US20060173044A1

US20060173044A1 - Substituted propargylamines

Info

Publication number: US20060173044A1
Application number: US11/391,077
Authority: US
Inventors: Harald Jakobi; Susan Cramp; Joachim Dickhaut; Stephen Lindell; Jorg Tiebes; Maria Canales; Daniela Jans; Waltraud Hempel; Reed Royalty; Susan McComb; Maria-Theresia Thonessen; Jutta Waibel; Vincent Salgado
Original assignee: Bayer CropScience SA
Current assignee: Merial Ltd
Priority date: 2001-08-23
Filing date: 2006-03-29
Publication date: 2006-08-03
Also published as: JP2005500392A; US20040014784A1; ATE327673T1; DE50207026D1; ES2266618T3; US7084158B2; EP1420644A1; EP1420644B1; WO2003017764A1

Abstract

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

where

a) R¹is heteroaryl or aryl, unsubstituted or mono- or polysubstituted by identical or different radicals,
b) A is a group CR⁴R⁵or C═O, where
- R⁴is hydrogen, halogen or alkyl;
- R⁵is hydrogen, halogen or a substituted or unsubstituted hydrocarbon radical;
c) R²and R³together 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.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This is a divisional of application Ser. No. 10/225,354, filed Aug. 22, 2002, now allowed, incorporated by reference herein in its entirety and relied upon, which claims the priority of German Application Nos. 10141339.4 of Aug. 23, 2001 and 10217697.3 of Apr. 20, 2002.
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 helminthicidal 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) R¹is heteroaryl or aryl, unsubstituted or mono- or polysubstituted by identical or different radicals,
b) A is a group CR⁴R⁵or C═O, where
- R⁴is hydrogen, halogen or alkyl;
- R⁵is hydrogen, halogen or a substituted or unsubstituted hydrocarbon radical;
c) R²and R³together 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) R¹is 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) R²and R³together 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 R²and R³together 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, R¹is 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, OCH₂CF₃and 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:
R¹is 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, heteroarylsulfonylamino, 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—.
R¹is 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 R¹may 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 CR⁴R⁵or C═O, where

- R⁴is preferably hydrogen, fluorine or methyl, particularly preferably hydrogen or fluorine and very particularly preferably hydrogen;
- R⁵is 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.

R²and R³together 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, 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, 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, R²and R³together 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, R²and R³together 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, R²and R³together 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 NaHSO₄and 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 —OSO₂CF₃or 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)₂and Pd(OAc)₂(PPh₃)₂or Pd(OAc)₂and 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 R⁵is 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 R¹X 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 CR⁴R⁵can 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 liftoralis, 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 lignosufonate 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 (S41311), 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, MTI446, 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, T1435, 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. Application 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
Me=methyl
Et=ethyl
Pr=n-propyl
Prⁱ=isopropyl
Bu=n-butyl
Bu^t=tert-butyl
Ph=phenyl
b.p.=boiling point

m.p.=melting point




	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
T⁵⁷	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
T¹¹⁷	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

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

T^j	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

T^k	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	CCl₃
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

T^l	U⁴	V⁴	W⁴

T⁴⁰⁰	H	H	H
T⁴⁰¹	Cl	H	H
T⁴⁰²	H	Cl	H
T⁴⁰³	H	H	Cl
T⁴⁰⁴	CF₃	H	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]

T^m	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

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./0.04mm 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	L⁴²	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	T-4	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, 1H), 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	m.p. 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, 1H)
161	T³²¹	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	T⁴³⁴	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 be 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	½ 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	½ 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	½ SO₄	m.p. 188° C.

1054	T³⁹	CH₂	L⁵⁰		m.p. 176° C.

1055	T³⁹	CH₂	L⁵⁰	½ 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 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 LD₉₀concentration (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 LD₉₀at 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 LD₉₀at 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 LD₉₀at 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 LC₉₀was determined as ppm concentration in the soil, using Abbott's formula. The compounds of Examples 152 and 1039 showed an LC₉₀at 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 1 st 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 KT₅₀was 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 KT₅₀of 11 and 10.5 minutes, respectively. In the case of Culex quinquefasciatus, the KT₅₀was 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 M

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. ⅔ 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 effective amount of a compound of the formula (I)

or an N-oxide or salt thereof, wherein:

a) R¹is heteroaryl, unsubstituted or mono- or polysubstituted by identical or different radicals;

b) A is a group CR⁴R⁵or C═O, wherein:

R⁴is hydrogen or alkyl; and

R⁵is hydrogen or a hydrocarbon radical; and

c) R²and R³together 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.

2. A compound of the formula (I)

or its N-oxide or salt, wherein:

a) R¹is heteroaryl which is unsubstituted or mono- or polysubstituted by identical or different radicals;

b) A is a group CR⁴R⁵or C═O, wherein

R⁴is hydrogen or alkyl; and

R⁵is hydrogen or a hydrocarbon radical; and

c) R²and R³together with the nitrogen atom to which they are attached form a piperidine radical which is unsubstituted or mono- or polysubstituted by identical or different radicals.

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—CF₃or halogen and

R¹is 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, R²and R³are 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 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 claimed in claim 2.