DE4210281A1 - New insecticides, acaricides and nematocides - are 1,2,4-triazol-5-yl-phosphoric- or -phosphonic-acid derivs. - Google Patents

Abstract

1,2,4-Triazol-5-yl-phosphoric- or -phosphonic- acid derivs. of formula (I) are new. R1 = 1-4C alkyl; R2 = 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, NH2, mono- or di- (1-4C alkyl)amino, or phenyl, phenylamno or N-(1-4C alkyl)-N-phenylamino (each opt. ring substd. by 1-5 halo and/or 1-3 1-4C alkyl, 1-4C haloalkyl, 1-4C alkoxy, 1-4C haloalkoxy or 1-4C alkylthio; R3 = H or 1-3C alkyl; R4 = 3-6C cycloalkyl opt. substd. by 1-2 halo and/or 1-3C alkyl; X, Y = O or S. USE - (I) are insecticides, acaricides or nematocides, useful in plant protection, hygiene, veterinary medicine and in protection of stored goods. For plant protection, dosage is 0.01-3 (esp. 0.05-1) kg/ha.

Description

The present invention relates to 1,2,4-triazol-5-yl phosphoric acids or -phosphonic acids of the general formula I.

in which the substituents have the following meaning:
R¹ C₁-C₄ alkyl;
R² is C₁-C₄ alkyl; C₁-C₄ alkoxy; C₁-C₄ alkylthio; Amino; C₁-C₄ alkylamino; Di- C₁-C₄ alkylamino; Phenyl, phenylamino or N-C₁-C₄-alkyl-N-phenylamino, where the aromatic rings can in turn carry one to five halogen atoms and / or one to three of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy or C₁-C₄ alkylthio;
R³ is hydrogen or C₁-C₃ alkyl;
R⁴ C₃-C₆-cycloalkyl, which can carry one or two of the following groups: halogen and / or C₁-C₃-alkyl;
R⁵ C₁-C₄-alkyl or C₃-C₆-cycloalkyl, which can carry one or two of the following groups: halogen and / or C₁-C₃-alkyl;
X and Y are independent of each other
Oxygen or sulfur.

The invention also relates to processes for the preparation of these compounds, they contain pesticides and methods of Pest control.  

From the literature there are 1,2,4-triazol-5-yl phosphoric acids or phosphonic acids, Known with pest control in the 3 position of the triazolyl ring are unsubstituted or one of the following, if appropriate may in turn be substituted or carry residues: alkyl, phenyl, Benzyl or phenylethyl (DE-A 31 18 257). Your action against pests for example at low application rates is not always satisfying.

The object of the present invention was new pest control suitable compounds and processes for their preparation and their Use.

Accordingly, the 1,2,4-triazol-5-yl phosphoric acids defined at the outset or -phosphonic acids I found. In addition, manufacturing processes of these compounds, pesticides and them Processes for their use found.

The compounds I are accessible in various ways.

Compounds of the general formula I are obtained particularly advantageously, by using a triazolyl derivative of the general formula II known per se Way (DE-A 31 18 257) in an inert organic solvent with the salt of a general phosphoric acid or phosphonic acid ester Formula III, esterified.

In formula II, Hal means a halogen atom such as fluorine, chlorine, bromine and Iodine, preferably chlorine or bromine.

Z in formula III stands for one equivalent of an inorganic or organic cations.

As inorganic cations come metal ions, e.g. B. of alkali metals such as Lithium, sodium and potassium, preferably sodium and potassium, of alkaline earth metals  such as preferably magnesium and calcium, and of transition metals such as iron, cobalt, nickel, cupfer, zinc, titanium and chrome or tin.

Among organic cations are in particular the ammonium ion and onium Ions of primary, secondary or tertiary aliphatic or aromatic Understand amines and quaternary ammonium ions. As examples for this its C₁-C₄ alkylammonium ions such as especially the methylammonium ion, Di-C₁-C₄ alkylammonium ions such as especially the dimethylammonium ion and the diethylammonium ion, tri-C₁-C₄-alkylammonium ions such as in particular the trimethylammonium ion and the triethylammonium ion, Tetra-C₁-C₄-alkylammonium ions such as, in particular, the tetramethylammonium Ion and the tetraethylammonium ion, the phenylammonium ion, the diphenylammonium ion, the triphenylammonium ion, C₁-C₄ alkylphenylammonium ions such as in particular the methylphenylammonium ion, di-C₁-C₄-alkylphenylammonium ions such as especially the dimethylphenylammonium ion and the Diethylphenylammonium ion, tri-C₁-C₄-alkylphenylammonium ions such as in particular the trimethylphenylammonium ion and the triethylphenylammonium Ion, C₁-C₄ alkyldiphenylammonium ions such as in particular the methyldiphenylammonium ion, Di-C₁-C₄-alkyldiphenylammonium ions such as in particular the dimethyldiphenylammonium ion and the diethyldiphenylammonium ion and C₁-C₄ alkyltriphenylammonium ions such as especially the methyltriphenylammonium ion called.

The reaction is usually carried out at temperatures from 0 to 120 ° C., preferably from 20 to 70 ° C.

The reaction is generally sufficient above 40 ° C Speed. 70 ° C usually need for a complete turnover not be exceeded.

The reaction can proceed with the generation of heat, which is why it is advantageous can be to provide a cooling facility.

Suitable solvents are, for example, aliphatic hydrocarbons such as pentane, hexane, cyclohexane and petroleum ether, aromatic hydrocarbons such as toluene, o-, m- and p-xylene, halogenated hydrocarbons such as methylene chloride, ethylene chloride, chloroform and chlorobenzene, Ethers such as diethyl ether, diisopropyl ether, tert-butyl methyl ether, dioxane, Anisole and tetrahydrofuran, nitriles such as acetonitrile and propionitrile, Ketones such as acetone, methyl ethyl ketone, diethyl ketone and tert-butyl methyl ketone,  and aprotic dipolar solvents such as dimethyl sulfoxide, Dimethylformamide and pyridine, particularly preferably acetonitrile and Dimethylformamide.

Mixtures of the solvents mentioned can also be used.

The starting materials are usually together in stoichiometric amounts implemented. For example, to increase the yield, be advantageous to one of the starting materials in an excess of 0.1 to 10 mole eq., Preferably 0.2 to 1.5 mole eq. to use.

If Hal in the formula II is chlorine or bromine, the reaction can generally by adding catalytic amounts of potassium iodide or a complexing agent such as crown ether, e.g. B. 18-Krone-6 accelerated will. The catalyst is usually used in amounts of 1 to 20 mol% used.

The reaction mixtures are worked up in a conventional manner, for. B. by Mix with water, separate the phases and, if necessary, chromatographic Cleaning the raw products. The intermediate and end products fall e.g. T. in the form of colorless or slightly brownish, viscous oils, the under reduced pressure and at a moderately elevated temperature of volatile components be freed or cleaned. Provided the intermediate and end products can be obtained as solids, the cleaning can also be carried out by recrystallization or digestion.

The triazole derivatives of the general formula II required for the reaction are known or can be produced by known methods (EP-A 2 87 959; DE-A 31 18 258; Comprehensive Heterocyclic Chemistry, Katritzky et al., Vol. 5, page 733 ff, Pergamon Press, 1984).

The phosphoric acid or phosphonic acid esters of the general formula III are described for example in DE-A 31 18 257.

With regard to the intended use of the compounds I in pesticides, the following substituents are suitable:
R¹ C₁-C₄-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, preferably C₁-C₃-alkyl, especially ethyl and propyl;
R¹ C₁-C₄-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, preferably ethyl, propyl and butyl, especially ethyl and propyl;
C₁-C₄ alkoxy such as methoxy, ethoxy, propyloxy, 1-methylethoxy, butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy and 1,1-dimethylethoxy, preferably methoxy, ethoxy, propyloxy, 1-methylethoxy and 2-methylpropyloxy, in particular Ethoxy, propyloxy and 2-methylpropyloxy;
C₁-C₄-alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methyl-propylthio, 2-methylpropylthio and 1,1-dimethylethylthio, in particular ethylthio, propylthio, 1-methylethylthio, 1-methylpropylthio and 2-methylpropylthio ;
Amino;
C₁-C₄ alkylamino such as methylamino, ethylamino, propylamino, 1-methylethylamino, butylamino, 1-methylpropylamino, 2-methylpropylamino and 1,1-dimethylethylamino, preferably methylamino, ethylamino and 1-methylethylamino, especially 1-methylethylamino;
Di-C₁-C₄-alkylamino such as N, N-dimethylamino, N, N-diethylamino, N, N-dipropylamino, N, N-di- (1-methylethyl) amino, N, N-dibutylamino, N, N-Di - (1-methylpropyl) amino, N, N-di- (2-methylpropyl) amino, N, N-di- (1,1-dimethylethyl) amino, N-ethyl-N-methylamino, N-methyl-N- propylamino, N-methyl-N- (1-methylethyl) amino, N-butyl-N-methylamino, N-methyl-N- (1-methylpropyl) - amino, N-methyl-N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) -N-methylamino, N-ethyl-N-propylamino, N-ethyl-N- (1-methyl-ethyl) amino, N-butyl-N-ethylamino, N-ethyl-N - (1-methyl-propyl) amino, N-ethyl-N- (2-methylpropyl) amino, N-ethyl-N- (1,1-dimethylethyl) amino, N- (1-methylethyl) -N-propylamino, N-butyl-N-propylamino, N- (1-methylpropyl) -N-propylamino, N- (2-methylpropyl) -N-propylamino, N- (1,1-dimethylethyl) -N-propylamino, N-butyl- N- (1-methyl-ethyl) amino, N- (1-methylethyl) -N- (1-methylpropyl) amino, N- (1-methylethyl) -N- (2-methylpropyl) amino, N- (1, 1-dimethylethyl) -N- (1-methyl-ethyl) amino, N-butyl-N- (1-methyl-propyl) amino, N-butyl-N- (2-met hylpropyl) amino, N-butyl-N- (1,1-dimethylethyl) amino, N- (1-methylpropyl) -N- (2-methylpropyl) amino, N- (1,1-dimethylethyl) -N- (1 -methylpropyl) amino and N- (1,1-dimethylethyl) -N- (2-methylpropyl) amino, preferably N, N-dimethylamino and N, N-diethylamino, in particular N, N-dimethylamino;
Phenyl, phenylamino or N-C₁-C₄-alkyl-N-phenylamino such as methyl-N-phenylamino, ethyl-N-phenylamino, propyl-N-phenylamino, 1-methylethyl-N-phenylamino, butyl-N-phenylamino, 1- Methylpropyl-N-phenylamino, 2-methylpropyl-N-phenylamino and 1,1-dimethylethyl-N-phenylamino, especially phenylamino,
the aromatic rings in turn can carry one to five halogen atoms such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine, in particular in the 2- or 4-position of the phenyl ring and / or one to three of the following groups:
C₁-C₄-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, preferably methyl, in particular in the 2- or 4-position of the phenyl ring;
C₁-C₄-haloalkyl, especially C₁-C₂-haloalkyl such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2 Trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2-fluoroethyl, 2,2,2-trichloroethyl and pentafluoroethyl, preferably trichloromethyl and trifluoromethyl, especially trifluoromethyl;
C₁-C₄ alkoxy such as methoxy, ethoxy, propyloxy, 1-methylethoxy, butyloxy, 1-methyl-propyloxy, 2-methylpropyloxy and 1,1-dimethylethoxy, especially methoxy;
C₁-C₄-haloalkyl, especially C₁-C₂-haloalkoxy such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, dichlorofluoromethoxy, chlorodifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-2,2-difluoro Trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoroethoxy, 2,2-dichloro-2-fluoroethoxy, 2,2,2-trichloroethoxy and pentafluoroethoxy;
or C₁-C₄ alkylthio such as methylthio, ethylthio, propylthio, 1-methylethylthio, butylthio, 1-methylpropylthio, 2-methylpropylthio and 1,1-dimethylethylthio, especially methylthio;
R³ is hydrogen or
C₁-C₃-alkyl such as methyl, ethyl, propyl and 1-methylethyl, preferably C₁-C₂-alkyl, especially methyl;
R⁴ C₃-C₆-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, in particular cyclopropyl and cyclohexyl;
which can carry one or two of the following groups: halogen such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine;
and / or C₁-C₃-alkyl such as methyl, ethyl, propyl and 1-methylethyl, preferably C₁-C₂-alkyl, especially methyl;
R⁵ C₁-C₄-alkyl such as methyl, ethyl, propyl, 1-methylethyl, butyl, 1-methylpropyl, 2-methylpropyl and 1,1-dimethylethyl, preferably C₁-C₂-alkyl, especially methyl;
or C₃-C₆-cycloalkyl such as cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl, preferably cyclopropyl and cyclohexyl, especially cyclopropyl,
which can carry one or two of the following groups: halogen such as fluorine, chlorine, bromine and iodine, preferably fluorine and chlorine, in particular chlorine,
and / or C₁-C₃-alkyl such as methyl, ethyl, propyl and 1-methylethyl, preferably C₁-C₂-alkyl, especially methyl;
X and Y are independent of each other
Oxygen or sulfur.

Compounds of the general formula I in which the substituent R¹ C₁-C₃-alkyl such as methyl, ethyl, propyl and 1-methylethyl, preferably C₁-C₂-alkyl, in particular ethyl.

Compounds of the general formula I in which the substituent R 2 has the following meaning are also particularly preferred:
C₁-C₂ alkyl as mentioned above;
C₁-C₄ alkoxy as mentioned above in general and in particular;
C₁-C₄ alkylthio as mentioned above in general and in particular;
Amino;
C₁-C₃ alkylamino as mentioned above;
Di-C₁-C₂-alkylamino as mentioned above;
Phenyl, phenylamino or N-C₁-C₂-alkyl-N-phenylamino as mentioned above,
the aromatic rings in turn can carry one to five fluorine and / or chlorine atoms and / or one to three of the following groups:
C₁-C₃-alkyl as mentioned above in general and in particular, C₁-C₂-haloalkyl as mentioned above in general and in particular, C₁-C₃-alkoxy as mentioned above in general and in particular, C₁-C₂-haloalkoxy as above in general and in particular or C₁-C₃ alkylthio as mentioned above in general and in particular.

In addition, compounds of the general formula I are preferred in which the substituent R³ is hydrogen or methyl.

Further preferred compounds are those in which the substituent R⁴ C₃-C₆-cycloalkyl as mentioned above, which one or two of the following groups: fluorine, chlorine and / or methyl.

In addition, compounds of the general formula I are preferred in which the substituent R⁵ has the following meaning:
C₁-C₃-alkyl as mentioned above or C₃-C₆-cycloalkyl as mentioned above, which can carry one or two of the following groups: fluorine, chlorine and / or methyl.

Examples of particularly preferred compounds of the general Formula I are summarized in the following table:  

table

The compounds of the formula I are suitable for pests from the class of Effectively control insects, arachnids and nematodes. You can in Plant protection as well as in the hygiene, protection of stocks and veterinary sector can be used as pesticides.

Harmful insects belong to the order of the butterflies (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamme, Bupalus piniarius, Cacoecia murinane, Capua reticulana, Cheimatobia brumate, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomenella, Dendrolimus pini, Diaphania nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea, Hyponomeuta malinellus, Keifferia lycopersicella, Lambdina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugta, ostrinia nubilalis, Panolis flamea, Pectoniphora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea opercullella, Phyllocnistis citrella, Pieris brassicae, Plathypena scarbra, Plutella xylostella, Pseudoplusia includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Trichoplusia ni, Zeiraphera canadensius.

From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linaris, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzae,  Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.

From the order of the two-winged species (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Phagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.

From the order of the thrips (Thysanoptera), for example Frankliniella fusca, Franklinealla occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

From the order of the hymenoptera (Hymenoptera), for example, Athalia pink, Atta cephalotes, Atta secdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.

From the order of the bugs (Heteroptera), for example, Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezara viridula, Piesma quadrata, Solubea insularis, Thyanta perditor.

From the order of the plant suckers (Homoptera) for example Acyrothosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis pomi, Aphis sambuci, Brachycaudus cardui, Brevicoryne brassicae, Cerosipha gossypii, Dreyfusia nordmannianae, Dreyfusia piceae, Dyasphis radicola, Dysaulacorthum pseudosolani, Empoasca fabae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerase, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.  

From the order of the termites (Isoptera), for example, Calotermes flavicollis, Leucotermes flavipes, Reticulitermes lucifugus, Termes natalensis.

From the order of the straight wing aircraft (Orthoptera), for example Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.

From the arachnoid class, for example, arachnids (Acarina) such as Amblyomma americanum, Amglyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriophyes sheldoni, Hyalomaa truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranycus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagotarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius, Tetranychus urticae.

From the class of nematodes, for example, root gall nematodes, e.g. B. Maloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cysts forming nematodes, e.g. B. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Heterodera triflolii, stick and Leaf flakes, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchlorhynchus claytoni, Tylenchorhynchus dubius, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi.

The active ingredients as such, in the form of their formulations or use forms prepared from it, e.g. B. in the form of directly sprayable Solutions, powders, suspensions or dispersions, emulsions, Oil dispersions, pastes, dusts, spreading agents, granules Spraying, atomizing, dusting, scattering or pouring applied will. The application forms depend entirely on the purposes; in any case, they should have the finest possible distribution of the Ensure active ingredients according to the invention.  

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions can contain mineral oil fractions from medium to high Boiling point, such as kerosene or diesel oil, as well as coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, e.g. B. benzene, toluene, xylene, paraffin, Tetrahydronaphthalene, alkylated naphthalenes or their derivatives, Methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, Cyclohexanol, cyclohexanone, chlorobenzene, isophorone, strongly polar solvents, e.g. B. dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, Water.

Aqueous application forms can be made from emulsion concentrates, pastes or wettable powders (wettable powders, oil dispersions) by adding water be prepared. For the production of emulsions, pastes or oil dispersions can use the substances as such or in an oil or solvent dissolved, by means of wetting, adhesive, dispersing or emulsifying agents in Water can be homogenized. But it can also be made from effective substance Wetting agents, adhesives, dispersants or emulsifiers and possibly solvents or oil existing concentrates are made to be diluted with Water are suitable.

Alkali, alkaline earth, ammonium salts come as surface-active substances of ligninsulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalenesulfonic acid, Alkylarylsulfonates, alkylsulfates, alkylsulfonates, Fatty alcohol sulfates and fatty acids and their alkali and alkaline earth salts, Salts of sulfated fatty alcohol glycol ether, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, Octylphenol, nonylphenol, alkylphenol polyglycol ether, tributylphenyl polyglycol ether, Alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, Sorbitol esters, lignin sulfite liquors and methyl cellulose in Consider.

Powders, materials for spreading and dusts can be mixed or combined Grinding the active substances with a solid carrier will.  

The formulations generally contain between 0.01 and 95% by weight, preferably between 0.1 and 90% by weight of the active ingredient. The active ingredients are in a purity of 90% to 100%, preferably 95% to 100% (according to the NMR spectrum).

Examples of formulations are:

• I. 5 parts by weight of compound no. 7 are mixed with 95 parts by weight finely divided kaolin mixed intimately. You get this way a dust containing 5% by weight of the active ingredient.
• II. 30 parts by weight of compound no. 10 are mixed with 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil that is on the surface of this silica gel was sprayed, mixed intimately. You get one in this way Preparation of the active ingredient with good adhesiveness (active ingredient content 23% by weight).
• III. 10 parts by weight of compound no. 15 are mixed solved, the 90 parts by weight of xylene, 6 parts by weight of Addition product of 8 to 10 moles of ethylene oxide with 1 mole Oleic acid-N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzenesulfonic acid and 2 parts by weight of the adduct of There is 40 moles of ethylene oxide with 1 mole of castor oil (active ingredient content 9% by weight).
• IV. 20 parts by weight of compound No. 8 are mixed dissolved, from 60 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 5 parts by weight of the adduct of 7 moles Ethylene oxide in 1 mole of isooctylphenol and 5 parts by weight of the adduct of 40 moles of ethylene oxide to 1 mole of castor oil exists (active ingredient content 16 wt .-%).
• V. 80 parts by weight of compound no. 1 are mixed with 3 parts by weight of the Sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignosulfonic acid a sulfite waste liquor and 7 parts by weight of powdered silica gel well mixed and ground in a hammer mill (active ingredient content 80% by weight).
• VI. 90 parts by weight of compound no. 5 are mixed with 10 parts by weight. Share N-methyl-α-pyrrolidone and get a solution for Use in the form of tiny drops is suitable (active ingredient content 90% by weight).  
• VII. 20 parts by weight of compound no. 17 are mixed dissolved, from 40 parts by weight of cyclohexanone, 30 parts by weight Isobutanol, 20 parts by weight of the adduct of 7 moles Ethylene oxide in 1 mole of isooctylphenol and 10 parts by weight of Addition product of 40 moles of ethylene oxide with 1 mole of castor oil consists. By pouring and finely distributing the solution in 100,000 parts by weight of water are obtained in an aqueous dispersion, which contains 0.02% by weight of the active ingredient.
• VIII. 20 parts by weight of active ingredient no. 3 are mixed with 3 parts by weight of the Sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17% by weight Share the sodium salt of a lignosulfonic acid from a Sulfite waste liquor and 60 parts by weight of powdered silica gel well mixed and ground in a hammer mill. By fine The mixture is distributed in 20,000 parts by weight of water a spray mixture which contains 0.1% by weight of the active ingredient.

Granules, e.g. B. coating, impregnation and homogeneous granules by binding the active ingredients to solid carriers. Solid carriers are e.g. B. mineral earths, such as silica gel, silicas, Silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, Bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, Magnesium oxide, ground plastics, fertilizers such. B. ammonium sulfate, Ammonium phosphate, ammonium nitrate, urea and vegetable Products such as flour, tree bark, wood and nutshell flour, Cellulose powder and other solid carriers.

The active ingredient concentrations in the ready-to-use preparations can be varied in larger areas.

Generally they are between 0.0001 and 10%, preferably between 0.01 and 1%.

The active ingredients can also be used with great success in the ultra-low-volume process (ULV) can be used, whereby it is possible to use formulations with more than 95% by weight of active ingredient or even the active ingredient without additives.

The amount of active ingredient applied under field conditions is 0.01 to 3, preferably 0.05 to 1 kg / ha.

Oils of various types, herbicides, fungicides, other pesticides, bactericides, if necessary first immediately before use (tank mix). This means can to the agents according to the invention in a weight ratio of 1:10 to 10: 1 can be added.  

Synthesis examples

The rules set out in the synthesis examples below were modified accordingly with the starting compounds Obtaining further compounds I used. The compounds thus obtained are listed in the tables below with physical details.

Example 1

A mixture of 7.9 g (0.033 mol) of potassium O-ethyl-S-n-propyl-dithiophosphate, 0.08 g 18-Krone-6 and 40 ml abs. Acetonitrile was at 25 ° C dropwise with a solution of 5.2 g (0.03 mol) of 5-chloromethyl-3- cyclopropyl-1-methyl-1,2,4-triazole in 6 ml abs. Acetonitrile added. To The reaction mixture was worked up for 12 hours at 40 ° C. For this the solvent was distilled off under reduced pressure, the so residue obtained taken up in t-butyl methyl ether and the ethereal Washed solution with water. The organic phase became The crude product is isolated and purified by chromatography (silica gel; Toluene / ethyl acetate 1: 2).

5.6 g (55% of theory) of the product were thus obtained as a colorless oil (active ingredient example No. 1.13).

Elemental analysis: C₁₂H₂₂N₃O₂PS₂
calc .:
C: 42.97; H: 6.61; N: 12.53;
found:
C: 42.8; H: 6.8; N: 12.4;

300 MHz ¹H-NMR spectrum in CDCl₃ (δ values in ppm against tetramethylsilane as internal standard):

0.87-0.92 (m, 4H); 1.01 (t, 3H); 1.36 (t, 3H); 1.67-1.79 (m, 2H); 1.93-2.03 (m, 1H); 2.80-2.95 (m, 2H); 3.86 (s, 3H); 4.13-4.24 (m, 4H);

Infrared absorptions (cm ^-1 ): 1249, 1229, 1014, 995

Table 1

Examples of use

The insecticidal activity of the compounds of general formula I let were shown by the following tests:

The active ingredients were

• a) as a 0.1% solution in acetone or
• b) as a 10% emulsion in a mixture of 70% by weight cyclohexanol, 20% by weight Nekanil® LN (Lutensol® AP6, wetting agent with emulsifying and dispersing action based on ethoxylated alkylphenols) and 10% by weight emulphor ® EL (Emulan® EL, emulsifier based on ethoxylated fatty alcohols)
  processed and diluted according to the desired concentration with acetone in the case of a) or with water in the case of b).

After the end of the tests, the lowest concentration was determined, where the compounds compared to untreated controls cause 80-100% inhibition or mortality (Effective threshold or minimum concentration).

A. Aphis fabae (black louse), contact effect

Badly infested bush beans (Vicia faba) were washed with the watery Treatment of active ingredients. After 5 d the mortality rate determined using a binocular. In this test, compounds 1, 5, 8, 12 and 13 thresholds from 4 to 100 ppm.

B Musca domestica (housefly), attempted contact

The bottom of a test vessel was covered with the acetone solution of the Active ingredient wetted and after evaporation of the solvent 10 flies occupied. The mortality rate was determined after 24 h. In this test showed the compounds 5, 7, 8, 10 and 12 thresholds of action from 0.01 to 1 mg.  

C. Plutella maculipennis (cockroach caterpillar), feeding inhibition

Young kohlrabi leaves were treated with the aqueous active ingredient preparation wetted and then placed on a moistened filter. The Prepared leaves were then each with 10 caterpillars of the 4th stage of development documented. After 48 hours the feeding inhibition certainly. In this test, compounds 2, 3, 5, 6 and 13 showed Thresholds from 40 to 400 ppm.

D. Plutella maculipennis (cockroach caterpillar), contact effect

Leaves of young kohlrabi plants were treated with the aqueous active ingredient preparation wetted and then on a moistened filter placed. The prepared leaves were then each with 10 caterpillars of the 4th stage of development occupied. After 48 hours the mortality rate is determined. In this test the compounds showed 2, 3, 5, 6 and 13 thresholds from 40 to 400 ppm.

Claims (5)

1. 1,2,4-triazol-5-yl phosphoric acids or phosphonic acids of the general formula I, in which the substituents have the following meaning:
R¹ C₁-C₄ alkyl;
R² is C₁-C₄ alkyl; C₁-C₄ alkoxy; C₁-C₄ alkylthio; Amino; C₁-C₄ alkylamino; Di-C₁-C₄ alkylamino; Phenyl, phenylamino or N-C₁-C₄-alkyl-N-phenylamino, where the aromatic rings can in turn carry one to five halogen atoms and / or one to three of the following groups: C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁ -C₄ alkoxy, C₁-C₄ haloalkoxy or C₁-C₄ alkylthio;
R³ is hydrogen or C₁-C₃ alkyl;
R⁴ C₃-C₆-cycloalkyl, which can carry one or two of the following groups: halogen and / or C₁-C₃-alkyl;
R⁵ C₁-C₄-alkyl or C₃-C₆-cycloalkyl, which can carry one or two of the following groups: halogen and / or C₁-C₃-alkyl;
X and Y are independent of each other
Oxygen or sulfur. 2. A process for the preparation of the compounds of the general formula I according to claim 1, characterized in that a triazolyl derivative of the general formula II, in which Hal represents a halogen atom, in a manner known per se in an inert organic solvent with the salt of a phosphoric acid or phosphonic acid ester of the general formula III, in which Z represents an equivalent of an inorganic or organic cation, esterified. 3. Pesticide containing an effective amount of a compound of the general formula I according to claim 1 and inert additives. 4. A method for controlling pests, characterized in that to control the pests and / or their habitat with an effective amount a compound of general formula I treated according to claim 1. 5. Use of compounds of general formula I according to claim 1 to control pests.