitrogen-containing heterocycles.
Surprisingly, it has now been found that compounds of this type have insecticidal, acaricidal and helminticidal action. Some of the compounds are novel.
The invention provides a method for controlling harmful arthropods, such as insects and Acarina, and helminths, such as parasites of animals and plant-damaging nematodes, which comprises applying to these pests or to the plants or animals, areas or substrates infected by them an effective amount of a compound of the formula (I)




where

    a) R1 is heteroaryl or aryl, unsubstituted or mono- or polysubstituted by identical or different radicals,
    b) A is a group CR4R5 or C═O, where
    
        R4 is hydrogen, halogen or alkyl;
        R5 is hydrogen, halogen or a substituted or unsubstituted hydrocarbon radical;
    
    
    c) R2 and R3 together with the nitrogen atom to which they are attached form N-heteroaryl or N-heterocyclyl, unsubstituted or mono- or polysubstituted by identical or different radicals,

if appropriate also as N-oxide and/or salt.



The invention also provides the use of compounds of the formula (I) for controlling arthropods, such as insects and Acarina, and helminths, such as parasites of animals and plant-damaging nematodes.
Many of the compounds of the formula (I) are novel, and the invention embraces all novel compounds of the formula (I), in particular those in which

    a) R1 is heteroaryl which is unsubstituted or mono- or polysubstituted by identical or different radicals or is aryl which is mono- or polysubstituted by identical or different radicals,
    b) A is as defined above;
    c) R2 and R3 together with the nitrogen atom to which they are attached form a piperidine which is unsubstituted or mono- or polysubstituted by identical or different radicals,

with the proviso that, if R2 and R3 together with the nitrogen atom to which they are attached form a piperidine radical which is unsubstituted or substituted in the 4-position by unsubstituted or substituted alkyl, R1 is not 3,5-bistrifluoromethylphenyl.



In the above formula, a hydrocarbon radical is a straight-chain, branched or cyclic saturated, partially saturated, unsaturated or aromatic organic radical having preferably 1 to 20 carbon atoms, for example alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, aryl or benzyl. This definition also applies to composite terms, such as cycloalkylalkenyl, cycloalkynylalkyl and arylalkynyl. If a hydrocarbon radical contains additional heteroatoms, these can in principle, i.e. the chemical structure permitting, be located in any position of the hydrocarbon radical.
In formula (I) and all subsequent formulae, carbon-containing radicals in the form of a chain, such as alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino and alkylthio, and the corresponding radicals which are unsaturated and/or substituted in the carbon skeleton, such as alkenyl and alkynyl, can in each case be straight-chain or branched. Unless indicated otherwise, in these radicals the lower carbon skeletons, preferably those having 1 to 6 carbon atoms or, in the case of unsaturated groups, 2 to 4 carbon atoms, are preferred.
Alkyl radicals, also in composite groups such as alkoxy, haloalkyl, etc., are, for example, methyl, ethyl, n- or isopropyl, n-, iso-, t- or 2-butyl, pentyl radicals, hexyl radicals, such as n-hexyl, isohexyl and 1,3-dimethylbutyl, heptyl radicals, such as n-heptyl, 1-methylhexyl, 1,4-dimethylpentyl, and benzyl; alkenyl and alkynyl radicals, also in the composite groups, have the meaning of the unsaturated radicals which are possible and correspond to the alkyl radicals; alkenyl is, for example, allyl, 1-methylprop-2-en-1-yl, 2-methyl-prop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, 1-methyl-but-3-en-1-yl and 1-methyl-but-2-en-1-yl; alkynyl is, for example, propargyl, but-2-yn-1-yl, but-3-yn-1-yl, 1-methyl-but-3-yn-1-yl. The multiple bond can be located in any position of the unsaturated radical.
Cycloalkyl is a carbocyclic saturated ring system having preferably three to eight carbon atoms, for example cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl. Analogously, cycloalkenyl is a monocyclic alkenyl group having three to eight carbon ring members, for example cyclopropenyl, cyclobutenyl, cyclopentenyl and cyclohexenyl, where the double bond can be located in any position.
In the case of composite radicals, such as cycloalkylalkenyl, the first-mentioned radical can be located in any position of the second-mentioned radical.
In the case of an amino group which is doubly substituted, such as dialkylamino, these two substituents can be identical or different.
Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl, -alkenyl and -alkynyl, etc., is alkyl, alkenyl and alkynyl, respectively, which is partially or fully substituted by halogen, preferably by fluorine, chlorine and/or bromine, in particular by fluorine or chlorine, for example CF3, CHF2, CH2F, CF2CF3, CHClCH2F, CCl3, CCl2F, CClF2, CHCl2, CH2CH2Cl; haloalkoxy is, for example, OCF3, OCHF2, OCH2F, OCF2CF3, OCH2CF3 and OCH2CH2Cl; this applies correspondingly to other halogen-substituted radicals.
The term “heterocyclyl” is to be understood as meaning a saturated or partially unsaturated mono- or polycyclic ring system having preferably 3 to 14 ring members which contains one or more, preferably one to three, heteroatoms, preferably from a group consisting of oxygen, nitrogen (“N-heterocyclyl”) and sulfur. If chemically possible, the point of attachment can be in any position of the heterocycle. Examples are oxiranyl, aziridinyl, tetrahydrofuranyl, tetrahydrothienyl, pyrrolidinyl, isoxazolidinyl, isothioazolidinyl, pyrazolidinyl, oxazolidinyl, thiazolidinyl, imidazolidinyl, 1,2,4-oxadiazolidinyl, 1,2,4-thiadiazolidinyl, 1,2,4-triazolidin-3-yl, 1,3,4-thiadiazolidin-2-yl, 1,3,4-triazolidin-1-yl, 1,3,4-triazolidin-2-yl, 2,3-dihydrofuryl, 2,5-dihydrofuryl, 2,3-dihydrothienyl, 2,5-dihydrothienyl, 2,3-dihydropyrrolyl, 2,5-dihydropyrrolyl, 2,3-dihydroisoxazolyl, 4,5-dihydroisoxazolyl, 2,5-dihydroisothiazolyl, 2,3-dihydropyrazolyl, 4,5-dihydropyrazolyl, 2,5-dihydropyrazolyl, 2,3-dihydrooxazolyl, 4,5-dihydrooxazolyl, 2,5-dihydrooxazolyl, 2,3-dihydrothiazolyl, 4,5-dihydrothiazolyl, 2,5-dihydrothiazolyl, 2,3-dihydroimidazolyl, 4,5-dihydroimidazolyl, 2,5-dihydroimidazolyl, morpholinyl, piperidinyl, piperazinyl, tetrahydropyridazinyl, tetrahydropyrimidinyl, tetrahydropyrazinyl, 1,3,5-tetrahydrotriazinyl, 1,2,4-tetrahydrotriazin-1-yl, 1,2,4-tetrahydrotriazin-3-yl, 1,3-dihydrooxazinyl, 1,3-dithian-2-yl, tetrahydropyranyl, 1,3-dioxolan-2-yl, 3,4,5,6-tetrahydropyridin-2-yl, 1,2,5,6-tetrahydropyridin-1-yl, 1,2,3,4-tetrahydropyridin-1-yl, 1,2-dihydropyridin-1-yl, 1,4-dihydropyridin-1-yl, 4H-1,3-thiazinyl, 4H-3,1-benzothiazin-2-yl, 1,3-dithian-2-yl, 1,1-dioxo-2,3,4,5-tetrahydrothien-2-yl, 2H-1,4-benzothiazinyl, 1,3-dihydrooxazin-2-yl, hexahydroazepin-1-yl, homopiperazin-1-yl, 1,2,3,4-tetrahydroquinolin-1-yl, decahydroquinolin-1-yl, 1,2,3,4-tetrahydroisoquinolin-1-yl, decahydroisoquinolin-1-yl, 1,3,3-trimethyl-6-azabicyclo[3.2.1]octan-6-yl, 2,5-diazabicyclo[2.2.1]heptan-2-yl, 2-aza-5-oxabicyclo[2.2.1]heptan-2-yl, 2-aza-5-thiabicyclo[2.2.1]heptan-2-yl, 2-methyl-2,5-diazabicyclo[2.2.1]heptan-5-yl, 2-benzyl-2,5-diazabicyclo[2.2.1]heptan-5-yl, 4-azatricyclo[4.3.1.1(3,8)]undecan-5-on-4-yl.
Aryl is an aromatic mono- or polycyclic hydrocarbon radical having preferably 6 to 14, particularly preferably 6 to 12, carbon atoms, for example, phenyl, naphthyl, biphenyl and phenanthryl.
Heteroaryl is an aromatic mono-, bi- or tricyclic ring system having preferably 5 to 14 ring members which, in addition to carbon ring members, contains one to four nitrogen atoms or one to three nitrogen atoms (“N-heteroaryl”) and one oxygen or one sulfur atom or one oxygen or one sulfur atom. Examples of 5-membered heteroaryl are 1-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 1-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 1-imidazolyl, 2-imidazolyl, 4-imidazolyl, 1,2,4-triazol-3-yl, 1,3,4-triazol-2-yl, 1,2,3-triazol-1-yl, 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, 3-isothiazolyl, 4-isothiazolyl, 5-isothiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 1-imidazolyl, 2-imidazolyl, 1,2,4-oxadiazol-3-yl, 1,2,4-oxadiazol-5-yl, 1,2,4-thiadiazol-3-yl, 1,2,4-thiadiazol-5-yl, 1,3,4-oxadiazol-2-yl, 1,3,4-thiadiazol-2-yl. Examples of 6-membered heteroaryl are 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl and 1,2,4,5-tetrazin-3-yl. Examples of fused 5-membered heteroaryl are benzothiazol-2-yl and benzoxazol-2-yl. Examples of benzo-fused 6-membered heteroaryl are quinolinyl, isoquinolinyl, quinazolinyl and quinoxalinyl.
Depending on the nature and the attachment of the substituents, the compounds of the formula (I) can be present as stereoisomers. If, for example, one or more alkenyl groups are present, diastereomers may occur. If, for example, one or more asymmetrically substituted carbon atoms are present, enantiomers and diastereomers may occur. From the mixtures obtained in the preparation, stereoisomers can be obtained by customary separation methods, for example by chromatographic separation procedures. It is also possible to selectively prepare stereoisomers by using stereoselective reactions and employing optically active starting materials and/or auxiliaries. The invention also relates to all stereoisomers and mixtures thereof which are embraced by formula (I) but not specifically defined.
The term “partially or fully halogenated” is meant to express that in the groups thus characterized some or all of the hydrogen atoms may be replaced by identical or different halogen atoms as mentioned above.
If a group is polysubstituted, this is meant to be understood such that, when combining the different substituents, the general principles of the synthesis of chemical compounds are observed, i.e. that the formation of compounds is avoided of which the person skilled in the art knows that they are chemically unstable or impossible.
The symbols and indices of the formula (I) are preferably as defined below:
R1 is an aryl or heteroaryl radical which is unsubstituted or mono- or polysubstituted by identical or different substituents from the group consisting of: alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylalkynyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkenyl, heterocyclylalkynyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkylalkoxy, cycloalkylalkenyloxy, cycloalkylalkynyloxy, cycloalkenyloxy, aryloxy, arylalkoxy, arylalkenyloxy, arylalkynyloxy, heteroaryloxy, heteroarylalkoxy, heteroarylalkenyloxy, heteroarylalkynyloxy, heterocyclyloxy, heterocyclylalkoxy, heterocyclylalkenyloxy, heterocyclylalkynyloxy, thio, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkylalkylthio, cycloalkylalkenylthio, cycloalkylalkynylthio, cycloalkenylthio, arylthio, arylalkylthio, arylalkenylthio, arylalkynylthio, heteroarylthio, heteroarylalkylthio, heteroarylalkenylthio, heteroarylalkynylthio, heterocyclylthio, heterocyclylalkylthio, heterocyclylalkenylthio, heterocyclylalkynylthio, amino, unsubstituted or substituted mono- or dialkylamino, unsubstituted or substituted mono- or diarylamino, unsubstituted or substituted mono- or diheteroarylamino, unsubstituted or substituted N-alkyl-N-arylamino, unsubstituted or substituted N-alkyl-N-heteroarylamino, alkenylamino, alkynylamino, cycloalkylamino, cycloalkenylamino, heterocyclylalkylamino, heterocyclylalkenylamino, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkylalkylsulfonyl, cycloalkylalkenylsulfonyl, cycloalkylalkynylsulfonyl, arylsulfonyl, arylalkylsulfonyl, arylalkenylsulfonyl, arylalkynylsulfonyl, heteroarylsulfonyl, heteroarylalkylsulfonyl, heteroarylalkenylsulfonyl, heteroarylalkynylsulfonyl, heterocyclylsulfonyl, heterocyclylalkylsulfonyl, heterocyclylalkenylsulfonyl, heterocyclylalkynylsulfonyl, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkylalkylsulfinyl, cycloalkylalkenylsulfinyl, cycloalkylalkynylsulfinyl, arylsulfinyl, arylalkylsulfinyl, arylalkenylsulfinyl, arylalkynylsulfinyl, heteroarylsulfinyl, heteroarylalkylsulfinyl, heteroarylalkenylsulfinyl, heteroarylalkynylsulfinyl, heterocyclylsulfinyl, arylalkylsulfinyl, heterocyclylalkenylsulfinyl, heterocyclylalkynylsulfinyl, aminosulfonyl, unsubstituted or substituted mono- or dialkylaminosulfonyl, unsubstituted or substituted mono- or diarylaminosulfonyl, unsubstituted or substituted mono- or diheteroarylaminosulfonyl, unsubstituted or substituted N-alkyl-N-arylaminosulfonyl, unsubstituted or substituted N-alkyl-N-heteroarylaminosulfonyl, alkylsulfonyloxy, alkenylsulfonyloxy, alkynylsulfonyloxy, cycloalkylsulfonyloxy, cycloalkylalkylsulfonyloxy, cycloalkylalkenylsulfonyloxy, cycloalkylalkynylsulfonyloxy, arylsulfonyloxy, arylalkylsulfonyloxy, arylalkenylsulfonyloxy, arylalkynylsulfonyloxy, heteroarylsulfonyloxy, heteroarylalkylsulfonyloxy, heteroarylalkenylsulfonyloxy, heteroarylalkynylsulfonyloxy, heterocyclylsulfonyloxy, heterocyclylalkylsulfonyloxy, heterocyclylalkenylsulfonyloxy, heterocyclylalkynylsulfonyloxy, alkylsulfonylamino, alkenylsulfonylamino, alkynylsulfonylamino, cycloalkylsulfonylamino, cycloalkylalkylsulfoamino, cycloalkylalkenylsulfonylamino, cycloalkylalkynylsulfonylamino, arylsulfonylamino, arylalkylsulfonylamino, arylalkenylsulfonoamino, arylalkynylsulfonylamino, heteroaryisulfonylamino, heteroarylalkylsulfonylamino, heteroarylalkenylsulfonoamino, heteroarylalkynylsulfonylamino, alkylsulfonyl-N-alkylamino, alkenylsulfonyl-N-alkylamino, N-alkylalkynylsulfonyl-N-alkylamino, cycloalkylsulfonyl-N-alkylamino, cycloalkylalkylsulfonyl-N-alkylamino, cycloalkylalkenylsulfonyl-N-alkylamino, cycloalkylalkynylsulfonyl-N-alkylamino, arylsulfonyl-N-alkylamino, heteroarylsulfonyl-N-alkylamino, arylalkylsulfonyl-N-alkylamino, heteroarylalkylsulfonyl-N-alkylamino, arylalkenylsulfonyl-N-alkylamino, heteroarylalkenylsulfonyl-N-alkylamino, arylalkynylsulfonyl-N-alkylamino, heteroarylalkynylsulfonyl-N-alkylamino, heterocyclylsulfonyl-N-alkylamino, heterocyclylalkylsulfonyl-N-alkylamino, heterocyclylalkenylsulfonyl-N-alkylamino, heterocyclylalkynylsulfonyl-N-alkylamino, formyl, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, cycloalkylalkylcarbonyl, cycloalkylalkenylcarbonyl, cycloalkylalkynylcarbonyl, arylcarbonyl, arylalkylcarbonyl, arylalkenylcarbonyl, arylalkynylcarbonyl, heteroarylcarbonyl, heteroarylalkylcarbonyl, heteroarylalkenylcarbonyl, heteroarylalkynylcarbonyl, heterocyclylcarbonyl, heterocyclylalkylcarbonyl, heterocyclylalkenyl, heterocyclylalkynylcarbonyl, formyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkylalkylcarbonyloxy, cycloalkylalkenylcarbonyloxy, cycloalkylalkynylcarbonyloxy, arylcarbonyloxy, arylalkylcarbonyloxy, arylalkenylcarbonyloxy, arylalkynylcarbonyloxy, heteroarylcarbonyloxy, heteroarylalkylcarbonyloxy, heteroarylalkenylcarbonyloxy, heteroarylalkynylcarbonyloxy, heterocyclylcarbonyloxy, heterocyclylalkylcarbonyloxy, heterocyclylalkenyloxy, heterocyclylalkynylcarbonyloxy, carboxyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, cycloalkylalkenyloxycarbonyl, cycloalkylalkynyloxycarbonyl, aryloxycarbonyl, arylalkoxycarbonyl, arylalkenyloxycarbonyl, arylalkynyloxycarbonyl, heteroaryloxycarbonyl, heteroarylalkoxycarbonyl, heteroarylalkenyloxycarbonyl, heteroarylalkynyloxycarbonyl, heterocyclyloxycarbonyl, heterocyclylalkoxycarbonyl, heterocyclylalkenyloxycarbonyl, heterocyclylalkynyloxycarbonyl, aminocarbonyl, unsubstituted or substituted mono- or dialkylaminocarbonyl, unsubstituted or substituted mono- or diarylaminocarbonyl, unsubstituted or substituted mono- or diheteroarylaminocarbonyl, unsubstituted or substituted N-alkyl-N-arylaminocarbonyl, unsubstituted or substituted N-alkyl-N-heteroarylaminocarbonyl, unsubstituted or substituted alkylcarbonylamino, unsubstituted or substituted alkylcarbonyl-N-alkylamino, unsubstituted or substituted arylcarbonylamino, unsubstituted or substituted arylcarbonyl-N-arylamino, unsubstituted or substituted heteroarylcarbonylamino, unsubstituted or substituted heteroarylcarbonyl-N-heteroarylamino, unsubstituted or substituted alkylcarbonyl-N-arylamino, unsubstituted or substituted arylcarbonyl-N-alkylamino, unsubstituted or substituted alkylcarbonyl-N-heteroarylamino, unsubstituted or substituted heteroarylcarbonyl-N-alkylamino, alkoxycarbonylamino, alkenyloxycarbonylamino, alkynyloxycarbonylamino, cycloalkoxycarbonylamino, cycloalkylalkoxycarbonylamino, cycloalkylalkenyloxycarbonylamino, cycloalkylalkynyloxycarbonylamino, aryloxycarbonylamino, arylalkoxycarbonylamino, arylalkenyloxycarbonylamino, arylalkynyloxycarbonylamino, heteroaryloxycarbonylamino, heteroarylalkoxycarbonylamino, heteroarylalkenyloxycarbonylamino, heteroarylalkynyloxycarbonylamino, heterocyclyloxycarbonylamino, heterocyclylalkoxycarbonylamino, heterocyclylalkenyloxycarbonylamino, heterocyclylalkynyloxycarbonylamino, alkoxycarbonyl-N-alkylamino, alkenyloxycarbonyl-N-alkylamino, alkynyloxycarbonyl-N-alkylamino, cycloalkoxycarbonyl-N-alkylamino, cycloalkylalkoxycarbonyl-N-alkylamino, cycloalkylalkenyloxycarbonyl-N-alkylamino, cycloalkylalkynyloxycarbonyl-N-alkylamino, aryloxycarbonyl-N-alkylamino, arylalkoxycarbonyl-N-alkylamino, arylalkenyloxycarbonyl-N-alkylamino, arylalkynyloxycarbonyl-N-alkylamino, heteroarylalkoxycarbonyl-N-alkylamino, heteroarylalkenyloxycarbonyl-N-alkylamino, heteroarylalkynyloxycarbonyl-N-alkylamino, heterocyclylalkoxycarbonyl-N-alkylamino, heterocyclylalkenyloxycarbonyl-N-alkylamino, heterocyclylalkynyloxycarbonyl-N-alkylamino, formyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloalkylthio, haloalkenylthio, haloalkynylthio, haloalkylamino, haloalkenylamino, haloalkynylamino, haloalkylsulfonyl, haloalkenylsulfonyl, haloalkynylsulfonyl, haloalkylsulfinyl, haloalkenylsulfinyl, haloalkynylsulfinyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, haloalkylcarbonyloxy, haloalkenylcarbonyloxy, haloalkynylcarbonyloxy, haloalkoxycarbonyl, haloalkenyloxycarbonyl, haloalkynyloxycarbonyl, haloalkylaminocarbonyl, haloalkenylaminocarbonyl, haloalkynylaminocarbonyl, haloalkoxycarbonylamino, haloalkenyloxycarbonylamino, haloalkynyloxycarbonylamino, alkoxyalkoxy, arylalkoxyalkoxy, cyano, nitro, or a radical from the group consisting of alkyl-NH—N═CH—, aryl-(CH2)n—NH—N═CH—, alkoxy-N═CH—, aryl-(CH2)n—O—N═CH—, alkyl-NH—NH—CO— and arylalkyl-NH—NH—CO—.
R1 is particularly preferably aryl or heteroaryl, unsubstituted or mono- or polysubstituted by identical or different substituents from the group consisting of halogen, nitro, cyano, alkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, alkylcarbonyloxy, alkylthio, alkylsulfinyl, alkylsulfonyl, alkylsulfonyloxy, aryl, aryloxy, heteroaryl, heterocyclyl, heterocyclylalkyl, benzyl—where the seventeen last-mentioned groups may be unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, alkyl, haloalkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy and alkylthio.
Very particularly preferred substituents with which the aryl or heteroaryl radical of group R1 may be substituted are halogen, nitro, cyano, (C1–C4)-alkyl, (C1–C4)-haloalkyl, (C2–C4)-haloalkenyl, (C2–C4)-haloalkynyl, (C1–C4)-haloalkoxy, (C2–C4)-haloalkenyloxy, (C2–C4)-haloalkynyloxy, unsubstituted or substituted aryl, heteroaryl, (C1–C4)-alkoxycarbonyl, (C1–C4)-alkoxy, (C1–C4)-alkylthio, (C1–C4)-alkylcarbonyloxy, (C1–C4)-alkylsulfonyl, aryloxy, (C1–C4)-alkylcarbonyl, heterocyclyl, heterocyclylalkyl, where aryl, heteroaryl and/or heterocyclyl systems may be unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-haloalkyl and (C1–C4)-alkoxy, or two substituents together form a group —O—CH2—O— or —O—(CH2)2—O—.
Especially preferred are halogen, (C1–C4)-alkyl, (C1–C4)-haloalkyl, nitro, cyano, (C1–C4)-alkoxycarbonyl, (C1–C4)-alkoxy, (C1–C4)-alkylthio, phenyl, (C1–C4)-alkylcarbonyloxy, (C1–C4)-alkylsulfonyl, phenoxy, (C1–C4)-alkylcarbonyl, (C1–C4)-alkyl-piperidin-1-yl, where phenyl and piperidyl radicals may be unsubstituted or substituted by one or more radicals from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-alkoxy and (C1–C4)-haloalkyl, or that two substituents together form a group —O—CH2—O— or —O—(CH2)2—O—.
From among the last-mentioned group of substituents, the following are preferred: F, Cl, CF3, methyl, ethyl, isopropyl, n-propyl, nitro, cyano, —COOCH3, —OCH3, —OC2H5, —SCH3, phenyl, o-phenyl, —O—C(O)-isopropyl, —SO2CH3, —C(O)CH3, —O—CH2—O— and —CH3—(4-methylpiperidin-1-yl).
In group R1, the aryl or heteroaryl radical is preferably from the group consisting of 2-thienyl, 3-thienyl, 2-pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 6-pyrimidinyl, 2-pyrazinyl, 1,3,5-triazin-2-yl, 1,2,4-triazin-3-yl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, naphthyl or phenyl, in particular from the group consisting of phenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 2-thienyl, 3-thienyl and quinolin-4-yl.
A is a group CR4R5 or C═O, where

    
    
        R4 is preferably hydrogen, fluorine or methyl, particularly preferably hydrogen or fluorine and very particularly preferably hydrogen;
        R5 is preferably hydrogen, fluorine, (C1–C4)-alkyl, (C2–C4)-alkenyl, (C2–C4)-alkynyl, (C3–C6)-cycloalkyl, (C3–C8)-cycloalkenyl, (C3–C6)-cycloalkyl-(C1–C4)-alkyl, aryl, aryl-(C1–C4)-alkyl, heteroaryl, heteroaryl-(C1–C4)-alkyl, particularly preferably hydrogen, fluorine or methyl and very particularly preferably hydrogen.
    
    


R2 and R3 together with the nitrogen atom to which they are attached form a N-heterocyclyl- or N-heteroaryl group which is unsubstituted or mono- or polysubstituted by identical or different substituents from the group consisting of alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkylalkyl, cycloalkylalkenyl, cycloalkylalkynyl, aryl, arylalkyl, arylalkenyl, arylalkynyl, heteroaryl, heteroarylalkyl, heteroarylalkenyl, heteroarylalkynyl, heterocyclyl, heterocyclylalkyl, heterocyclylalkenyl, heterocyclylalkynyl, hydroxy, alkoxy, alkenyloxy, alkynyloxy, cycloalkoxy, cycloalkylalkoxy, cycloalkylalkenyloxy, cycloalkylalkynyloxy, cycloalkenyloxy, aryloxy, arylalkoxy, arylalkenyloxy, arylalkynyloxy, heteroaryloxy, heteroarylalkoxy, heteroarylalkenyloxy, heteroarylalkynyloxy, heterocyclyloxy, heterocyclylalkoxy, heterocyclylalkenyloxy, heterocyclylalkynyloxy, thio, alkylthio, alkenylthio, alkynylthio, cycloalkylthio, cycloalkylalkylthio, cycloalkylalkenylthio, cycloalkylalkynylthio, cycloalkenylthio, arylthio, arylalkylthio, arylalkenylthio, arylalkynylthio, heteroarylthio, heteroarylalkylthio, heteroarylalkenylthio, heteroarylalkynylthio, heterocyclylthio, heterocyclylalkylthio, heterocyclylalkenylthio, heterocyclylalkynylthio, amino, unsubstituted or substituted mono- or dialkylamino, unsubstituted or substituted mono- or diarylamino, unsubstituted or substituted mono- or diheteroarylamino, unsubstituted or substituted N-alkyl-N-arylamino, unsubstituted or substituted N-alkyl-N-heteroarylamino, alkenylamino, alkynylamino, cycloalkylamino, cycloalkenylamino, heterocyclylalkylamino, heterocyclylalkenylamino, alkylsulfonyl, alkenylsulfonyl, alkynylsulfonyl, cycloalkylsulfonyl, cycloalkylalkylsulfonyl, cycloalkylalkenylsulfonyl, cycloalkylalkynylsulfonyl, arylsulfonyl, arylalkylsulfonyl, arylalkenylsulfonyl, arylalkynylsulfonyl, heteroarylsulfonyl, heteroarylalkylsulfonyl, heteroarylalkenylsulfonyl, heteroarylalkynylsulfonyl, heterocyclylsulfonyl, heterocyclylalkylsulfonyl, heterocyclylalkenylsulfonyl, heterocyclylalkynylsulfonyl, alkylsulfinyl, alkenylsulfinyl, alkynylsulfinyl, cycloalkylsulfinyl, cycloalkylalkylsulfinyl, cycloalkylalkenylsulfinyl, cycloalkylalkynylsulfinyl, arylsulfinyl, arylalkylsulfinyl, arylalkenylsulfinyl, arylalkynylsulfinyl, heteroarylsulfinyl, heteroarylalkylsulfinyl, heteroarylaIkenylsulfinyl, heteroarylalkynylsulfinyl, heterocyclylsulfinyl, arylalkylsulfinyl, heterocyclylalkenylsulfinyl, heterocyclylalkynylsulfinyl, aminosulfonyl, unsubstituted or substituted mono- or dialkylaminosulfonyl, unsubstituted or substituted mono- or diarylaminosulfonyl, unsubstituted or substituted mono- or diheteroarylaminosulfonyl, unsubstituted or substituted N-alkyl-N-arylaminosulfonyl, unsubstituted or substituted N-alkyl-N-heteroarylaminosulfonyl, alkylsulfonyloxy, alkenylsulfonyloxy, alkynylsulfonyloxy, cycloalkylsulfonyloxy, cycloalkylalkylsulfonyloxy, cycloalkylalkenylsulfonyloxy, cycloalkylalkynylsulfonyloxy, arylsulfonyloxy, arylalkylsulfonyloxy, arylalkenylsulfonyloxy, arylalkynylsulfonyloxy, heteroarylsulfonyloxy, heteroarylalkylsulfonyloxy, heteroarylalkenylsulfonyloxy, heteroarylalkynylsulfonyloxy, heterocyclylsulfonyloxy, heterocyclylalkylsulfonyloxy, heterocyclylalkenylsulfonyloxy, heterocyclylalkynylsulfonyloxy, alkylsulfonylamino, alkenylsulfonylamino, alkynylsulfonylamino, cycloalkylsulfonylamino, cycloalkylalkylsulfoamino, cycloalkylalkenylsulfonylamino, cycloalkylalkynylsulfonylamino, arylsulfonylamino, arylalkylsulfonylamino, arylalkenylsulfonoamino, arylalkynylsulfonylamino, heteroarylsulfonylamino, heteroarylalkylsulfonylamino, heteroarylalkenylsulfonoamino, heteroarylalkynylsulfonylamino, alkylsulfonyl-N-alkylamino, alkenylsulfonyl-N-alkylamino, N-alkyl-alkynylsulfonyl-N-alkylamino, cycloalkylsulfonyl-N-alkylamino, cycloalkylalkylsulfonyl-N-alkylamino, cycloalkylalkenylsulfonyl-N-alkylamino, cycloalkylalkynylsulfonyl-N-alkylamino, arylsulfonyl-N-alkylamino, heteroarylsulfonyl-N-alkylamino, arylalkylsulfonyl-N-alkylamino, heteroarylalkylsulfonyl-N-alkylamino, arylalkenylsulfonyl-N-alkylamino, heteroarylalkenylsulfonyl-N-alkylamino, arylalkynylsulfonyl-N-alkylamino, heteroarylalkynylsulfonyl-N-alkylamino, heterocyclylsulfonyl-N-alkylamino, heterocyclylalkylsulfonyl-N-alkylamino, heterocyclylalkenylsulfonyl-N-alkylamino, heterocyclylalkynylsulfonyl-N-alkylamino, alkylcarbonyl, alkenylcarbonyl, alkynylcarbonyl, cycloalkylcarbonyl, cycloalkylalkylcarbonyl, cycloalkylalkenylcarbonyl, cycloalkylalkynylcarbonyl, arylcarbonyl, arylalkylcarbonyl, arylalkenylcarbonyl, arylalkynylcarbonyl, heteroarylcarbonyl, heteroarylalkylcarbonyl, heteroarylalkenyl, heteroarylalkynylcarbonyl, heterocyclylcarbonyl, heterocyclylalkylcarbonyl, heterocyclylalkenyl, heterocyclylalkynylcarbonyl, formyloxy, alkylcarbonyloxy, alkenylcarbonyloxy, alkynylcarbonyloxy, cycloalkylcarbonyloxy, cycloalkylalkylcarbonyloxy, cycloalkylalkenylcarbonyloxy, cycloalkylalkynylcarbonyloxy, arylcarbonyloxy, arylalkylcarbonyloxy, arylalkenylcarbonyloxy, arylalkynylcarbonyloxy, heteroarylcarbonyloxy, heteroarylalkylcarbonyloxy, heteroarylalkenylcarbonyloxy, heteroarylalkynylcarbonyloxy, heterocyclylcarbonyloxy, heterocyclylalkylcarbonyloxy, heterocyclylalkenyloxy, heterocyclylalkynylcarbonyloxy, carboxyl, alkoxycarbonyl, alkenyloxycarbonyl, alkynyloxycarbonyl, cycloalkoxycarbonyl, cycloalkylalkoxycarbonyl, cycloalkylalkenyloxycarbonyl, cycloalkylalkynyloxycarbonyl, aryloxycarbonyl, arylalkoxycarbonyl, arylalkenyloxycarbonyl, arylalkynyloxycarbonyl, heteroaryloxycarbonyl, heteroarylalkoxycarbonyl, heteroarylalkenyloxycarbonyl, heteroarylalkynyloxycarbonyl, heterocyclyloxycarbonyl, heterocyclylalkoxycarbonyl, heterocyclylalkenyloxycarbonyl, heterocyclylalkynyloxycarbonyl, aminocarbonyl, unsubstituted or substituted mono- or dialkylaminocarbonyl, unsubstituted or substituted mono- or diarylaminocarbonyl, unsubstituted or substituted mono- or diheteroarylaminocarbonyl, unsubstituted or substituted N-alkyl-N-arylaminocarbonyl, unsubstituted or substituted N-alkyl-N-heteroarylaminocarbonyl, unsubstituted or substituted alkylcarbonylamino, unsubstituted or substituted alkylcarbonyl-N-alkylamino, unsubstituted or substituted arylcarbonylamino, unsubstituted or substituted arylcarbonyl-N-arylamino, unsubstituted or substituted heteroarylcarbonylamino, unsubstituted or substituted heteroarylcarbonyl-N-heteroarylamino, unsubstituted or substituted alkylcarbonyl-N-arylamino, unsubstituted or substituted arylcarbonyl-N-alkylamino, unsubstituted or substituted alkylcarbonyl-N-heteroarylamino, unsubstituted or substituted heteroarylcarbonyl-N-alkylamino, alkoxycarbonylamino, alkenyloxycarbonylamino, alkynyloxycarbonylamino, cycloalkoxycarbonylamino, cycloalkylalkoxycarbonylamino, cycloalkylalkenyloxycarbonylamino, cycloalkylalkynyloxycarbonylamino, aryloxycarbonylamino, arylalkoxycarbonylamino, arylalkenyloxycarbonylamino, arylalkynyloxycarbonylamino, heteroaryloxycarbonylamino, heteroarylalkoxycarbonylamino, heteroarylalkenyloxycarbonylamino, heteroarylalkynyloxycarbonylamino, heterocyclyloxycarbonylamino, heterocyclylalkoxycarbonylamino, heterocyclylalkenyloxycarbonylamino, heterocyclylalkynyloxycarbonylamino, alkoxycarbonyl-N-alkylamino, alkenyloxycarbonyl-N-alkylamino, alkynyloxycarbonyl-N-alkylamino, cycloalkoxycarbonyl-N-alkylamino, cycloalkylalkoxycarbonyl-N-alkylamino, cycloalkylalkenyloxycarbonyl-N-alkylamino, cycloalkylalkynyloxycarbonyl-N-alkylamino, aryloxycarbonyl-N-alkylamino, arylalkoxycarbonyl-N-alkylamino, arylalkenyloxycarbonyl-N-alkylamino, arylalkynyloxycarbonyl-N-alkylamino, heteroarylalkoxycarbonyl-N-alkylamino, heteroarylalkenyloxycarbonyl-N-alkylamino, heteroarylalkynyloxycarbonyl-N-alkylamino, heterocyclylalkoxycarbonyl-N-alkylamino, heterocyclylalkenyloxycarbonyl-N-alkylamino, heterocyclylalkynyloxycarbonyl-N-alkylamino, formyl, halogen, haloalkyl, haloalkenyl, haloalkynyl, haloalkoxy, haloalkenyloxy, haloalkynyloxy, haloalkylthio, haloalkenylthio, haloalkynylthio, haloalkylamino, haloalkenylamino, haloalkynylamino, haloalkylsulfonyl, haloalkenylsulfonyl, haloalkynylsulfonyl, haloalkylsulfinyl, haloalkenylsulfinyl, haloalkynylsulfinyl, haloalkylcarbonyl, haloalkenylcarbonyl, haloalkynylcarbonyl, haloalkylcarbonyloxy, haloalkenylcarbonyloxy, haloalkynylcarbonyloxy, haloalkoxycarbonyl, haloalkenyloxycarbonyl, haloalkynyloxycarbonyl, haloalkylaminocarbonyl, haloalkenylaminocarbonyl, haloalkynylaminocarbonyl, haloalkoxycarbonylamino, haloalkenyloxycarbonylamino, haloalkynyloxycarbonylamino, alkoxyalkoxy, arylalkoxyalkoxy, cyano, nitro, or a radical from the group consisting of alkyl-NH—N═CH—, aryl-(CH2)n—NH—N═CH—, alkoxy-N═CH—, aryl-(CH2)n—O—N═CH—, alkyl-NH—NH—CO— and arylalkyl-NH—NH—CO—.
Particularly preferably, R2 and R3 together with the nitrogen atom to which they are attached form N-heteroaryl or N-heterocyclyl, unsubstituted or mono- or polysubstituted by identical or different substitutents from the group consisting of (C1–C4)-alkyl, (C2–C4)-alkenyl, (C2–C4)-alkynyl, (C3–C6)-cycloalkyl, (C3–C6)-heterocyclyl, (C3–C8)-cycloalkenyl, (C3–C6)-cycloalkyl-(C1–C4)-alkyl, aryl-(C1–C4)-alkyl, heteroaryl-(C1–C4)-alkyl, (C1–C4)-alkylcarbonyl, (C1–C4)-alkylcarbonyloxy, (C1–C4)-alkylsulfonyl, (C1–C4)-alkylsulfonyloxy, (C1–C4)-alkoxycarbonyl, SCN, (C1–C4)-dialkylamino, formyl—where the groups mentioned are unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, alkyl, haloalkyl, cycloalkyl, alkenyl, alkynyl, phenyl, alkoxy, haloalkoxy and alkylthio. Two substituents together may form a group —O—CH2—O— or —O—(CH2)2—O— or, at the same carbon atom, ═O.
Very particularly preferably, R2 and R3 together with the nitrogen atom to which they are attached form N-heteroaryl or N-heterocyclyl, unsubstituted or mono- or polysubstituted by identical or different substituents from the group consisting of (C1–C4)-alkyl, (C2–C4)-alkenyl, (C2–C4)-alkynyl, (C3–C6)-cycloalkyl, (C3–C6)-heterocyclyl, (C3–C8)-cycloalkenyl, (C3–C6)-cycloalkyl-(C1–C4)-alkyl, aryl-(C1–C4)-alkyl, heteroaryl-(C1–C4)-alkyl, (C1–C4)-alkylcarbonyl, (C1–C4)-alkylcarbonyloxy, (C1–C4)-alkoxycarbonyl, (C1–C4)-alkylsulfonyl, (C1–C4)-alkylsulfonyloxy—where the groups mentioned are unsubstituted or substituted by one or more identical or different radicals from the group consisting of halogen, nitro, cyano, alkyl, haloalkyl, cycloalkyl, alkenyl, alkynyl, alkoxy, haloalkoxy and alkylthio —SCN, (C1–C4)-dialkylamino, formyl, ═O, —O—CH2—O—, —O—(CH2)2—O—.
Preferably, R2 and R3 together with the nitrogen atom to which they are attached form a 6-azabicyclo[3.2.1]octane, 1,2,5,6-tetrahydropyridine, decahydroquinoline, azepam, morpholine, piperazine, piperidine, unsubstituted or mono- or polysubstituted by identical or different substituents mentioned above, particularly preferably a piperidine.
Depending on the nature of the substituents defined above, the compounds of the formula (I) have acidic or basic properties and are able to form salts. Here, preference is given to the salts which are tolerable and customary in the field of pest control. 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 give salts. Suitable bases are, for example, hydroxides, carbonates, bicarbonates of the alkali metals and alkaline earth metals, in particular those of sodium, potassium, magnesium and calcium, furthermore those of ammonia, of primary, secondary and tertiary amines having (C1–C4)-alkyl radicals and of mono-, di- and trialkanolamines of (C1–C4)-alkanols. If, for example, the compounds of the formula (I) carry groups such as amino, alkylamino and other groups which induce basic properties, these compounds can be reacted with acids to give salts. Suitable acids are, for example, mineral acids, such as hydrochloric acid, sulfuric acid 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 have insectidical, acaricidal and/or helminthicidal/nematicidal properties, too.
The compounds of the formula (I) may have one or more asymmetrically substituted carbon atoms or stereoisomers on double bonds. Accordingly, enantiomers or diastereomers may occur. 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 by customary methods into the enantiomers.
The compounds according to the invention are prepared 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 preparation is carried out under reaction conditions which are suitable and known for the reactions mentioned. It is also possible to employ variants known per se which are not mentioned in more detail here.
If desired, the starting materials can also be formed in situ, such that they are not isolated from the reaction mixture but immediately converted further into the compounds of the formula (I).
In all of the formulae mentioned below, the substituents and symbols have the same meaning as described under formula (I) unless defined otherwise.
Depending on the meaning of the substituents, the compounds of the formula (I) can be prepared, for example, by one or more of the processes shown in the schemes below.




The palladium-catalyzed crosscoupling (Sonogashira coupling) shown in scheme 1 of a compound of the formula (II) in which X is —OSO2CF3 or halogen, preferably iodine, with a compound of the formula (III) gives the compounds of the formula (I) according to the invention. This reaction is preferably carried out in the presence of an amine base, for example diethylamine, triethylamine, piperidine, pyrrolidine or DBU, which, in addition to other solvents such as benzene, toluene, DMF, THF or diethyl ether, may also serve as solvent, or in the presence of another suitable base, for example an alkali metal alkoxide, such as potassium tert-butoxide in an inert organic solvent, such as DMSO, acetonitrile; and in the presence of a solvent and a palladium catalyst and also a copper(I) salt (Y is preferably I, Cl, Br, cyano or SCN), preferably copper(I) iodide (Y=I). Suitable palladium catalyst systems are, for example, Pd(PPh3)4, PdCl2(PPh3)2 and Pd(OAc)2(PPh3)2 or Pd(OAc)2 and a triarylphosphine, preferably triphenylphosphine or tri-(o-tolyl)phosphine. These methods are described, for example, in Tetrahedron Lett. 4467 (1975), Comprehensive Organic Synthesis (B. M. Trost, I. Flemming, Eds), Pergamon Press, Oxford, Vol 3, 521–549 (1991), Org. Prep. Proct. Int. 129 (1995), J. Med. Chem. 40, 3542 (1997), J. Org. Chem. 63, 1109 (1998).
Compounds of the formula (II) are either commercially available or can be prepared according to generally known methods, for example Houben-Weyl, Methoden der Organischen Chemie, Georg-Thieme-Verlag, Stuttgart or Chem. Pharm. Bull. 27, 270 (1979).
Compounds of the formula (III) can be prepared, for example, according to scheme 2 from compounds of the formula (IV), in which X′ is a leaving group, for example a chlorine, bromine or iodine atom or an alkylsulfonyloxy or arylsulfonyloxy radical, for example a tosyloxy radical.




The compounds of the formula (III) are obtained in the presence of an inorganic or organic base, such as potassium carbonate or excess amine of the formula (V), in an inert organic solvent, such as methanol, acetone or DMF. Such methods are known, for example, from Org. Magn. Reson. 14, 161 (1980), Tetrahedron 41, 5685 (1985), J. Med. Chem. 34, 746 (1991), J. Org. Chem. 56, 3707 (1991), J. Org. Chem. 57, 3000 (1992), J. Med. Chem. 37, 2735 (1994).
Compounds of the formula (I) in which A is CR4R5, where R5 is hydrogen, in particular those in which A is CH2, are also obtainable, for example, according to scheme 3.




Compounds of the formula (I) are obtained according to scheme 3 by reacting compounds of the formula (V) with compounds of the formula (VI) and an aldehyde, such as, for example, benzaldehyde, acetaldehyde or formaldehyde, or an aldehyde source, such as paraformaldehyde or formalin, in the presence of a copper(I) salt, preferably copper(I) chloride (Y=Cl), in an inert organic solvent, such as, for example, dioxan. Such methods are known, for example, from Chem. Ber. 66, 418 (1933), J. Prakt. Chem. 331, 187 (1989), Tetrahedron Lett. 39, 967 (1998).
Compounds of the formula (VI) are either commercially available, or they can be obtained by Sonogashira coupling and subsequent removal of the protective group from R1 X and a protected acetylene equivalent, such as, for example, trimethylsilylacetylene or 2-methylbut-3-yn-2-ol, according to known methods. Such methods are described, for example, in Comprehensive Organic Synthesis (B. M. Trost, I. Flemming, Eds), Pergamon Press, Oxford, Vol 3, 521–549 (1991), Synthesis. (1980), 627, J. Org. Chem. 50, 1763 (1985), Tetrahedron Lett. 34, 2071 (1993), Angew. Chem. Int. Ed. Engl. 18, 406 (1993), Synthesis (1996), 589.
In particular compounds of the formula (I), in which A is CR4R5 can also be obtained, for example, according to scheme 4.




According to scheme 4, the compounds of the formula (I) are obtained by reacting compounds of the formula (VII) in which Z is a chlorine, bromine or iodine atom or an alkylsulfonyloxy or arylsulfonyloxy radical, for example a tosyloxy radical, with compounds of the formula (VIII), in which M is an alkali metal atom, preferably a lithium atom. If Z in the formula (VII) is chlorine, bromine or iodine, M in the formula (VIII) may furthermore be a hydrogen atom. If M in the formula (VIII) is a hydrogen atom, the reaction is carried out in the presence of an inorganic base, such as potassium carbonate, and in an inert organic solvent, such as acetone or DMF. If M in the formula (VIII) is not hydrogen, preference is given to inert organic solvents, such as diethyl ether or THF.
Compounds of the formula (VII) can be prepared by or analogously to known methods. These methods are known, for example, from Chem. Phys. Lipids 13, 159 (1974), Synthesis (1975), 255, J. Am. Chem. Soc. 60, 2662 (1938), Bull. Chem. Soc. Jpn. 46, 954 (1973), J. Med. Chem. 21, 253 (1978), Bull. Soc. Chim. Fr. (1969), 4514, J. Org. Chem. 49, 4344 (1984), J. Med. Chem. 41, 1084 (1998), J. Org. Chem. 63, 7472 (1998).
Collections of compounds of the formula (I) which can be synthesized by the abovementioned schemes 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, the work-up or the 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 number of commercially available apparatuses as are offered by, for example, Stem Corporation, Woodrolfe Road, Tollesbury, Essex, CM9 8SE, England or H+P Labortechnik GmbH, Bruckmannring 28, 85764 Oberschleiβheim, Germany or Radleys, Shirehill, Saffron Walden, Essex, England 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 have to be performed between the process steps. This can be avoided by employing semiintegrated 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 method 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”, Verlag 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 according to the processes described herein yields compounds of the formula (I) in the form of substance collections which are referred to as 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 arthropods such as insects, Acarina and helminths, such as parasites of animals and plant-damaging nematodes, very especially preferably for controlling insects and arachnids, which are encountered in agriculture, in animal husbandry, in livestock breeding, in horticulture, in forests, in the protection of stored goods and materials and in the domestic sector 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 development stages. The above mentioned pests include:

    From the order of the Isopoda, for example, Armadillidium spp., Oniscus spp., Porcellio spp.
    From the order of the Diplopoda, for example, Blaniulus spp.
    From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.
    From the order of the Symphyla, for example, Scutigerella spp.
    From the order of the Thysanura, for example, Lepisma spp.
    From the order of the Collembola, for example, Onychiurus spp.
    From the order of the Orthoptera, for example, Blattella spp., Blattella germanica, Blatta orientalis, Periplaneta spp., Periplaneta americana, Periplaneta australasiae, Leucophaea spp., Acheta spp., Acheta domesticus, Gryllotalpa spp., Gryllus spp., Gryllus bimaculatus, Locusta spp., Locusta migratoria migratorioides, Melanoplus spp., Schistocerca spp.
    From the order of the Dermaptera, for example, Forficula spp., Forficula auricularia. 
    From the order of Isoptera, for example, Reticulitermes spp., Reticulitermes speratus, Coptotermes spp., Coptotermes formosanus. 
    From the order of the Anoplura, for example, Pediculus spp., Pediculus humanus humanus, Pediculus humanus capitis, Haematopinus spp., Linognathus spp.
    From the order of the Mallophaga, for example, Trichodectes spp., Damalinea spp.
    From the order of the Thysanoptera, for example, Frankliniella spp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Kakothrips spp., Hercinothrips spp., Scirtothrips spp., Scirtothrips citri, Scirtothrips aurantii, Taeniothrips spp., Thrips spp., Thrips oryzae, Thrips palmi, Thrips tabaci. 
    From the order of the heteroptera, for example, Eurygaster spp., Stephanitis spp., Lygus spp., Aelia spp., Eurydema spp., Dysdercus spp., Piesma spp., Piesma quadrata, Rhodnius prolixus, Triatoma spp., Cimex lectularius. 
    From the order of the Homoptera, for example, Aleurodes spp., Aleurodes brassicae, Aleurodes proletella, Bemisia spp., Bemisia tabaci, Trialeurodes spp., Trialeurodes vaporariorum, Brevicoryne spp., Brevicoryne brassicae, Cryptomyzus spp., Aphis spp., Aphis fabae, Aphis gossypii, Aphis pomi, Eriosoma spp., Hyalopterus spp., Phylloxera spp., Pemphigus spp., Macrosiphum spp., Macrosiphum avenae, Myzus spp., Myzus persicae, Phorodon spp., Phorodon humuli, Rhopalosiphum spp., Rhopalosiphum padi, Empoasca spp., Euscelis spp., Eulecanium spp., Saissetia spp., Aonidiella spp., Aonidiella aurantii, Aspidiotus spp., Nephotettix spp., Nephotettix cincticeps, Laodelphax spp., Laodelphax striatellus, Nilaparvata spp., Nilaparvata lugens, Sogatella spp., Pseudococcus spp., Psylla spp., Psylla mali, Aphrophora spp., Aeneolamia spp.
    From the order of the Lepidoptera, for example, Pectinophora spp., Pectinophora gossypiella, Bupalus spp., Cheimatobia spp., Cnephasia spp., Hydraecia spp., Lithocolletis spp., Hyponomeuta spp., Plutella spp., Plutella xylostella, Malacosoma spp., Euproctis spp., Lymantria spp., Bucculatrix spp., Phytometra spp., Scrobipalpa spp., Phthorimaea spp., Gnorimoschema spp., Autographa spp., Evergestis spp., Lacanobia spp., Cydia spp., Cydia pomonella, Pseudociaphila spp., Phyllocnistis spp., Agrotis spp., Agrotis segetum, Agrotis ipsilon, Euxoa spp., Feltia spp., Earias spp., Heliothis spp., Heliothis virescens, Heliothis armigera, Heliothis zea, Helicoverpa spp., Helicoverpa armigera, Helicoverpa zea, Bombyx spp., Bombyx mori, Laphygma spp., Mamestra spp., Mamestra brassicae, Panolis spp., Prodenia spp., Prodenia litura, Spodoptera spp., Spodoptera littoralis, Spodoptera litura, Spodoptera exigua, Trichoplusia spp., Trichoplusia ni, Carpocapsa spp., Carpocapsa pomonella, Pieris spp., Pieris brassicae, Chilo spp., Chilo suppressalis, Ostrinia spp., Ostrinia nubilalis, Pyrausta spp., Pyrausta nubilalis, Ephestia spp., Ephestia kuehniella, Galleria spp., Galleria mellonella, Cacoecia spp., Capua spp., Choristoneura spp., Clysia spp., Hofmannophila spp., Homona spp., Tineola spp., Tinea spp., Tinea pellionella, Tortrix spp. Tortrix vitisana, Lobesia spp., Lobesia botrana. 
    From the order of the Coleoptera, for example, Anobium spp., Rhizopertha spp., Rhizopertha dominica, Bruchidius spp., Bruchidius obtectus, Acanthoscelides spp., Acanthoscelides obtectus, Hylotrupes spp., Aclypea spp., Agelastica spp., Leptinotarsa spp., Leptinotarsa decemlineata, Psylliodes spp., Chaetocnema spp., Cassida spp., Bothynoderes spp., Clivina spp., Ceutorhynchus spp., Ceutorhynchus assimilis, Phyllotreta spp., Apion spp., Sitona spp., Bruchus spp., Phaedon spp., Phaedon cochleariae, Diabrotica spp., Diabrotica undecimpunctata, Diabrotica virgifera, Psylloides spp., Epilachna spp., Epilachna varivestis, Atomaria spp., Atomaria linearis, Oryzaephilus spp., Anthonomus spp., Anthonomus grandis, Sitophilus spp., Sitophilus granarius, Sitophilus oryzae, Otiorhynchus spp., Otiorrhynchus sulcatus, Cosmopolites spp., Ceuthorrynchus spp., Hypera spp., Dermestes spp., Trogoderma spp., Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes spp., Meligethes aeneus, Ptinus spp., Niptus spp., Gibbium spp., Tribolium spp., Tenebrio spp., Tenebrio molitor, Agriotes spp., Agriotes lineatus, Conoderus spp., Melolontha spp., Melolontha melolontha, Amphimallon spp., Costelytra spp., Costelytra zealandica. 
    From the order of the Hymenoptera, for example, Diprion spp., Diprion pini, Hoplocampa spp., Lasius spp., Monomorium spp., Vespa spp.
    From the order of the Diptera, for example, Drosophila spp., Drosophila melanogaster, Chrysomyxa spp., Hypoderma spp., Tannia spp., Bibio spp., Bibio hortulanus, Oscinella spp., Oscinella frit, Phorbia spp., Pegomyia spp., Anastrepha spp., Ceratitis spp., Dacus spp., Rhagoletis spp., Bactrocera spp., Toxotrypana spp., Tipula spp., Tipula paludosa, Tipula oleracea, Dermatobia spp., Dermatobia hominis, Cordylobia spp., Cordylobia anthropophaga, Gasterophilus spp., Hypoderma spp., Cuterebra spp., Cochliomyia spp., Wohlfahrtia spp., Stomoxys spp., Calliphora spp., Calliphora erythrocephala, Gastrophilus spp., Hyppobosca spp., Lucilia spp., Lucilia sericata, Musca spp., Musca domestica, Fannia spp., Fannia canicularis, Oestrus spp., Tabanus spp., Aedes spp., Aedes aegypti, Culex spp., Culex quinquefasciatus, Anopheles spp., Anopheles arabiensis. 
    From the order of the Siphonaptera, for example, Xenopsylla spp., Xenopsylla cheopsis, Ctenocephalides spp., Ctenocephalides felis, Ctenocephalides canis, Ceratophyllus spp., Pulex spp., Pulex irritans. 
    From the order of the Acarina, for example, Acarus spp., Acarus siro, Bryobia spp., Bryobia praetiosa, Panonychus spp., Panonychus ulmi, Panonychus citri, Tetranychus spp., Tetranychus urticae, Eotetranychus spp., Oligonychus spp., Eutetranychus spp., Eriophyes spp., Eriophyes ribis, Phyllocoptruta spp., Phyllocoptruta oleivora, Tarsonemus spp., Argas spp., Argas reflexus, Argas persicus, Ornithodoros spp., Ornithodoros moubata, Dermacentor spp., Dermacentor marginatus, Hyalomma spp., Dermanyssus spp., Dermanyssus gallinae, Boophilus spp., Boophilus microplus, Haemaphysalis spp., Psoroptes spp., Chorioptes spp., Sarcoptes spp., Rhipicephalus spp., Rhipicephalus sanguineus, Ixodes spp., Ixodes ricinus, Amblyomma spp.
    From the class of the helminths, for example, Schistosomen spp., Fasciola spp., Dicrocoelium spp., Opisthorchis spp., Clonorchis spp., Paragonimus spp., Taenia saginata, Taenia solium, Echinococcus granulosus, Echinococcus multilocularis, Hymenolepis nana, Diphyllobothrium latum, Onchocerca volvulus, Wuchereria bancrofti, Brugia malayi, Brugia timori, Loa Loa, Dracunculus medinensis, Enterobius vermicularis, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Ascaris spp., Ascaris lumbricoides, Trichuris trichuria, Ancylostoma duodenale, Ancylostoma ceylanicum, Ancylostoma braziliensis, Strongyloides stercoralis, Strongyloides fuelleborni, Haemonchus spp., Ostertagia spp., Trichostrongulus spp., Cooperia spp., Bunostomum spp., Nematodirus spp., Chabertia spp., Strongyloides spp., Oesophagostomum spp., Hyostrongulus spp., Ancylostoma spp., Dictyocaulus filaria, Heterakis spp; and from the sub-group of the phytoparasitic nematodes, for example, Meloidogyne spp., Meloidogyne incognita, Meloidogyne hapla, Meloidogyne javanica, Heterodera spp., Heterodera trifolii, Heterodera avenae, Heterodera schachtii, Heterodera glycines, Globodera spp., Globodera rostochiensis, Globodera pallida, Radopholus spp., Radopholus similis, Pratylenchus spp., Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus; Tylenchulus spp., Tylenchulus semipenetrans, Tylenchorhynchus spp., Tylenchorhynchus dubius, Tylenchorhynchus claytoni, Rotylenchus spp., Rotylenchus robustus, Heliocotylenchus spp., Haliocotylenchus multicinctus, Belonoaimus spp., Belonoaimus longicaudatus, Longidorus spp., Longidorus elongatus, Trichodorus spp., Trichodorus primitivus, Xiphinema spp., Xiphinema index, Ditylenchus spp., Ditylenchus dipsaci, Ditylenchus destructor, Aphelenchoides spp., Aphelenchoides ritzemabosi, Anguina spp., Anguina tritici. 


The compounds of the formula (I) are also suitable for controlling animal pests, in particular arthropods, such as insects and Acarina, in rooms, specifically for controlling flies, such as, for example, from the family Muscidae (for example common house-flies, domestic flies), Calliphoridae (for example greenbottles, “death flies” (Cynomyia mortuorum), bluebottles) and Sarcophagidae (for example flesh-flies), mosquitoes, such as, for example, Aedes aegypti, Anopheles arabiensis and Culex quinquefasciatus, and cockroaches, such as, for example Blattella germanica and Periplaneta americana. 
The invention relates to compositions, for example pesticidal compositions, preferably insecticidal, acaricidal, ixodicidal, or helminthicidal/nematicidal, particularly preferably insecticidal, acaricidal and helminthicidal/nematicidal compositions which comprise one or more compounds of the formula (I) in addition to suitable formulation auxiliaries.
In general, the compositions according to the invention comprise from 1 to 95% by weight of the active compounds of the formula (I).
For preparing the compositions according to the invention, the active compound and the other additives are combined and formulated as a suitable use form.
They can be formulated in various ways, depending on how this is predetermined by the biological and/or chemico-physical parameters. Suitable formulation possibilities are therefore:
Wettable powders (WP), emulsifiable concentrates (EC), aqueous solutions (SL), emulsions, sprayable solutions, oil- or water-based dispersions (SC), suspoemulsions (SE), dusting powders (DP), seed dressings, granules in the form of microgranules, sprayed granules, absorption granules and adsorption granules, water-dispersible granules (WG), ULV formulations, microcapsules, waxes or baits. In addition, the compositions can be employed as dips or mist applications, in the form of foams, pastes, gels, ointments, lotions, shampoos, hair-setting compositions, active-compound-containing mats (for example flat or in the form of a cushion), impregnated articles, aerosols, pressurized and non-pressurized sprays, additives to color lacques and foodstuff, and also for use as fumigants and evaporator compositions, as combustible solids (for example in the form of a cone or coil) or as combustible oils (distributed, for example, via a heated wick) and in further formulations familiar to the person skilled in the art.
These individual types of formulation 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 Edition 1972–73; K. Martens, “Spray Drying Handbook”, 3rd Edition 1979, G. Goodwin Ltd. London.
The necessary formulation auxiliaries, i.e. carrier and/or surface-active substances such as inert materials, surfactants, solvents and further additives, are likewise known and are described, for example, in: Watkins, “Handbook of Insecticide Dust Diluents and Carriers”, 2nd Edition, Darland Books, Caldwell N.J.; H. v. Olphen, “Introduction to Clay Colloid Chemistry”, 2nd Edition, J. Wiley –Sons, N.Y.; Marsden, “Solvents Guide”, 2nd Edition, 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” [Chemical Technology], Volume 7, C. Hanser Verlag Munich, 4th Edition 1986.
Combinations with other substances having a pesticidal action, fertilizers and/or growth regulators can be prepared on the basis of these formulations, for example in the form of a ready-to-use formulation or as a tank mix. Wettable powders are preparations which are uniformly dispersible in water and which, alongside the active compound, and in addition to a diluent or inert substance, also comprise wetting agents, for example polyethoxylated alkylphenols, polyethoxylated fatty alcohols or alkyl- or alkylphenolsulfonates, and dispersing agents, for example sodium lignosulfonate or sodium 2,2′-dinaphthylmethane-6,6′-disulfonate.
Emulsifiable concentrates are prepared by dissolving the active compound in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or also higher-boiling aromatics or hydrocarbons, with the addition of one or more emulsifiers. Emulsifiers which can be used are, for example: calcium alkylaryl-sulfonates, such as Ca dodecylbenzenesulfonate, or nonionic emulsifiers, such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ethylene oxide condensation products, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
Dusting powders are obtained by, for example, grinding the active compound with finely divided solid substances, for example talc, naturally occurring clays, such as kaolin, bentonite and pyrophyllite, or diatomaceous earth. Granules can be prepared either by spraying the active compound onto granular inert material capable of adsorption or by applying active compound concentrates to the surface of carrier substances, such as sand, kaolinites or granular inert material, by means of adhesives, for example polyvinyl alcohol, sodium polyacrylate or mineral oils. Suitable active compounds can also be granulated in the manner customary for the preparation of fertilizer granules—if desired as a mixture with fertilizers.
Aerosols, sold, for example, in cans, are prepared by dissolving the active compound in water and/or organic solvents, such as, for example, acetone, deodorized petroleum, saturated C8–C13-hydrocarbons, vegetable oils, with addition of further suitable substances, such as, for example, emulsifiers, piperonyl butoxide, sorbitan monooleate, polyoxyethylene glycerol monooleate, fragrances and suitable propellents, such as, for example, carbon dioxide or butane. Ready-to-use sprays, for example for use in rooms, are obtained, for example, by mixing the active compound with odorless kerosine and antioxidants, it being possible to admix further additives, such as, for example, emulsifiers, synergists (for example piperonyl butoxide) or fragrances. Baits can be prepared, for example, by mixing the active compound with attractants and/or foodstuffs, such as, for example, sugar, and also carrier materials, such as, for example, paraffin wax.
A further advantageous embodiment for use in rooms is the use as a fumigant and an evaporator composition, which can be employed by various methods. In one of these methods, combustible solids, such as, for example, sawdust (for example pine sawdust), starch and coconut shell powder and also powdered leaves and stalks of further plants (for example pyrethrum, cedar) are, with addition of colorants and, if appropriate, fungicides, solidifed in specific forms, such as, for example, a meander, a coil or a cone, using suitable binders, and the active compound is then applied. The active compound is then distributed in the room by slow and controlled burning. In another method, mats or cushions of non-combustible fibers are used as carriers into which the active compound and, if appropriate, further substances are incorporated. These carriers are placed onto a heating plate which is heated under controlled conditions, thus releasing the active compound. In a further method, an oil is used to which the active compound is added and into which a wick consisting, for example, of cotton and/or cellulose in compressed form, is dipped, which wick releases the active compound from the oil into the room on burning. In a variant of this method, a wick of non-combustible fibers is used which is heated by an electric device, thus effecting the distribution of the active compound contained in the oil throughout the room. In the above-mentioned methods, the active compound is applied either directly or in already formulated form. Frequently, for example, colorants and fragrances are added, and also suitable fungicides for protecting the carriers made of natural products against natural decomposition.
In wettable powders, the active compound concentration is usually about 10 to 90% by weight, the remainder to make up 100% by weight comprising customary formulation constituents. In emulsifiable concentrates, the active compound concentration can be about 5 to 80% by weight. Dust-like formulations usually comprise 5 to 20% by weight of active compound, and sprayable solutions about 2 to 20% by weight. In granules, the content of active compound partly depends on whether the active compound is present in liquid or solid form and what granulating auxiliaries, fillers and the like are used. Baits generally comprise from 0.01 to 60% by weight of active compound, preferably from 0.1 to 5% by weight; aerosols generally comprise from 0.01 to 50% by weight, preferably from 0.1 to 5% by weight; ready-to-use sprays generally comprise from 0.01 to 50% by weight, preferably from 0.05 to 10% by weight. The active compound contents in fumigants and evaporator compositions are, in the case of combustible solids, generally in the range from 0.01 to 60% by weight, in the case of active-compound-comprising mats and cushions in the range from 0.01 to 60% by weight and in the case of active-compound-comprising oils in the range from 0.01 to 90% by weight.
In addition, the active compound formulations mentioned comprise, if appropriate, the particular customary tackifiers, wetting agents, dispersing agents, emulsifiers, penetration agents, solvents, fillers or carrier substances.
For use, the concentrates in the commercially available form are diluted in the customary manner, if appropriate, for example by means of water in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules. Dust-like and granular formulations as well as sprayable solutions are usually not diluted further with additional inert substances before use.
The required amount applied varies with the external conditions, such as temperature or humidity. It can vary within wide limits, for example between 0.0005 and 10.0 kg/ha or more of active substance, but is preferably between 0.001 and 5 kg/ha.
The active compounds according to the invention can be present in their commercially available formulations and in the use forms prepared from these formulations in mixtures with other active compounds, for example pesticides such as insecticides, attractants, sterilizing agents, acaricides, nematicides, fungicides, molluscides, growth-regulating substances or herbicides.
The pesticides include, for example, phosphoric acid esters, carbamates, carboxylic acid esters, formamidines, tin compounds and substances produced by microorganisms.
Preferred partners for the mixtures are:

    1. from the group of 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, phosphocarb (BAS-301), phosmet, phosphamidon, phoxim, pirimiphos, primiphos-ethyl, pirimiphos-methyl, profenofos, propaphos, proetamphos, prothiofos, pyraclofos, pyridapenthion, quinalphos, sulprofos, temephos, terbufos, tebupirimfos, tetrachlorvinphos, thiometon, triazophos, trichlorphon, vamidothion;
    2. from the group of carbamates
    alanycarb (OK-135), aldicarb, 2-sec-butylphenyl methylcarbamate (BPMC), carbaryl, carbofuran, carbosulfan, cloethocarb, benfuracarb, ethiofencarb, furathiocarb, HCN-801, isoprocarb, methomyl, 5-methyl-m-cumenyl butyryl(methyl)carbamate, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, 1-methylthio(ethylideneamino) N-methyl-N-(morpholinothio)carbamate (UC 51717), triazamate;
    3. from the group of carboxylic acid esters
    acrinathrin, allethrin, alphametrin, 5-benzyl-3-furylmethyl (E)-(1R)-cis-2,2-di-methyl-3-(2-oxothiolan-3-ylidenemethyl)cyclopropanecarboxylate, beta-cyfluthrin, beta-cypermethrin, bioallethrin, bioallethrin ((S)-cyclopentyl isomer), 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, pheothrin ((R) isomer), prallethrin, pyrethrins (natural products), resmethrin, tefluthrin, tetramethrin, theta-cypermethrin (TD-2344), tralomethrin, transfluthrin and zeta-cypermethrin (F-56701);
    4. from the group of amidines
    amitraz, chlordimeform;
    5. from the group of 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 cyclopropanecarboxylate (Ro12-0470), cyromazin, diacloden (thiamethoxam), diafenthiuron, N-(3,5-dichloro-4-(1,1,2,3,3,3-hexafluoro-1-propyloxy)phenyl)carbamoyl)-2-chlorobenzocarboxamide acid ethyl ester, 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), 2-fluoro-5-(4-(4-ethoxyphenyl)-4-methyl-1-pentyl)diphenyl ether (MTI 800), granulosis and nuclear polyhedrosis viruses, fenpyroximate, fenthiocarb, flubenzimine, flucycloxuron, flufenoxuron, flufenprox (ICI-A5683), fluproxyfen, gamma-HCH, halofenozide (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, pyrimidifen (SU-8801), RH-0345, RH-2485, RYI-210, S-1283, S-1833, SB7242, SI-8601, silafluofen, silomadine (CG-177), spinosad, SU-9118, 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 are known active substances, many of which are described in C D S Tomlin (Editor), The Pesticide Manual, 12th edition, The British Crop Protection Council, Farnham, UK, 2000.
The active compound content of the use forms prepared from the commercially available formulations can be from 0.00000001 to 95% by weight of active compound, preferably between 0.00001 and 1% by weight. The active compounds are used in a customary manner appropriate for the use forms.
The compounds of the formula (I) can be employed in their commercially available formulations, also in combination with fungicides. These fungicides are generally active compounds which are described in C D S Tomlin (Editor), The Pesticide Manual, 12th edition, The British Crop Protection Council, Farnham, UK, 2000. Appiication is carried out in a customary manner adapted to suit the use forms, for example in the control of pathogenic fungi by applying a fungicidally effective amount of a compound according to the invention or a composition according to the invention to these fungi or to the plants, areas or substrates infected with them, or to seed.
The compounds of the formula (I) can also be employed for controlling harmful organisms in crops of known or yet to be developed genetically engineered plants. As a rule, the transgenic plants are distinguished by particular advantageous properties, for example by resistances to certain crop protection agents, resistances to plant diseases or pathogens of plant diseases such as certain insects or microorganisms such as fungi, bacteria or viruses. Other particular properties relate, for example, to the harvested material with regard to quantity, quality, storage properties, composition and specific constituents. Thus, transgenic plants with an elevated starch content or altered starch quality, or those with a different fatty acid spectrum of the harvested material, are known.
The use in economically important transgenic crops of useful plants and ornamentals, for example, cereals such as wheat, barley, rye, oats, millet, rice, manioc and corn or else crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types of vegetables is preferred.
When being used in transgenic crops, in particular those in which the plants express an insecticide, effects are frequently found (in addition to the pesticidal effects which can be observed in other crops) which are specific to 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 can be used for application.
The compounds of the formula (I) according to the invention or the compositions comprising them are used, for example, in agriculture, in horticulture, in forests and in the protection of materials and food. They are preferably used in economically important crops of useful plants and ornamentals, for example of cereals, such as wheat, barley, rye, oats, millet, rice, manioc and corn, or else crops of sugar beet, cotton, soya, oilseed rape, potatoes, tomatoes, peas and other types of vegetables.
The use of the compounds according to the invention embraces, in addition to direct application onto the harmful organisms, any other application in which compounds of the formula (I) act on the harmful organisms. Such indirect applications can, for example, be the use of compounds which, for example in the soil, the plant or the harmful organism, decompose into compounds of the formula (I) or are degraded into compounds of the formula (I).
The use according to the invention of compounds of the formula (I) or compositions comprising them, for example as insecticide, acaricide or helminthicide/nematicide, also includes the case where the compound of the formula (I) or its salt is formed from a precursor only after application, for example in the harmful organism, in a plant or in the soil.
In addition to the above mentioned and customary 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 (for example root, stolons, stem, trunk, leaf), if the active compounds are applied, in liquid or solid form, on or into the plant or into the direct vicinity of the plant (for example granules in soil application, application in flooded rice paddies, trunk injection in the case of trees, stem bandages in the case of perennial plants).
In addition, the active compounds according to the invention are particularly suitable 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 treatment methods for plant propagation material and the plant propagation material treated in this manner are also provided by the invention.
The active compounds according to the invention are also suitable for use in the veterinary field, preferably for controlling endoparasites and ectoparasites, and in the field of animal husbandry. The active compounds according to the invention can be applied 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 in livestock keeping (for example cattle, sheep, pigs and poultry such as chicken, 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 established and determined readily by customary methods. In cattle the compounds can be employed at dosages of, for example, from 0.01 to 1 mg/kg of body weight.
In addition, the compounds according to the invention are also suitable for use in technical fields, for example as wood preservatives, as preservatives in paints, in cooling lubricants for metal working, or as preservatives in drilling and cutting oils.
Further preferred areas of use are the protection of stored products and materials, the hygiene sector and the domestic sector where, in a preferred embodiment of the invention, the composition according to the invention is used in the buildings in question and, if appropriate, combined with further measures, such as, for example, sticky boards or traps. Here, too, suitable dosages and formulations depend in particular on the type and the intensity of the risk of infestation and can be established and determined readily by customary methods.
The invention is illustrated by the examples below. The Preparation Examples may also comprise prior-art compounds which serve to illustrate the preparation process for the compounds according to the invention. Prior-art compounds, listed in the tables below in addition to compounds according to the invention, are also used in the process according to the invention.


A. CHEMICAL EXAMPLES
Example 1
1-(3-o-Tolyl-2-propynyl)piperidine
A mixture of 2-iodotoluene (6.54 g), N-(2-propynyl)piperidine (3.69 g), dichlorobis(triphenylphosphino)palladium(II) (0.05 g) and copper(I) iodide (0.1 g) in dry diethylamine (50 ml) was heated under reflux for 5 hours. The solvent was removed under reduced pressure and the residue was taken up in diethyl ether and washed with water. The organic phase was dried over magnesium sulfate and concentrated completely under reduced pressure. Distillation of the residue under reduced pressure gave 3.98 g of an oil of boiling point 96–98° C./0.08 mm Hg.
Preparation of the starting material 1-(2-propynyl)piperidine:
With stirring, a solution of 2-propynyl chloride (40.31 g) in dry methanol (50 ml) was added dropwise to a solution of piperidine (92.14 g) in dry methanol (100 ml). The mixture was stirred at 25° C. for 3 hours and then filtered. The filtrate was concentrated under reduced pressure and the residue was distilled (boiling point: 163–165° C./atmospheric pressure).
Example 2
1-(4-Methoxyphenyl-2-propynyl)piperidine hydrochloride
When 2-iodotoluene was replaced by 4-iodoanisole, the process of Example 1 gave a crude product to which excess hydrochloric acid in methanol was added. Removal of the solvent gave, after crystallization from isopropanol, colorless needles of melting point 223–225° C.
Example 3
1-[3-(4-Methoxyphenyl)-2-propynyl]piperidine
The product from Example 2 was dissolved in water and the solution was made alkaline using 2N aqueous sodium hydroxide solution and extracted with diethyl ether. The ether extracts were dried using magnesium sulfate, and the solvent was then removed and the residue was distilled under reduced pressure. This gave an oil of boiling point 126–128° C./0.1 mm Hg.
Example 4
1-[3-(3-Fluorophenyl)-2-propynyl]-4-methylpiperidine
A mixture of 3-fluoroiodobenzene (8.88 g), 4-methyl-1-(2-propynyl)piperidine (6.80 g), palladium acetate (0.045 g), tri-o-toloylphosphine (0.24 g) and copper(I) iodide (0.1 g) in dry diethylamine (50 ml) was heated under reflux for 5 hours. The solvent was removed under reduced pressure and the residue was taken up in diethyl ether and washed with water. The organic phase was dried over magnesium sulfate and the solvent was removed under reduced pressure. Distillation of the residue under reduced pressure gave an oil (5.20 g) of boiling point 105° C./0.07 mm Hg.
Preparation of the starting material 4-methyl-1-(2-propynyl)piperidine: At 0–5° C., propargyl bromide (12.01 g) was added dropwise with stirring to a suspension of 4-methylpiperidine (10.0 g) and potassium carbonate (13.96 g) in dry acetone (80 ml). The mixture was stirred at 50° C. for 6 hours and then filtered. The filtrate was concentrated under reduced pressure and the residue was taken up in dichloromethane. The organic phase was washed with water (3×15 ml), dried with sodium sulfate and concentrated under reduced pressure. Distillation of the residue under reduced pressure gave 12.73 g of an oil of boiling point 60° C./16 mm Hg.
Example 5
1-(3-phenyl-2-propynyl)piperidine
With stirring, a solution of phenylacetylene (10.2 g) in dioxane (10 ml), a solution of piperidine (13.3 g) in dioxane (10 ml) and copper(I) chloride (0.1 g) were added successively to a suspension of paraformaldehyde (3.6 g) in dioxane (10 ml). The mixture was heated under reflux for 6 hours, allowed to cool to 25° C. and acidified using 20% strength hydrochloric acid. The solution was washed with diethyl ether and the aqueous phase was made alkaline using 50% strength aqueous sodium hydroxide solution and extracted with diethyl ether (3×100 ml). The organic phase was dried with magnesium sulfate and concentrated completely. Distillation of the residue under reduced pressure gave an oil (13.0 g) of boiling point 95° C./0.045 mm Hg.
Example 6
1-[3-(3,5-Bistrifluoromethylphenyl)-2-propynyl]piperidine
A mixture of 1-(3,5-bistrifluoromethylphenyl)-3-bromoprop-1-yne (2.53 g), piperidine (5 ml) and anhydrous potassium carbonate (5 g) in dry acetone (50 ml) was heated at reflux with stirring for 18 h. Removal of the solvent under reduced pressure and distillation of the residue under reduced pressure gave 2.26 g of an oil of boiling point 95° C./0.025 mm Hg.
Example 7
1-[3-(3,5-Bistrifluoromethylphenyl)-2-propynyl]piperidine hydrochloride
An excess of dry HCl gas was passed through a solution of 1-(3,5-bistrifluoromethylphenyl)-3-piperidinoprop-1-yne (2.26 g) in dry diethyl ether (200 ml). Filtration, washing (diethyl ether) and drying of the resulting white precipitate gave 2.16 g of a fine white powder of melting point 214.5° C.
The compounds of the tables below were obtained analogously to Examples 1 to 7.
In the tables, the following abbreviations are used
















L1







 



L2







 



L3







 



L4







 



L5







 



L6







 



L7







 



L8







 



L9







 



L10







 



L11







 



L12







 



L13







 



L14







 



L15







 



L16







 



L17







 



L18







 



L19







 



L20







 



L21







 



L22







 



L23







 



L24







 



L25







 



L26







 



L27







 



L28







 



L29







 



L30







 



L31







 



L32







 



L33







 



L34







 



L35







 



L36







 



L37







 



L38







 



L39







 



L40







 



L41







 



L42







 



L43







 



L44







 



L45







 



L46







 



L47







 



L48







 



L49







 



L50







 



L51







 



L52







 



L53







 



L54







 



L55







 



L56







 



L57







 



L58







 



L59







 



L60







 



L61







 



L62







 



L63







 



L64







 



L65







 



L66







 



L67







 



L68







 



L69







 



L70







 



L71







 



L72







 



L73







 



L74







 



L75







 



L76







 



L77







 



L78







 



L79







 



L80







 



L81







 



L82







 



L83







 



L84







 



L85







 



L86







 



L87







 



L88







 



L89







 



L90







 



L91







 



L92







 



L93





















 












Ti
U1
V1
W1
X1
Y1





T1
H
H
H
H
H


T2
Cl
H
H
H
H


T3
H
Cl
H
H
H


T4
H
H
Cl
H
H


T5
Cl
Cl
H
H
H


T6
Cl
H
Cl
H
H


T7
Cl
H
H
Cl
H


T8
Cl
H
H
H
Cl


T9
H
Cl
Cl
H
H


T10
H
Cl
H
Cl
H


T11
H
Cl
H
H
Cl


T12
Cl
Cl
Cl
H
H


T13
Cl
Cl
H
Cl
H


T14
Cl
Cl
H
H
Cl


T15
Cl
H
Cl
Cl
H


T16
Cl
H
Cl
H
Cl


T17
Cl
Cl
Cl
Cl
H


T18
Cl
Cl
Cl
H
Cl


T19
Cl
Cl
H
Cl
Cl


T20
Cl
Cl
Cl
Cl
Cl


T21
F
H
H
H
H


T22
H
F
H
H
H


T23
H
H
F
H
H


T24
F
F
H
H
H


T25
F
H
F
H
H


T26
F
H
H
F
H


T27
F
H
H
H
F


T28
H
F
F
H
H


T29
H
F
H
F
H


T30
H
F
H
H
F


T31
CF3
H
H
H
H


T32
H
CF3
H
H
H


T33
H
H
CF3
H
H


T34
CF3
CF3
H
H
H


T35
CF3
H
CF3
H
H


T36
CF3
H
H
CF3
H


T37
CF3
H
H
H
CF3


T38
H
CF3
CF3
H
H


T39
H
CF3
H
CF3
H


T40
H
CF3
H
H
CF3


T41
H
CF3
CF3
CF3
H


T42
Cl
CF3
H
H
H


T43
Cl
H
CF3
H
H


T44
Cl
H
H
CF3
H


T45
Cl
H
H
H
CF3


T46
H
Cl
CF3
H
H


T47
H
Cl
H
CF3
H


T48
H
Cl
H
H
CF3


T49
H
H
Cl
CF3
H


T50
H
H
Cl
H
CF3


T51
H
H
H
Cl
CF3


T52
Me
Cl
H
H
H


T53
H
Cl
Me
H
H


T54
H
Cl
H
Me
H


T55
H
Me
Cl
H
H


T56
Me
H
Cl
H
H


T51
H
F
Cl
H
H


T58
H
F
H
Cl
H


T59
H
Cl
F
H
H


T60
H
NO2
H
H
H


T61
H
H
NO2
H
H


T62
H
CN
H
H
H


T63
H
H
CN
H
H


T64
H
NO2
Cl
H
H


T65
H
NO2
H
Cl
H


T66
H
Cl
NO2
H
H


T67
H
CN
Cl
H
H


T68
H
CN
H
Cl
H


T69
H
Cl
CN
H
H


T70
H
NO2
CF3
H
H


T71
H
NO2
H
CF3
H


T72
H
CF3
NO2
H
H


T73
H
CN
CF3
H
H


T74
H
CN
H
CF3
H


T75
H
CF3
CN
H
H


T76
H
Me
H
H
H


T77
H
H
Me
H
H


T78
COOMe
H
H
H
H


T79
H
COOMe
H
H
H


T80
H
H
COOMe
H
H


T81
H
Cl
Cl
OMe
H


T82
H
Cl
OMe
Cl
H


T83
H
CF3
OMe
CF3
H


T84
H
CF3
OMe
Cl
H


T85
OMe
H
H
H
H


T86
H
OMe
H
H
H


T87
H
H
OMe
H
H


T88
Me
H
H
H
H


T89
H
SMe
H
H
H


T90
H
H
SMe
H
H


T91
H
Ph
H
H
H


T92
H
Ph
Cl
H
H


T93
H
Ph
CF3
H
H


T94
H
H
Ph
H
H


T95
H
Cl
Ph
H
H


T96
H
CF3
Ph
H
H


T97
H
Cl
Ph
Cl
H


T98
H
CF3
Ph
CF3
H


T99
H
H
HC═CH—CF3
H
H


T100
H
Cl
HC═CH—CF3
H
H


T101
H
HC═CH—CF3
H
H
H


T102
H
HC═CH—CF3
Cl
H
H


T103
H
H
OEt
H
H


T104
H
H
Et
H
H


T105
H
Me
F
H
H


T106
Me
H
F
H
H


T107
Cl
H
H
Me
H


T108
Me
H
H
F
H


T109
H
OC(O)Pr
H
H
H


T110
Me
H
H
Cl
H


T111
Me
H
Me
H
H


T112
Cl
H
H
H
Me


T113
Me
Me
H
H
H


T114
Me
H
H
H
Me


T115
Et
H
H
H
H


T116
H
Me
Me
H
H


T111
H
SO2Me
H
H
H


T118
Pri
H
H
H
H


T119
F
H
F
H
F


T120
EtO
H
H
H
H


T121
F
H
H
F
H


T122
F
H
F
H
H


T123
H
Cl
Cl
Me
H


T124
H
H
Pri
H
H


T125
F
F
F
F
F


T126
Me
H
H
Me
H


T127
H
H
OPh
H
H


T128
H
H
C(O)Me
H
H











T129
H
OCH2O
H
H












T130
H
Me
H
Me
H


T131
H
CF3
H
OMe
H


T132
H
F
Me
H
H


 


T133
H
H




H
H


 


T134
H
Cl
F
Cl
H


T135
H
CF3
COOMe
H
H


T136
H
OMe
OMe
H
H


T137
H
Cl
Cl
Cl
H


T138
H
NO2
H
NO2
H


T139
H
CF3
H
NO2
H


T140
Cl
H
CF3
H
Cl


T141
H
C(O)Me
H
H
H


T142
H
H
(2-Cl,5-CF3)Ph
H
H


T143
H
H
(4-CF3)Ph
H
H


T144
H
H
(3-Cl)Ph
H
H


T145
H
H
(2-Cl)Ph
H
H


T146
H
H
(3-Me,5-Me)Ph
H
H


T147
H
H
(4-OMe)Ph
H
H


T148
H
H
(2-Cl,4-Cl)Ph
H
H


T149
H
H
(3-F,5-NO2)Ph
H
H


T150
H
H
(3-CO2Et)Ph
H
H


T151
H
H
(2-Me,5-NO2)Ph
H
H


T152
H
H
(2-Cl,3-Cl)Ph
H
H


T153
H
H
(3-CF3)Ph
H
H


T154
H
H
(2-Me)Ph
H
H


 


T155
H
H




H
H


 


T156
H
H




H
H


 


T157
H
H




H
H


 


T158
H
H




H
H


 


T159
H
H




H
H


 


T160
H
H




H
H


 


T161
H
H
(4-CN)Ph
H
H


T162
H
H
2-thienyl
H
H


T163
H
H
(2-F,6-F)Ph
H
H


 


T164
H
H




H
H


 


T165
H
H




H
H


 


T166
H
H
(4-OCH2CF3)Ph
H
H


T167
H
H
(4-Me)Ph
H
H


T168
H
F
Br
H
H


T169
H
CF3
Br
H
H


T170
H
(4-CF3)Ph
H
H
H


T171
H
(3-CF3,5-
H
H
H




CF3)Ph


T172
H
(3-Cl)Ph
H
H
H


T173
H
(4-NO2)Ph
H
H
H


T174
H
1-Naphthyl
H
H
H


T175
H
(4-Cl)Ph
H
H
H


 


T176
H




H
H
H


 


T177
H




H
H
H


 


T178
H




H
H
H


 


T179
H
(4-CN)Ph
H
H
H


 


T180
H




H
H
H


 


T181
H
F
(4-F)Ph
H
H


T182
H
F
Et
H
H


T183
H
CF3
Et
H
H


T184
H
CF3
H
Me
H


T185
H
Cl
OCF2CHFCl
Cl
H


T186
H
CF3
Me
H
H


T187
H
CF3
F
H
H


T188
F
Cl
F
H
H


T189
H
F
(4-OMe)Ph
H
H


T190
H
F
(4-Me)Ph
H
H


T191
H
F
(3-Cl,4-F)Ph
H
H


T192
H
F
(4-CF3)Ph
H
H


T193
H
F
(3,4-
H
H





OCH2CH2O)Ph


T194
H
F
[4-C(O)Me]Ph
H
H


T195
H
F
(4-OCF3)Ph
H
H


T196
H
F
(4-tBu)Ph
H
H


T197
H
F
(4-Cl)Ph
H
H


T198
H
F
(3-Me)Ph
H
H


T199
H
F
(3-Cl)Ph
H
H


T600
H
CF3
(4-SMe)Ph
H
H


T601
H
CF3
3-thienyl
H
H


T602
H
CF3
(4-CF3)Ph
H
H


T603
H
CF3
(4-OCF3)Ph
H
H


T604
H
CF3
[4-C(O)Me]Ph
H
H


T605
H
CF3
(4-Cl)Ph
H
H


T606
H
CF3
1-Naphthyl
H
H


T607
H
CF3
(2-F)Ph
H
H


T608
H
CF3
(2-Cl)Ph
H
H


T609
H
F
3-thienyl
H
H
















 













Tj
U2
V2
W2
X2







T200
Cl
H
CF3
H



T201
H
Cl
CF3
H



T202
H
H
CF3
Cl



T203
H
CF3
H
Cl



T204
CF3
H
H
Cl



T205
Cl
CF3
H
H



T206
Cl
H
H
CF3



T207
H
Cl
H
CF3



T208
H
H
Cl
CF3



T209
CF3
Cl
H
H



T210
H
CF3
Cl
H



T211
CF3
H
Cl
H



T212
Br
H
H
H



T213
H
Br
H
H



T214
H
H
Br
H



T215
H
H
H
Br



T216
CF3
H
H
H



T217
H
CF3
H
H



T218
H
H
CF3
H



T219
H
H
H
CF3



T220
H
H
H
H



T221
CN
H
H
H



T222
H
CN
H
H



T223
H
H
CN
H



T224
H
H
H
CN



T225
NO2
H
H
H



T226
H
NO2
H
H



T227
H
H
NO2
H



T228
H
H
H
NO2



T229
CF3
CF3
H
H



T230
CF3
H
CF3
H



T231
CF3
H
H
CF3



T232
H
CF3
CF3
H



T233
H
CF3
H
CF3



T234
H
H
CF3
CF3



T235
Cl
H
OCF2CF2H
H



T236
H
CF3
H
Me



T237
H
Me
H
Me



T238
H
CF3
CN
Cl

















 












Tk
U3
V3
W3







T300
H
Me
Me



T301
H
Me
SMe



T302
H
Me
Cl



T303
Cl
Me
Cl



T304
H
Me
CF3



T305
Cl
Me
CF3



T306
Br
Me
CF3



T307
Br
Me
Cl



T308
F
Me
Cl



T309
F
Me
CF3



T310
H
Et
Me



T311
F
Et
Me



T312
Cl
Et
Me



T313
Cl
Et
H



T314
Cl
Et
CF3



T315
F
Et
CF3



T316
H
Et
CF3



T317
H
CF3
H



T318
F
CF3
H



T319
Cl
CF3
H



T320
Br
CF3
H



T321
H
CF3
Me



T322
F
CF3
Me



T323
Cl
CF3
Me



T324
Br
CF3
Me



T325
H
CF3
SMe



T326
F
CF3
SMe



T327
Cl
CF3
SMe



T328
Br
CF3
SMe



T329
H
CF3
Cl



T330
F
CF3
Cl



T331
Cl
CF3
Cl



T332
Br
CF3
Cl



T333
H
CF3
CF3



T334
F
CF3
CF3



T335
Cl
CF3
CF3



T336
Br
CF3
CF3



T337
H
CF3
CF3



T338
F
CF3
CCl3



T339
Cl
CF3
CCl3



T340
Br
CF3
CCl3



T341
H
Me
CCl3



T342
F
Me
CCl3



T343
Cl
Me
CCl3



T344
Br
Me
CCl3



T345
Br
H
CCl3



T346
Cl
H
CF2CF2CF3



T347
CF3
H
CF2CF2CF3



T348
COOEt
H
CF3



T349
Me
Me
CF3



T350
H
H
CF3

















 












Tl
U4
V4
W4







T400
H
H
H



T401
Cl
H
H



T402
H
Cl
H



T403
H
H
Cl



T404
CF3
H
H



T405
H
CF3
H



T406
H
H
CF3



T407
H
H
COMe



T408
H
CF3
Cl



T409
H
Cl
CF3



T410
H
Cl
Cl



T411
H
NO2
Br



T412
H
H
CHO



 



T413
H
H







 



T414
H
H







 



T415
H
H
NO2



T416
H
Me
Br



T417
H
H
Br



T418
H
H
(3-CF3)Ph



T419
H
H
(4-F)Ph



T420
H
Me
(4-F)Ph



T421
H
Me
(4-Me)Ph



T422
H
Me
(4-Ph)Ph



T423
H
Me
3-thienyl



T424
H
Me
(4-Cl)Ph



T425
H
H
Ph



T426
H
H
(4-Me)Ph



T427
H
H
(4-CF3)Ph



T428
H
H
(2-Cl)Ph



T429
H
H
(4-OCF3)Ph



T430
H
H
(4-Cl)Ph



T431
H
H
(3-Cl)Ph



T432
H
H
(3-Me)Ph



T433
H
H
(3-CF3, 5-CF3)Ph



T434
H
H
(2-Cl,4-Cl)Ph



T435
H
H
(3-Cl,5-Cl)Ph



T436
H
H
(2-Cl,4-Cl)Ph



T437
H
H
—HC═NOCH2Ph



T438
H
H
Me



T439
H
H
—HC═NOCH2[(2-Cl,






4-Cl)Ph]

















 












Tm
U5
V5
W5







T450
H
H
H



T451
H
CF3
H



T452
H
H
CF3



T453
H
Cl
H



T454
H
H
Cl



T455
Cl
H
H














T500







 



T501







 



T502







 



T503







 



T504







 



T505







 



T506







 



T507







 



T508







 



T509







 



T510







 



T511







 



T512







 



T513







 



T514







 



T515







 



T516







 



T517







 



T518







 



T519







 



T520







 



T521







 



T522







 



T523







 



T524







 



T525







 



T526







 



T527







 



T528







 



T529







 



T530







 



T531











Me = methyl



Et = ethyl



Pr = n-propyl



Pri = isopropyl



Bu = n-butyl



But = tert-butyl



Ph = phenyl



b.p. = boiling point



m.p. = melting point













TABLE 1













 











Comp.No.
R1
A




Physico-chemical data














8
T76
CH2
L2
b.p. 92° C./0.1 mm Hg


9
T78
CH2
L2
b.p. 120–124° C./0.015 mm Hg


10
T60
CH2
L2
b.p. 155° C./0.03 mm Hg


11
T26
CH2
L50
b.p. 110° C./0.04 mm Hg


12
T27
CH2
L50
b.p. 98° C./0.05 mm Hg


13
T8
CH2
L50
m.p. 37–38° C.


14
T49
CH2
L50
b.p. 123–125° C./0.06 mm Hg


15
T12
CH2
L50
m.p.67–68° C.


16
T15
CH2
L50
m.p.79–79.5° C.


17
T82
CH2
L50
m.p. 52–53° C.


18
T49
CH2
L51
b.p. 135° C./0.05 mm Hg


19
T12
CH2
L51
b.p. 142–144° C./0.2 mm Hg


20
T77
CH2
L50
b.p. 118° C./0.05 mm Hg


21
T85
CH2
L50
b.p. 145° C./0.1 mm Hg


22
T63
CH2
L50
m.p. 64–65° C.


23
T61
CH2
L50
m.p. 90–91° C.


24
T32
CH2
L50
b.p. 92–93° C./0.06 mm Hg


25
T88
CH2
L50
b.p. 106–108° C./0.015 mm Hg


26
T31
CH2
L50
b.p. 87–89° C./0.04 mm Hg


27
T76
CH2
L50
b.p. 121° C./0.05 mm Hg


28
T23
CH2
L50
b.p. 91–93° C./0.03 mm Hg


29
T33
CH2
L50
b.p. 96–98° C./0.02 mm Hg


30
T44
CH2
L50
b.p. 97–98° C./0.01 mm Hg


31
T39
CH2
L37
b.p. 90–96° C./0.1 mm Hg


32
T39
CH2
L51 
pale yellow oil


33
T39
CH2
L52
b.p. 88–90° C./1.0 mm Hg


34
T39
CH2
L53
b.p. 110–115° C./0.07 mm Hg


35
T1
CH2
L52
b.p. 98–99° C./0.085 mm Hg


36
T311
CH2
L50
1H-NMR (CDCl3): δ =






0.95 (d, 3H), 1.31 (t, 3H),






2.62 (s, 3H), 3.61 (s, 2H)


37
T313
CH2
L50
1H-NMR (CDCl3): δ =






0.95 (d, 3H), 1.30 (t, 3H),






2.95 (q, 2H), 3.68 (s, 2H)






8.92 (s, 1H)


38
T310
CH2
L50
1H-NMR (CDCl3): δ =






0.95 (d, 3H), 1.30 (t, 3H)






2.70 (s, 3H), 2.75 (q, 2H),






3.56 (s, 2H), 7.06 (s, 1H)


39
T39
CH2
L14
1H-NMR (CDCl3): δ =






1.17 (d, 3H), 3.57 (d, 1H)






3.85 (d, 1H), 7.77 (s, 1H)






7.83 (s, 2H)


40
T39
CH2
L3
1H-NMR (CDCl3): δ =






1.58–1.80 (m, 8H),






2.78 (m, 4H), 3.61 (s, 2H),






7.77 (s, 1H), 7.83 (s, 2H)


41
T39
CH2
L18
1H-NMR (CDCl3): δ =






2.24 (m, 2H), 2.76 (t, 2H),






3.18 (m, 2H), 3.62 (S, 2H),






5.75 (m, 2H)


42
T39
CH2
L6
1H-NMR (CDCl3): δ =






3.56 (d, 1H), 3.91 (d, 1H)


43
T39
CH2
L22
1H-NMR (CDCl3): δ =






1.00 (d, 6H), 1.30 (t, 2H)






1.98 (m, 2H), 2.22 (m, 2H)






2.58 (m, 2H), 3.50 (s, 2H)


44
T39
CH2
L23
1H-NMR (CDCl3): δ =






0.90 (d, 6H), 1.75 (m, 6H),






2.88 (m, 2H), 3.55 (s, 2H)


45
T39
CH2
L24
1H-NMR (CDCl3): δ =






0.90 (t, 3H), 3.52 (s, 2H)


46
T39
CH2
L30
1H-NMR (CDCl3): δ =






1.28 (t, 3H), 3.56 (s, 2H),






4.17 (q, 2H)


47
T39
CH2
L31
1H-NMR (CDCl3): δ =






1.43 (s, 9H), 2.58 (t, 4H),






3.50 (t, 4H), 3.58 (s, 2H)


48
T39
CH2
L36
1H-NMR (CDCl3): δ =






1.82 (t, 4H), 2.73 (t, 4H),






3.57 (s, 2H), 3.98 (s, 4H)


49
T39
CH2
L44
1H-NMR (CDCl3): δ =






0.95 (t, 3H), 3.56 (d, 1H),






3.87(d, 1H)


50
T39
CH2
L47
1H-NMR (CDCl3): δ =






2.96 (m, 4H), 3.77 (s, 2H),






3.83 (s, 2H), 7.0–7.2 (m, 4H)


51
T39
CH2
L17
1H-NMR (CDCl3): δ =






2.45 (s, 3H), 3.59 (s, 2H)


52
T33
CH2
L17
1H-NMR (CDCl3): δ =






2.36 (s, 3H), 3.57 (s, 2H),






7.55 (m, 4H)


53
T44
CH2
L17
1H-NMR (CDCl3): δ =






2.33 (s, 3H), 3.60 (s, 2H)


54
T33
CH2
L12
1H-NMR (CDCl3): δ =






2.62 (t, 4H), 3.55 (s, 2H),






3.78 (t, 4H)


55
T44
CH2
L12
1H-NMR (CDCl3): δ =






2.68 (t, 4H), 3.60 (s, 2H),






3.78 (t, 4H), 7.5 (m, 2H),






7.76(d, 1H)


56
T200
CH2
L12
1H-NMR (CDCl3): δ =






2.70 (t, 4H), 3.65 (s, 2H),






3.78 (t, 4H), 7.97 (d, 1H),






8.72 (d, 1H)


57
T200
CH2
L50
1H-NMR (CDCl3): δ =






0.96 (d, 3H), 1.20–1.43 (m, 3H),






1.7 (m, 2H), 2.39 (m, 2H),






2.95 (m, 2H), 3.65 (s, 2H),






7.97 (d, 1H), 8.71 (d, 1H)


58
T218
CH2
L50
1H-NMR (CDCl3): δ =






0.96 (d, 3H), 3.58 (s, 2H),






7.52 (d, 1H), 7.86 (dd, 1H),






8.81 (d, 1H)


59
T214
CH2
L50
1H-NMR (CDCl3): δ =






0.94 (d, 3H), 3.55 (s, 2H),






7.30 (d, 1H), 7.78 (dd, 1H),






8.61 (d, 1H)


60
T233
CH2
L50
1H-NMR (CDCl3): δ =






0.96 (d, 3H), 3.58 (s, 2H),






7.78 (d, 1H), 7.80 (d, 1H)


61
T39
CH2
L33
1H-NMR (CDCl3): δ =






0.95 (s, 3H), 1.06 (s, 3H),






1.24 (s, 3H), 3.57 (d, 1H),






3.65 (d, 1H)


62
T200
CH2
L17
1H-NMR (CDCl3): δ =






2.48 (s, 3H), 3.68 (s, 2H),






7.96 (d, 1H), 8.72 (d, 1H)


63
T39
CH2
L34
1H-NMR (CDCl3): δ =






1.6–2.1 (m, 8H), 2.75 (m, 3H),






2.97 (m, 2H), 3.46 (s, 2H)


64
T44
CH2
L34
1H-NMR (CDCl3): δ =






2.4 (m, 2H), 2.60 (m, 4H),






2.95 (m, 2H), 3.60 (s, 2H),






7.45 (dd, 1H), 7.51 (d, 1H),






7.73 (d, 1H)


65
T33
CH2
L43
1H-NMR (CDCl3): δ =






2.57 (d, 2H), 3.48 (s, 2H),






7.13 (m, 3H), 7.27 (m, 2H),






7.54 (m, 4H)


66
T44
CH2
L43
1H-NMR (CDCl3): δ =






2.57 (d, 2H), 3.58 (s, 2H),






7.13 (m, 3H), 7.27 (m, 2H),






7.48 (m, 2H), 7.70 (d, 1H)


67
T39
CH2
L43
1H-NMR (CDCl3): δ =






2.58 (d, 2H), 3.50 (s, 2H),






7.13 (m, 3H), 7.27 (m, 2H),






7.78 (s, 1 H), 7.82 (s, 2H)


68
T33
CH2
L34
1H-NMR (CDCl3): δ =






1.82 (m, 4H), 2.32 (m, 2H),






2.62 (m, 4H), 2.97 (m, 2H),






3.53 (s, 2H), 7.55 (m, 4H)


69
T1
CH2
L14


70
T46
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 1.36 (m, 3H),






2.21 (m, 2H), 2.94 (m, 2H),






3.52 (s, 2H), 7.20 (dd, 1H),






7.57 (d, 1H), 7.60 (d, 1H)


71
T400
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 3.50 (s, 2H),






6.97 (dd, 1H), 7.18 (dd, 1H),






7.22 (dd, 1H)


72
T450
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 3.47 (s, 2H),






7.10 (d, 1H), 7.24 (dd, 1H),






7.40 (d, 1H)


73
T39
CH(CH3)
L50


74
T39
C(CH3)2
L50


75
T39
CO
L50


76
T39
CF2
L50


77
T39
CH(CH2Ph)
L50
b.p. 140° C./0.01 mm Hg


78
T46
CH(CH3)
L50


79
T46
C(CH3)2
L50


80
T46
CO
L50


81
T46
CF2
L50


82
T46
CH(CH2Ph)
L50


83
T1
CH2
L45


84
T1
CH2
L19
oil


85
T39
CH2
L45


86
T39
CH2
L19


87
T1
CH2
L12


88
T39
CH2
L14


89
T21
CH2
L50
b.p. 95° C./0.02 mm Hg


90
T62
CH2
L50
b.p. 144° C./0.03 mm Hg


91
T4
CH2
L50
m.p. 48–49° C.


92
T103
CH2
L50
m.p. 89.5–90° C.


93
T86
CH2
L50
b.p. 122–124° C./0.01 mm Hg


94
T3
CH2
L50
b.p. 110–114° C./0.015 mm Hg


95
T104
CH2
L50
b.p. 113° C./0.04 mm Hg


96
T105
CH2
L50
b.p. 108° C./0.03 mm Hg


97
T52
CH2
L50
b.p. 119–120° C./0.005 mm Hg


98
T89
CH2
L50
b.p. 144–146° C./0.015 mm Hg


99
T106
CH2
L50
b.p. 124° C./0.8 mm Hg


100
T56
CH2
L50
b.p. 126–128° C./0.05 mm Hg


101
T107
CH2
L50
b.p. 127° C./0.002 mm Hg


102
T108
CH2
L50
b.p. 110–112° C./0.05 mm Hg


103
T53
CH2
L50
b.p. 123–126° C./0.01 mm Hg


104
T111
CH2
L50
b.p. 135° C./0.05 mm Hg


105
T112
CH2
L50
b.p. 125° C./0.06 mm Hg


106
T5
CH2
L50
b.p. 140–142° C./0.05 mm Hg


107
T7
CH2
L50
b.p. 125° C./0.005 mm Hg


108
T116
CH2
L50
m.p. 36–37° C.


109
T117
CH2
L50
m.p. 57–58° C.


110
T118
CH2
L50
b.p. 119° C./0.005 mm Hg


111
T39
CH2
L22
b.p. 97–101° C./0.2 mm Hg


112
T39
CH2
L90
b.p. 120–125° C./0.07 mm Hg


113
T39
CH2
L24
b.p. 130° C./0.35 mm Hg


114
T87
CH2
L50
b.p. 126–129° C./0.11 mm Hg


115
T119
CH2
L50
m.p. 66–68° C.


116
T120
CH2
L50
b.p. 138–143° C./0.05 mm Hg


117
T79
CH2
L50
m.p. 62–63° C.


118
T39
CH2
L76


119
T94
CH2
L50
m.p. 47–48° C.


120
T78
CH2
L50
b.p. 130° C./0.03 mm Hg


121
T26
CH2
L50
b.p. 110° C./0.04 mm Hg


122
T25
CH2
L50
b.p. 95° C./0.03 mm Hg


123
T123
CH2
L50


124
T59
CH2
L50


125
T39
CH2
L28
m.p. 47–48° C.


126
T124
CH2
L50
b.p. 118° C./0.05 mm Hg


127
T126
CH2
L50
b.p. 131° C./0.1 mm Hg


128
T39
CH2
L78
m.p. 86–87° C.


129
T39
CH2
L64
mp. 70–72° C.


130
T128
CH2
L50
b.p. 162° C./0.25 mm Hg


131
T129
CH2
L50
m.p. 58–59° C.


132
T39
CH2
L80
m.p. 45° C.


133
T130
CH2
L50
b.p. 132–134° C./0.2 mm Hg


134
T1
CH(Pri)
L2
b.p. 130–130° C./0.2 mm Hg


135
T141
CH2
L50
b.p. 126–132° C./0.1 mm Hg


136
T131
CH2
L50
b.p. 112–116° C./0.1 mm Hg


137
T132
CH2
L50
b.p. 105–110° C./0.1 mm Hg


138
T1
CH(Pri)
L50
b.p. 156–158° C./1.75 mm Hg


139
T39
CH2
L86
wax


140
T1
CO
L50
m.p. 56–57° C.


141
T134
CH2
L50
b.p. 160° C./0.2 mm Hg


142
T64
CH2
L50
m.p. 58–59° C.


143
T135
CH2
L50
b.p. 145° C./0.1 mm Hg


144
T133
CH2
L51


145
T136
CH2
L50
m.p. 46–47° C.


146
T137
CH2
L50


147
T39
CO
L50
m.p. 110–111° C.


148
T138
CH2
L50
m.p. 63–64° C.


149
T39
CH2
L79
b.p. 185–187° C./0.7 mm Hg


150
T140
CH2
L50
m.p. 50–51° C.


151
T6
CH2
L63
oil


152
T39
CH2
L50
b.p. 92–95°C./0.04 mm Hg;






m.p. 22° C.


153
T44
CH2
L33
1H-NMR (CDCl3): δ =






0.92 (s, 3H), 1.06 (s, 3H),






1.23 (s, 3H), 3.60 (d, 1H),






3.75 (d, 1H), 7.70 (d, 1H)


154
T33
CH2
L33
1H-NMR (CDCl3): δ =






0.86 (s, 3H), 1.06 (s, 3H),






1.25 (s, 3H), 3.53 (d, 1H),






3.65 (d, 1H), 7.50 (d, 2H), 7.58






(d, 2H)


155
T511
CH2
L50
1H-NMR (CDCl3): δ =






0.96 (d, 3H), 3.58 (s, 2H),






7.18 (dd, 1H), 7.68 (dd, 1H), 8.32






(dd,1H)


156
T512
CH2
L50
1H-NMR (CDCl3): δ =






0.95 (d, 3H), 3.48 (s, 2H),






7.78 (d, 1H), 8.36 (d, 1H)


157
T502
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 3.70 (s, 2H),






7.75 (t, 1H), 7.83 (s, 1H), 8.19 (d,






1H), 8.55 (d, 1H)


158
T219
CH2
L50
m.p. 75–77° C.


159
T325
CH2
L22
1H-NMR (CDCl3): δ =






0.98 (d, 6H), 1.30 (t, 3H), 3.56 (d,






2H), 7.25 (s, 1H)


160
T325
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 2.60 (s, 3H), 3.57






(s, 2H), 7.27 (s, 1 H)


161
1321
CH2
L50
1H-NMR (CDCl3): δ =






0.97 (d, 3H), 2.80 (s, 3H), 3.59






(s, 2H), 7.49 (s, 1H)


162
T233
CH2
L22
1H-NMR (CDCl3): δ =






0.98 (d, 6H), 1.30 (t, 3H), 3.55 (s,






2H), 7.77 (s, 1H), 7.79 (s, 1H)


163
T233
CH2
L23
1H-NMR (CDCl3): δ =






0.90 (d, 6H), 1.65–1.85 (m, 6H),






3.58 (s, 2H), 7.76 (s, 1H), 7.80 (s,






1H)


164
T325
CH2
L3
1H-NMR (CDCl3): δ =






1.55–1.80 (m, 8H), 2.60 (s, 3H),






3.67 (s, 2H), 7.25 (s, 1H)


165
T231
CH2
L50
1H-NMR (CDCl3): δ =






0.95 (d, 3H), 3.65 (s, 2H),






7.70 (d, 1H), 8.16 (d, 1H)


166
T325
CH2
L23
1H-NMR (CDCl3): δ =






0.90 (d, 6H), 2.60 (t, 3H), 3.59 (s,






2H), 7.29 (s, 1H)


167
T350
CH2
L50
oil


168
T521
CH2
L50
oil


169
T39
CH2
L69
oil


170
T233
CH2
L69
oil


171
T142
CH2
L50
oil


172
T143
CH2
L50
oil


173
T144
CH2
L50
oil


174
T145
CH2
L50
oil


175
T146
CH2
L50
oil


176
T148
CH2
L50
oil


177
T149
CH2
L50
oil


178
T150
CH2
L50
oil


179
T151
CH2
L50
oil


180
T152
CH2
L50
oil


181
T147
CH2
L50
oil


182
T153
CH2
L50
oil


183
T154
CH2
L50
oil


184
T155
CH2
L50
oil


185
T156
CH2
L50
oil


186
T157
CH2
L50
oil


187
T158
CH2
L50
oil


188
T159
CH2
L50
oil


189
T160
CH2
L50
oil


190
T161
CH2
L50
oil


191
T162
CH2
L50
oil


192
T163
CH2
L50
oil


193
T164
CH2
L50
oil


194
T165
CH2
L50
oil


195
T166
CH2
L50
oil


196
T167
CH2
L50
oil


197
T236
CH2
L50
1H-NMR(CDCl3) δ = 0.97 (d,






3H), 2.62 (s, 3H), 3.55 (s, 2H),






7.29 (s, 1H), 7.45 (s, 1H).


198
T233
CH2
L72
oil


199
T39
CH2
L72
oil


200
T329
CH2
L50
oil


201
T237
CH2
L50
oil


202
T238
CH2
L50
oil


203
T217
CH2
L50
oil


204
T233
CH2
L91
1H-NMR(CDCl3): δ = 3.62 (d,






2H), 7.80 (s, 2H).


205
T39
CH2
L91
oil


206
T513
CH2
L50
oil


207
T168
CH2
L50
oil


208
T415
CH2
L50
m.p. 54° C.


209
T169
CH2
L50
oil


210
T514
CH2
L50
oil


211
T515
CH2
L50
oil


212
T516
CH2
L50
m.p. 77–78° C.


213
T416
CH2
L50
m.p. 96–97° C.


214
T407
CH2
L50
m.p. 73–74° C.


215
T417
CH2
L50
oil


216
T403
CH2
L50
oil


217
T170
CH2
L50
oil


218
T171
CH2
L50
oil


219
T172
CH2
L50
oil


220
T173
CH2
L50
oil


221
T174
CH2
L50
oil


222
T175
CH2
L50
oil


223
T176
CH2
L50
oil


224
T177
CH2
L50
oil


225
T178
CH2
L50
oil


226
T179
CH2
L50
oil


227
T180
CH2
L50
oil


228
T181
CH2
L50
oil


229
T418
CH2
L50
oil


230
T419
CH2
L50
oil


231
T189
CH2
L50
oil


232
T420
CH2
L50
oil


233
T517
CH2
L50
oil


234
T203
CH2
L50
1H-NMR(CDCl3): δ 0.96 (d,






3H), 3.56 (s, 2H), 7.45 (s, 1H),






7.55 (s, 1H).


235
T518
CH2
L50
oil


236
T421
CH2
L50
oil


237
T422
CH2
L50
oil


238
T423
CH2
L50
oil


239
T424
CH2
L50
oil


240
T425
CH2
L50
oil


241
T426
CH2
L50
oil


242
T427
CH2
L50
oil


243
T428
CH2
L50
oil


244
T429
CH2
L50
oil


245
T430
CH2
L50
oil


246
T432
CH2
L50
oil


247
T431
CH2
L50
oil


248
T190
CH2
L50
oil


249
T191
CH2
L50
oil


250
T192
CH2
L50
oil


251
T193
CH2
L50
oil


252
T195
CH2
L50
oil


253
T194
CH2
L50
oil


254
T182
CH2
L50
oil


255
T196
CH2
L50
oil


256
T197
CH2
L50
oil


257
T198
CH2
L50
oil


258
T199
CH2
L50
oil


259
T600
CH2
L50
oil


260
T601
CH2
L50
oil


261
T602
CH2
L50
oil


262
T603
CH2
L50
oil


263
T604
CH2
L50
oil


264
T183
CH2
L50
oil


265
T605
CH2
L50
oil


266
T606
CH2
L50
oil


267
T39
CH2
L53
oil


268
T607
CH2
L50
oil


269
T608
CH2
L50
oil


270
T609
CH2
L50
oil


271
T433
CH2
L50
oil


272
T424
CH2
L50
oil


273
T435
CH2
L50
oil


274
T436
CH2
L50
oil


275
T522
CH2
L50
m.p. 132° C.


276
T523
CH2
L50
m.p. 141° C.


277
T524
CH2
L50
m.p. 146° C.


278
T525
CH2
L50
m.p. 169° C.


279
T526
CH2
L50
m.p. 143° C.


280
T527
CH2
L50
m.p. 149° C.


281
T39
CH2
L93
oil


282
T233
CH2
L93
oil


283
T185
CH2
L50
oil


284
T186
CH2
L50
oil


285
T187
CH2
L50
oil


286
T188
CH2
L50
oil


287
T39
CH2
L92
oil


288
T233
CH2
L92
oil


289
T69
CH2
L50
m.p. 61° C.


290
T75
CH2
L50
m.p. 73° C.


291
T519
CH2
L50
1H-NMR(CDCl3): δ =0.96 (d,






3H), 3.5 (s, 2H), 7.23 (s, 2H).


292
T437
CH2
L50
oil


293
T438
CH2
L50
oil


294
T237
CH2
L50
oil


295
T140
CH2
L50
oil


296
T439
CH2
L50
oil


297
T32
CH2
L93
oil


298
T412
CH2
L50
oil


299
T413
CH2
L50
oil


300
T528
CH2
L50
oil


301
T529
CH2
L50
oil


302
T530
CH2
L50
oil


303
T531
CH2
L50
oil


304
T520
CH2
L50
1H-NMR(CDCl3): δ =0.97 (d,






3H), 3.57 (s, 2H), 7.82 (s, 2H).


305
T414
CH2
L50
oil









Further compounds not shown in this table can obtained using further combinations of the groups T, A and L defined.







TABLE 2













 












 Comp. No
 R1
 A




 X
 Physico-chemical data





1000
T6
CH2
L50
Cl
m.p. 183–184° C.


1001
T39
CH2
L27
Cl
m.p. 218° C.


1002
T46
CH2
L50
1⁄2 SO4
m.p. 139–141°C.


1003
T39
CH2
L54
Cl
m.p. 205° C.


 


1004
T46
CH2
L50




m.p. 172–173° C.


 


1005
T46
CH2
L50
CF3COO
m.p. 42–44° C.


1006
T46
CH2
L50
Cl
m.p. 178–183° C.


1007
T46
CH2
L50
1⁄2 OOC—COO
m.p. 165° C.


 


1008
T46
CH2
L50




m.p.95° C.


 


1009
T46
CH2
L50




m.p. 157° C.


 


1010
T9
CH2
L50
Cl
m.p. 185–186° C.


1011
T10
CH2
L50
Cl
m.p. 213–214° C.


1012
T2
CH2
L50
Cl
m.p. 164–165° C.


1013
T109
CH2
L50
Cl
m.p. 138–139° C.


1014
T110
CH2
L50
Cl
m.p. 200–202° C.


1015
T113
CH2
L50
Cl
m.p. 162° C.


1016
T114
CH2
L50
Cl
m.p. 185° C.


1017
T115
CH2
L50
Cl
m.p. 139–140° C.


1018
T39
CH2
L30
Cl
m.p. 168–172° C.


1019
T39
CH2
L77
Cl
m.p. 230–232° C.


1020
T125
CH2
L50
Cl
m.p. 188° C.


1021
T39
CH2
L79
Cl
m.p. 213–215° C.


1022
T127
CH2
L50
Cl
m.p. 200–202° C.


1023
T20
CH2
L50
Cl
m.p. 233–234° C.


1024
T39
CH2
L44
Cl
m.p. 178–179° C.


1025
T39
CH2
L81
Cl
m.p. 195° C.


1026
T39
CH2
L82
Cl
m.p. 65–110° C.


1027
T39
CH2
L83
Cl
m.p. 50–79° C.


1028
T39
CH2
L84
Cl
m.p. 214–216° C.


1029
T39
CH2
L85
Cl
m.p. 220–221° C.


1030
T39
CH2
L87
Cl
m.p. 192–193° C.


1031
T39
CH2
L13
Cl
m.p. 210–212° C.


1032
T133
CH2
L50
Cl2
m.p. 270° C.


1033
T39
CH2
L88
Cl2
m.p. 282–283° C.


1034
T39
CH2
L89
Cl
m.p. 202° C.


1035
T17
CH2
L50
Cl
m.p. 225° C.


1036
T46
CH2
L50
Cl
m.p. 207–209° C.


1037
T39
CHMe
L50
Cl
m.p. 205–210° C.


1038
T71
CH2
L50
Cl
m.p. 201–204° C.


1039
T39
C(Me)2
L50
Cl
m.p. 208–210° C.


1040
T46
CH2
L50
C8H17COO
1H-NMR(CDCl3):







δ = 0.85(t, 3H), 0.97







(d, 3H), 3.58(s, 2H),







7.39 (d, 1H), 7.56







(s, 1H), 7.61 (d, 1H)


1041
T39
CH2
L3
Cl
m.p. 206–208° C.


1042
T33
CH2
L50
Cl
m.p. 198–200° C.


1043
T44
CH2
L50
Cl
m.p. 222–224° C.


1044
T39
CH2
L22
Cl
m.p. 187–189° C.


1045
T233
CH2
L50
C8H17COO
1H-NMR(CDCl3):







δ = 0.85(t, 3H), 0.97







(d, 3H), 3.60(s, 2H),







7.78(s, 1H), 7.81







(s, 1H)


1046
T233
CH2
L50
CF3COO
1H-NMR(CDCl3):







δ = 1.05(d, 3H),







4.20(s, 2H), 8.89







(s, 1H), 8.91(s,1H)


1047
T233
CH2
L50
Cl
m.p. 203–206° C.


1048
T202
CH2
L50
Cl
m.p. 172° C.


1049
T236
CH2
L50
Cl
m.p. 150° C.


1050
T233
CH2
L91
Cl
m.p. 151° C.


1051
T39
CH2
L50
CF3COO
m.p. 188° C.


1052
T39
CH2
L50
Cl
m.p. 212° C.


1053
T39
CH2
L50
1⁄2 SO4
m.p. 188° C.


 


1054
T39
CH2
L50




m.p. 176° C.


 


1055
T39
CH2
L50
1⁄2 OOC—COO
m.p. 186° C.


 


1056
T39
CH2
L50




m.p. 128° C.


 


1057
T203
CH2
L50
Cl
m.p. 183° C.


1058
T517
CH2
L50
Cl
m.p. 192° C.


1059
T46
CH2
L50
EtSO2O
m.p. 132° C.


1060
T233
CH2
L50
EtSO2O
m.p. 104° C.


1061
T169
CH2
L50
Cl
m.p. 176° C.


 


1062
T169
CH2
L50




m.p. 161° C.


 


1063
T39
CH2
L50
EtSO2O
oil


1064
T236
CH2
L50
EtSO2O
viscous oil


1065
T169
CH2
L50
CF3COO
m.p. 78° C.


 


1066
T169
CH2
L50




m.p. 100° C.


 


1067
T169
CH2
L50
EtSO2O
viscous oil


1068
T518
CH2
L50
Cl
foam


1069
T184
CH2
L50
Cl
m.p. 198° C.


1070
T520
CH2
L50
Cl
m.p. 168–170° C.









B. FORMULATION EXAMPLES
Example A
A dust is obtained by mixing 10 parts by weight of active compound and 90 parts by weight of talc as inert material and comminuting the mixture in a hammer mill.
Example B
A wettable powder which is readily dispersible in water is obtained by mixing 25 parts by weight of active compound, 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.
Example C
A dispersion concentrate which is readily dispersible in water is prepared by mixing 40 parts by weight of active compound 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.
Example D
An emulsifiable concentrate can be prepared from 15 parts by weight of active compound, 75 parts by weight of cyclohexane as solvent and 10 parts by weight of ethoxylated nonylphenol (10 EO) as emulsifier.
Example E
Granules can be prepared from 2 to 15 parts by weight of active compound 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 from Example B with a solids content of 30%, which is sprayed onto the surface of the attapulgite granules, and these are dried and mixed intimately. The wettable powder amounts to approximately 5% by weight and the inert carrier material to approximately 95% by weight of the finished granules.
C. BIOLOGICAL EXAMPLES
In the Examples A to M, P to Z and AA to AI below, compounds were considered to be active when, at a concentration of 500 ppm or less, they had an activity on the harmful organisms of 50% or more.
Example A
The leaves of 12 rice plants having a stem length of 8 cm were dipped for 5 seconds into an aqueous solution of the formulated compound to be examined. After the solution had run off, the rice plants treated in this manner were placed into a Petri dish and populated with about 20 larvae (L3 stage) of the rice leafhopper species Nilaparvata lugens. The Petri dish was closed and then stored in a climatized chamber (16 hours of light/day, 25° C., 40–60% relative atmospheric humidity). After 6 days of storage, the mortality among the leafhopper larvae was determined. The compounds of the following examples were active: Nos. 29, 32, 42, 43, 51, 70, 84, 1002, 1004, 1005, 1040, 180, 184, 193, 197, 203, 209, 1059, 264, 265, 1066.
Example B
A Petri dish whose bottom was covered with filter paper and which contained about 5 ml of insect diet was prepared. Pieces of filter paper with about 30, 24-hour-old eggs of the American tobacco budworm (Heliothis virescens) were dipped for about 5 seconds into an aqueous solution of the formulated compound to be examined and were subsequently placed in the Petri dish. A further 200 μl of the aqueous solution were spread over the insect diet. 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 the larvae which might have hatched from these was determined (mortality). The compounds of the following examples were active: Nos. 14, 15, 17, 18, 29, 30, 32, 60, 70, 97, 100, 119, 124, 1000, 1002, 1004, 1005, 1011, 1038, 1040, 1042, 1044, 1045, 1046, 1047, 1036, 167, 171, 172, 173, 174, 175, 181, 176, 177, 178, 179, 180, 182, 183, 188, 189, 190, 191, 192, 193, 194, 195, 197, 201, 1048, 203, 204, 24, 207, 209, 210, 214, 215, 216, 217, 221, 222, 224, 225, 226, 229, 230, 152, 1051, 1052, 1054, 1055, 1056, 232, 234, 1057, 1059, 1060, 1061, 1062, 1063, 236, 239, 240, 241, 244, 245, 246, 247, 251, 252, 253, 254, 256, 263, 266, 1065, 1067, 270, 271, 272, 273, 283, 284, 285, 286, 289, 290, 291, 292, 295, 296, 300, 301, 302.
Example C
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 compound to be examined were pipetted onto the eggs, and the rest was pipetted onto the maize corn. The Petri dish was closed and stored at about 25° C. in a climatized chamber. After 6 days of storage, the effect of the compound on the eggs and the larvae which might have hatched from these was determined (mortality). The compounds of the following examples were active: Nos. 17, 18, 31, 32, 43, 58, 60, 70, 152, 1001, 1002, 1004, 1005, 1038, 1040, 1042, 1047, 1036, 185, 189, 190, 191, 193, 194, 196, 197, 201, 203, 1050, 204, 205, 298, 207, 209, 228, 152, 231, 1051, 1052, 1053, 1054, 1055, 1056, 234, 1057, 1058, 1059, 1060, 1061, 1062, 235, 1063, 1064, 1065, 1066, 1067, 1068, 1069, 267, 281, 282, 290, 291, 295, 297.
Example D
Apples were dipped into an aqueous solution of the formulated compound to be examined. The apples were then populated with 10 L1 larvae of the codling moth (Carpocapsa pomonella). After 14 days of storage at about 25° C., the effect of the compound on the larvae was determined (mortality). The compounds of the following examples were active: Nos. 14, 15, 17, 18, 70, 1007, 1008, 1009, 1036, 1038, 197.
Example E
Leaves of cotton plants were placed into a Petri dish, populated with 10 L2 larvae of the Egyptian cotton leafworm (Spodoptera littoralis) and sprayed with an aqueous solution of the formulated compound to be examined. After 4 days of storage at about 23° C., the effect of the compound on the larvae was determined (mortality). The compounds of the following examples were active: Nos. 18, 70, 1007, 1008, 1009, 1036 und 1038.
Example F
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 compound 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 3 and 6 days of storage, the effect of the compound on the aphids was determined (mortality). The compounds of the following examples were active: 30, 43, 228, 262, 291.
Example G
A Petri dish whose bottom was covered with filter paper and which contained about 5 ml of insect diet is prepared. Five L2 larvae of the Egyptian cotton leafworm (Spodoptera littoralis) 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 insect diet. 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 compound on the larvae was determined (mortality). The compounds of the following examples were active: 29, 70, 60, 159, 1005, 1040, 1042, 1044, 1045, 1046, 1047.
Example H
In a glass vessel, an aqueous solution of the formulated compound to be examined was added to about 3000 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 activity of the compound was determined in comparison to the untreated controls (contact activity). The compounds of the following examples were active: 39, 52, 159, 161, 162, 163, 164, 165, 1045, 1046, 1047, 179, 183, 187, 1048, 298, 206, 208, 227, 230, 1061, 237, 238, 245, 250, 255, 256, 260, 268, 269, 274, 275, 288, 290.
Example I
Ten L1 larvae of the codling moth (Carpocapsa pomonella) were placed into a Petri dish filled with insect diet. Insect diet and the larvae used were then sprayed with an aqueous solution of the formulated compound to be examined. The Petri dish was then closed with a lid. After 8 days of storage at about 23° C., the effect of the compound on the larvae was determined (mortality). The compounds of the following examples were active: 60, 70, 1002, 1005.
Example J
About 20 eggs of the codling moth (Carpocapsa pomonella) were placed into a Petri dish filled with insect diet. Insect diet and eggs were then sprayed with an aqueous solution of the formulated compound to be examined. The Petri dish was then closed with a lid. After 8 days of storage at about 23° C., the effect of the compound on the eggs and any larvae which may have hatched therefrom was determined (mortality). The compounds of the following examples were active: 70, 1036.
Example K
A white cabbage leaf was sprayed with an aqueous solution of the formulated compound to be examined. After the spray coating had dried, the treated leaf was populated with larvae of the diamondback moth (Plutella maculipennis). After 3 days of storage at about 23° C., the effect of the compound on the larvae was determined (mortality). The compounds of the following examples were active: 60, 70, 1002, 1004, 1005, 1036, 197.
Example L
Potato leaves were populated with larvae of the Colorado beetle (Leptinotarsa decemlineata). Leaves and larvae were then sprayed with an aqueous solution of the formulated compound to be examined. After 4 days of storage at about 25° C., the effect of the compound on the larvae was determined (mortality). The compounds of the following examples were active: 60, 70, 1002, 1004, 1005, 1036, 1047, 197.
Example M
The formulated compound was mixed with defibrinated cattle blood. 10 adult cat fleas (Ctenocephalides felis) were fed with this blood-preparation mixture. After 48 hours at about 38° C., the effect of the compound on the fleas was determined (mortality). The compounds of the following examples were active: 70, 1002, 1004, 1005, 1036, 60, 197, 1057.
Example N
Test 1
Disks of beet leaves (diameter 49 mm) were placed onto 20% agar in Petri dishes made of plastic (diameter 9 cm). Each dish was populated with 10 adults of Phaedon cochleariae which were cultivated on beets. The compound to be examined was prepared in an aqueous, 50% by volume strength acetone solution. The solution of the compound was then sprayed onto the infected leaf disks using a Potter tower, at an application rate of 660 liters per hectare. Each experiment was carried out with 4 repetitions. In the controls, the infected leaf disks were only sprayed with the 50% strength aqueous acetone solution, if at all.
After 48 h, the mortality was determined and, using Abbott's formula, compared to the mortality of the controls. The LD90 concentration (dosage which leads to 90% mortality, here stated in % by weight) as then calculated. The compounds of Examples 14, 18, 29, 33, 152, 1001 and 1039 showed an LD90 at a dosage of 0.05% or less.
Test 2
Instead of Phaedon cochleariae, 5 Pieris brassicae larvae of the 2nd development stage were used. The test was carried out analogously to the procedure described in Test 1. The compounds of Examples 14, 29, 33, 100, 152, 1005 and 1039 showed an LD90 at a dosage of 0.006% or less.
Test 3
Instead of Pieris brassicae, 10 Plutella xylostella larvae of the 2nd development stage were used. The test was carried out analogously to the procedure described in Test 2. The compounds of Examples 4, 6, 7, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 23, 24, 25, 26, 28, 29, 31, 32, 33, 34, 35, 152, 1000, 1001, 1005 and 1039 showed an LD90 at a dosage of 0.05% or less.
Test 4
The compound to be examined was dissolved in pure acetone and mixed into soil having a moisture of about 10%. The solvent was evaporated, and in each case 5 g of treated soil were then filled into a tube, and 0.5 ml of water was added. 10 Gryllus bimaculatus nymphs (1st development stage) and a disk of green cabbage as a source of food were placed into each tube. Each experiment was carried out with 4 repetitions. The controls were untreated soil and soil which had been treated only with acetone. The ventilated tubes were cultivated at 25° C. for 48 h, after which the mortality was determined.
Taking into account the control mortality, the LC90 was determined as ppm concentration in the soil, using Abbott's formula. The compounds of Examples 152 and 1039 showed an LC90 at a concentration of 50 ppm or less.
Test 5
The compound to be examined was dissolved in pure acetone, and a small amount of this solution was applied to the surface of a milk-yeast-agar diet (5 ml) in a small sample glass (7 cm×2.5 cm). After 24 h, about 10 Lucilia sericata larvae of the 1st development stage were placed on the treated diet. Each experiment was carried out with 3 repetitions. The diet in the tubes of the control was treated only with an equivalent amount of acetone. The ‘minimum effective dose’ (MED) was defined as the lowest dosage at which the further development of the larvae is stopped, and as a consequence, there is no subsequent hatching of adult flies.
The compounds of Example 4 and 1039 showed an MED at 100 μg/glass or less.
Test 6
The compound to be examined was made up in an aqueous 50% by volume strength acetone solution. Two-week-old Boophilus microplus larvae which were sandwiched between 2 disks of filter paper were dipped for 4 minutes into the solution of the compound. Each experiment was carried out with two repetitions. The corresponding controls were only treated with the 50% strength aqueous acetone solution. The larvae were then placed onto new filter paper disks and stored at about 25° C. and 95% relative atmospheric humidity. The ‘minimum effective concentration’ (MEC) was defined as the lowest concentration, expressed in % by weight of the compound to be examined in the solution, at which 100% mortality occurred within 48 h. The compounds of Examples 2, 4, 6, 9, 20, 22, 25, 27, 28 and 32 had an MEC of 0.04% or less.
Test 7
The compound to be examined was made up in an aqueous, 50% by volume strength acetone solution. Female cattle ticks (Boophilus microplus) which had sucked themselves full and had fallen off in a natural manner from artifically infected calves were washed and dried. With constant stirring, they were then dipped for 1 minute into the solution of the compound. After the solution had run off, the females were transferred into small sample glasses (7 cm×2.5 cm) and stored in an incubator at 30° C. and 94% relative atmospheric humidity. Each experiment involved 2×10 female ticks. The control group was treated only with the 50% strength aqueous acetone solution. Mortality and deposition of eggs were analyzed six days after treatment. The ‘minimum effective concentration’ (MEC) was defined as the lowest concentration, expressed in % by weight of the compound to be examined in the solution, at which the ticks were no longer able to produce viable eggs. The compounds of Examples 20, 27 and 32 had an MEC of less than 0.2%.
Example O
Test 1
The compound to be examined was dissolved in pure acetone, and a standard cockroach bait mixture comprising mainly water, corn syrup and glycerol, and minor portions of poultry liver and starch with small amounts of hydroxymethylcellulose, propyl- and methyl-para-hydroxybenzoic acid and an attractant scent was added. After the acetone had evaporated, 0.1 g of the bait was placed into a box made of plastic, and 20 adult Blattella germanica (in each case 10 male and 10 female) were then added (‘no choice’ test). After 7 days, the effect was determined. Present in the bait in an amount of 0.5% by weight, the compounds of Examples 70 and 1036 caused a mortality of 45% and 100%, respectively. When present in the bait in an amount of 1.0% by weight, the compounds of Examples 70 and 1036 additionally had a repellent effect.
Test 2
The compound to be examined was dissolved in pure acetone, and a standard cockroach bait mixture comprising mainly water, corn syrup and glycerol, and minor portions of poultry liver and starch with small amounts of hydroxymethylcellulose, propyl- and methyl-para-hydroxybenzoic acid and an attractant scent was added. After evaporation of the acetone, 0.1 g of the bait prepared in this manner and 0.1 g of an identical bait without test compound were placed into a box made of plastic. 20 adult Blattella germanica (in each case 10 male and 10 female) were then placed into the box (‘choice’ test). After 7 days, the effect was determined. Present in the bait in an amount of 0.5% by weight, the compounds of Examples 70 and 1036 caused a mortality of 30% and 60%, respectively. When present in the bait in an amount of 1.0% by weight, the compounds of Examples 70 and 1036 had a repellent effect without mortality, since the baits with the test compounds were not fed on.
Test 3
The compound to be examined was dissolved in pure acetone, and small amounts thereof were pipetted into vessels containing in each case 100 ml of water. Mosquito larvae of the 2nd development stage of Aedes aegypti, Anopheles arabiensis and Culex quinquefasciatus were pipetted into each of the vessels. After 24 h, the effect was determined. At 100 ppm, the compounds of Examples 70 and 1036 caused a mortality of 100% among the larvae of Aedes aegypti, Anopheles arabiensis and Culex quinquefasciatus. 
Test 4
In each case 50 mg of the compound to be examined were dissolved in pure acetone and pipetted onto an evaporation felt mat free of active compound (syn. ‘Emanator Mat’; ®Bengal Mosquito Mats, Zobele Industrie Chimiche S.p.A., Via Fersina, Trento, Italy). After the acetone had evaporated, the evaporation felt mat prepared in this manner was placed into an electric heater (®Bengal Heater, Zobele Industrie Chimiche S.p.A., Via Fersina, Trento, Italy). On heating of the felt mat at 150° C., the compound to be examined was volatilized in a test chamber having a volume of 2 m3. The activity of the compound was tested using in each case 100 female adult mosquitoes—Aedes aegypti and Culex quinquefasciatus—with 3 repetitions. Evaluation for immobility (syn. ‘knockdown’) was carried out at one-minute intervals and terminated after a total of 20 minutes. In 50% of the female Aedes aegypti, the compounds of Example 70 and 1036 caused a knockdown (syn. KT50; ‘knockdown time of 50% of individuals’, i.e. the time after which 50% of the mosquitoes were immobilized) after 12 and 11.5 minutes, respectively. For Culex quinquefasciatus, the KT50 was 8 and 9.25 minutes.
Test 5
In each case 50 mg of the compound to be examined were dissolved in pure acetone and pipetted onto an evaporation felt mat free of active compound (syn. ‘Emanator Mat’; ®Bengal Mosquito Mats, Zobele Industrie Chimiche S.p.A., Via Fersina, Trento, Italy). After the acetone had evaporated, the evaporation felt mat prepared in this manner was used once for 20 minutes and then stored for 2 weeks. Subsequently, the prepared evaporation felt mat was examined once more. The test was carried out according to the procedure described in test 4. In the case of Aedes aegypti, the compounds of Example 70 and 1036 caused a KT50 of 11 and 10.5 minutes, respectively. In the case of Culex quinquefasciatus, the KT50 was 7.5 and 9 minutes, respectively.
Example P
A cabbage leaf was dipped for about 5 seconds into an aqueous solution of the formulated compound to be examined. After drying, the cabbage leaf treated in this manner was transferred into a container and populated with 10 larvae of the diamondback moth (Plutella maculipennis). The container was then closed with a lid. After 3 days of storage at about 23° C., the effect of the compound on the larvae was determined. The following examples were active: 1036, 70, 60, 209.
Example Q
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 compound 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 mortality of the compound on all stages of the spider mites was determined. The following examples were active: 299, 305, 206, 268, 269, 287.
Example R
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 compound to be examined were pipetted into the brown glass bottle. The field bean was then heavily populated with approximately 100 black bean aphids (Aphis fabae). Plant 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 activity of the compound on the aphids was determined (mortality). The following examples were active: 184, 186, 305, 220, 265.
Example S
A Petri dish whose bottom was covered with filter paper and which contains about 5 ml of insect diet is prepared. Five L2 larvae of sugar beet army worm (Spodoptera exigua) were counted into a small beaker. 200 μl of an aqueous solution of the formulated compound 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 insect diet. The Petri dish was closed and then stored at 25° C. in a climatized chamber. After 6 days of storage, the mortality among the larvae was determined. The following examples were active: 1036, 175, 184, 1051, 1054, 1055, 234, 1057, 1059, 1060, 1063, 243, 245, 251, 257, 259, 266, 1065, 1067, 290, 291.
Example T
10 larvae of the turnip moth (Agrotis segetum) were placed into a Petri dish filled with insect diet. Insect diet and the larvae employed were then sprayed with an aqueous solution of the formulated compound to be examined. The Petri dish was then closed with a lid. After 7 days of storage at about 23° C., the mortality among the larvae was determined. The following example was active: 70.
Example U
Rice seed was germinated on moist cotton in cultivation glasses. After the plants had grown to a stem length of approximately 8 cm, the leaves were sprayed to run-off point with an aqueous solution of the formulated compound to be examined. After the solution had run off, the treated rice plants were placed in cultivation containers and populated with in each case 10 larvae (L3 stage) of the rice leafhopper species Nilaparvata lugens. Plants and animals were stored in a climatized chamber (16 hours of light/day, 25° C., 40–60% relative atmospheric humidity). After 4 days of storage, the mortality among the larvae was determined. The following example was active: 70.
Example V
Insect diet (as freeze-dried cube) was dipped into an aqueous solution of the formulated compound to be examined and then placed into a Petri dish. 10 L2 larvae of the American tobacco budworm (Heliothis virescens) were then added. The Petri dish was then closed with a lid. After 4 days of storage at about 23° C., the mortality among the larvae was determined. The following examples were active: 1036, 60.
Example W
2.4 ml of an aqueous solution of the formulated compound to be examined were pipetted into a bottle filled with 21.6 ml of water. A 14-day-old cabbage plant was transferred into the bottle. After one week, the plant was populated with 5 larvae of the diamondback moth (Plutella maculipennis). Plants and animals were then stored in a climatized chamber (23° C., 40–60% relative atmospheric humidity). After 3 days of storage, the root-systemic activity of the compound on the larvae was determined (mortality). The following examples were active: 1036, 70, 60.
Example X
Insect diet (as freeze-dried cube) was dipped into an aqueous solution of the formulated compound to be examined and then placed into a Petri dish. 10 L2 larvae of the sugar beet armyworm (Spodoptera exigua) were then added. The Petri dish was then closed with a lid. After 4 days of storage at about 23° C., the mortality among the larvae was determined. The following examples were active: 1036, 60.
Example Y
Cotton plants were sprayed with an aqueous solution of the formulated compound 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 mortality among the larvae was determined. The following examples were active: 1036, 70, 60, 1047, 197.
Example Z
Cotton leaves were populated with 5 L2 larvae of the sugar beet armyworm (Spodoptera exigua) and then sprayed with an aqueous solution of the formulated compound to be examined. After 4 days of storage at about 23° C., the mortality among the larvae was determined. The following examples were active: 1036, 70, 60, 1047, 197.
Example AA
Insect diet was mixed with an aqueous solution of the formulated compound 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 mortality among the larvae was determined. The following examples were active: 70, 197.
Example AB
Cotton leaves were placed into a Petri dish, populated with 5 L2 larvae of the American tobacco budworm (Heliothis virescens) and sprayed with an aqueous solution of the formulated compound to be examined. After 4 days of storage at about 25° C., the mortality among the larvae was determined. The following examples were active: 70, 1047, 197.
Example AC
An aqueous solution of the formulated compound to be examined was mixed with soil. After 0d, 21d and 42d, eggs of the southern corn rootworm (Diabrotica undecimpunctata) were placed together with 2 pre-swollen maize corns into a dish, covered with the treated soil and moisted with 10 ml of water. Soil and eggs were placed in a greenhouse (23° C., 60% relative atmosphere humidity). After 2 weeks of storage, the effect of the compound on the eggs and any larvae hatched therefrom was determined (mortality). The following examples were active: 70, 60, 197, 204.
Example AD
For oviposition, bush beans (Phaseolus vulgaris) were populated for 48 hours with adults of the white fly (Trialeurodes vaporariorum). After the larvae had hatched, the plants were sprayed to run-off point with an aqueous solution of the formulated compound to be examined. After 11 days, the larvicidal action was determined. The following examples were active: 1036, 70, 60, 1040, 197.
Example AE
An aqueous solution of the formulated compound to be examined was mixed with soil. 2⁄3 of the soil were filled into a pot and a pregerminated maize corn and about 30 larvae of the turnip moth (Agrotis segetum) were added and covered with the remaining soil. Soil and larvae were placed in a greenhouse (23° C., 60% relative atmospheric humidity). After 7 days of storage, the mortality among the larvae was determined. The following example was active: 70
Example AF
The formulated compound was pipetted onto filter paper. After the solvent had evaporated, 20–30 tick larvae (Rhipicephalus sanguineus) were placed onto the filter paper. After 24 hours at about 25° C., the effect of the compound on the ticks was determined (mortality). The following examples were active: 197, 1057.
Example AG
190 μl of culture solution and about 20 eggs of the yellow fever mosquito (Aedes aegypti) were placed into each well of a microtiter plate. After the larvae had hatched, 10 μl of an aqueous solution of the formulated compound to be examined were added with a pipette. After 3 days of storage at 25° C. and 60% relative atmospheric humidity, the larvicidal activity of the compound was determined. The following examples were active: 209, 211, 213, 215, 216, 218, 219, 234, 1057, 1059, 1060, 1061, 1062, 235, 1064, 242, 244, 245, 248, 249, 250, 251, 252, 254, 256, 258, 259, 261, 264, 265, 266, 1065, 1066, 1067, 1068, 1069, 267, 289, 290, 291, 292, 293, 294, 301, 303.
Example AH
Cotton leaves were placed into a Petri dish, sprayed with an aqueous solution of the formulated compound to be examined and, after drying, populated with 5 L2 larvae of the American tobacco budworm (Heliothis virescens). After 2, 3 and 4 days of storage at about 25° C., the antifeeding activity of the compound on the larvae was determined. The following examples were active: 1036, 70, 60.
Example AI
A potato plant was sprayed with an aqueous solution of the formulated compound to be examined and, together with an untreated plant, placed in a cage. The cage was populated with 100 larvae of the Colorado beetle (Leptinotarsa decemlineata). After 1 and 3 days of storage at about 25° C., the repellent effect of the compound on the larvae was determined. The following examples were active: 1036, 70, 60.

## Claims

1. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I)




or an N-oxide or salt thereof, wherein:
a) R1 is phenyl, unsubstituted or mono- or polysubstituted by identical or different radicals selected from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-haloalkyl, nitro, cyano, (C1–C4)-alkoxy, (C1–C4)-haloalkoxy, and phenyl, wherein phenyl is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-alkoxy, (C1–C4)-haloalkyl, (C1–C4)-haloalkoxy and (C1–C4)-alkythio, or two substituents together form a group —O—(CH2)2—O—;
b) A is a group CR4R5 wherein:
R4 is hydrogen or methyl; and
R5 is hydrogen or (C1–C4)-alkyl; and

c) R2 and R3 together with the nitrogen atom to which they are attached, form a piperidine radical which is unsubstituted or mono- or polysubstituted by identical or different substituents selected from the group consisting of (C1–C4)-alkyl, and (C1–C4)-haloalkyl.

2. A compound of the formula (I)




or its N-oxide or salt, wherein:
a) R1 is phenyl which is polysubstituted by identical or different radicals selected from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-haloalkyl, nitro, cyano, (C1–C4)-alkoxy, (C1–C4)-haloalkoxy, and phenyl wherein phenyl is unsubstituted or substituted by one or more radicals selected from the group consisting of halogen, (C1–C4)-alkyl, (C1–C4)-alkoxy, (C1–C4)-haloalkyl, (C1–C4)-haloalkoxy and (C1–C4)-alkylthio, or two substituents together form a group —O—(CH2)2—O—;
b) A is a group CR4R5, wherein:
R4 is hydrogen or methyl; and
R5 is hydrogen or (C1–C4)-alkyl; and

c) R2 and R3 together with the nitrogen atom to which they are attached form a piperidine radical which is mono- or polysubstituted by identical or different substituents selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 2-butyl and (C1–C4)-haloalkyl
with the proviso that, when R2 and R3 together with the nitrogen atom to which they are attached form a piperidine radical which is substituted in the position by unsubstituted or substituted alkyl, then R1 is not 3,5-bistrifluoromethylphenyl.

3. A process for preparing a compound of the formula (I) as claimed in claim 2, which comprises reacting a compound of the formula (II)
R1—X (II)
wherein:
X is —O—SO2)—CF3 or halogen and
R1 is as defined in formula (I) as claimed in claim 2 in the presence of a palladium catalyst, a base and a copper(I) salt with a compound of the formula (III)




wherein A, R2 and R3 are as defined in formula (I) as claimed in claim 2.

4. A pesticidal composition, comprising at least one compound of the formula (I) as claimed in claim 2 and at least one formulation auxiliary.

5. A pesticidal composition for application as an insecticidal, acaricidal or nematicidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 2 together with additives or auxiliaries customary for this application.

6. A pesticidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 2 and at least one further active compound together with auxiliaries and additives customary for this application.

7. A pesticidal composition for application in the protection of wood or as a preservative in sealants, in paints, in cooling lubricants for metal working or in drilling and cutting oils, comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 2 together with auxiliaries and additives customary for these applications.

8. A veterinary medicament comprising an insecticidally, acaricidally or nematicidally effective amount of a compound as claimed in claim 2 together with at least one additive or auxiliary customary for veterinary administration.

9. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 2.

10. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a composition as claimed in claim 4.

11. A compound as claimed in claim 2, wherein the radicals substituted on phenyl are selected from the group consisting of F, Cl, CF3, methyl, ethyl, isopropyl, n-propyl, nitro, cyano, —OCH3, —OC2H5, and phenyl.

12. A compound as claimed in claim 2, wherein R4 is hydrogen and R5 is hydrogen or methyl.

13. A compound as claimed in claim 11, wherein R4 is hydrogen and R5 is hydrogen or methyl.

14. The compound as claimed in claim 13, having the formula

15. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I) as defined by claim 2.

16. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I) as defined by claim 11.

17. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I) as defined by claim 12.

18. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I) as defined by claim 13.

19. A method for controlling harmful arthropods and/or helminths, which comprises applying to these or to the plants or animals, areas or substrates infected by them an arthropodicidally or helminthicidally effective amount of a compound of the formula (I) as defined by claim 14.

20. A pesticidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 11 and at least one formulation auxiliary therefor.

21. A pesticidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 12 and at least one formulation auxiliary therefor.

22. A pesticidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 13 and at least one formulation auxiliary therefor.

23. A pesticidal composition comprising an insecticidally, acaricidally or nematicidally effective amount of at least one compound of the formula (I) as claimed in claim 14 and at least one formulation auxiliary therefor.

24. A pesticidal composition for application in the protection of wood or as a preservative in sealants, in paints, in cooling lubricants for metal working or in drilling and cutting oils, comprising an insecticidally effective amount of at least one compound of the formula (I) as claimed in claim 11 together with auxiliaries and additives customary for these applications.

25. A pesticidal composition for application in the protection of wood or as a preservative in sealants, in paints, in cooling lubricants for metal working or in drilling and cutting oils, comprising an insecticidally effective amount of at least one compound of the formula (I) as claimed in claim 12 together with auxiliaries and additives customary for these applications.

26. A pesticidal composition for application in the protection of wood or as a preservative in sealants, in paints, in cooling lubricants for metal working or in drilling and cutting oils, comprising an insecticidally effective amount of at least one compound of the formula (I) as claimed in claim 13 together with auxiliaries and additives customary for these applications.

27. A pesticidal composition for application in the protection of wood or as a preservative in sealants, in paints, in cooling lubricants for metal working or in drilling and cutting oils, comprising an insecticidally effective amount of at least one compound of the formula (I) as claimed in claim 14 together with auxiliaries and additives customary for these applications.

28. A veterinary medicament comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 11 together with at least one auxiliary customary for veterinary administration.

29. A veterinary medicament comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 12 together with at least one auxiliary customary for veterinary administration.

30. A veterinary medicament comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 13 together with at least one auxiliary customary for veterinary administration.

31. A veterinary medicament comprising an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 14 together with at least one auxiliary customary for veterinary administration.

32. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 11.

33. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 12.

34. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 13.

35. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a compound of the formula (I) as claimed in claim 14.

36. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a composition as claimed in claim 20.

37. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a composition as claimed in claim 21.

38. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a composition as claimed in claim 22.

39. A seed, treated or coated with an insecticidally, acaricidally or nematicidally effective amount of a composition as claimed in claim 23.