DE3941296A1 - New N-hydroxy-azole ether derivs. - Google Patents

Abstract

N-Hydroxyazole ethers of formula (I) are new, X and Y = O, S, SO, SO2, or CH2, B = a 1-pyrazolyl gp. of formula B1 or a 1,2,4-triazol-1-yl gp. of formula B2, R1 and R2 = H or 1-3C alkyl, R3 = H, halogen, or 1-3C alkyl, z = 1-3, R4-R6 = H, halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C haloalkyl or 1-4C haloalkyl, n = 0-2,.

Description

N-Hydroxytriazoles of the general formula I

in which the substituents have the following meaning:

X, YO, S, SO, SO₂, CH₂,
R¹, R² are hydrogen, C₁-C₃-alkyl,
R³, R⁴, R⁵ hydrogen, halogen C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,
n 0, 1, 2.

From GB-A 21 15 812 certain O-substituted oximes are known. The However, the compound described there is insecticidal unsatisfactory.

The invention was based on the object, new insecticidal active ingredients To provide basis of N-hydroxytriazoles, which in their Effect known compounds are superior.

Accordingly, it was found that the substitutes defined at the outset N-hydroxytriazoles of the formula I are excellent for combating Pests.

The preparation of the substituted N-hydroxytriazoles I according to the invention is carried out by reacting compounds of the formula II

in which A represents a nucleophilically displaceable leaving group, with a N-hydroxytriazole of the formula III

in the presence of a base or directly with the alcoholate.

The reaction can be in the temperature range from (-20) to 250 ° C, preferably 20 to 120 ° C according to the following reaction equation:

Route 1:

In the above reaction equation, the radical A is a conventional one Leaving group such as a sulfonic acid residue or a halogen. Among the sulfonic acid residues are methanesulfonyl, trifluoromethanesulfonyl and p-toluenesulfonyl, chlorine and bromine are preferred among the halogen, chlorine is particularly preferred:

where R¹, R², R³, R⁴, R⁵, X, Y and n have the meanings defined above and R⁷ in the case of R² = hydrogen have a group -OR⁸ R⁸ = C₁-C₃-alkyl and in the case of R² = C₁-C₃-alkyl the corresponding one C₁-C₃ alkyl group.

The after the above Hydroxy compound obtained in can in itself in a known manner into other nucleophilically displaceable leaving groups be, e.g. B. by reaction with phosphorus tribromide.

If A in the starting material II represents a halogen atom, then the following route 2 can be used for the production.

Route 2:

The radicals R¹, R², R³-R⁵, X, Y and n have the above meaning, Hal stands for halogen, e.g. B. bromine or chlorine.

The exit connections used for both routes are known or can be carried out in a manner known per se (see, for example, Angew. Chem. 52, 915 (1938) or Japanese Patent Publication No. 62 033/1980) will.  

The N-hydroxytriazole can according to the in the older German application P 39 00 347.7 described processes are produced. Then you bet a 1-H-1,2,4-triazole IV with a peroxy compound, e.g. B. hydrogen peroxide at temperatures from -20 ° C to + 150 ° C. If necessary, you can add an agent, which first the 1-H-triazole in the salt transferred. The implementation is represented by the following reaction scheme, where Me for a metal, e.g. B. alkali metal:

In the event that the 1-H-1,2,4-triazoles IV with peroxoy groups carrying compounds without the addition of a salt-forming agent, proceed as follows:

1 to 3 molar equivalents of 1-H-1,2,4-triazole IV are in a solvent such as water, water / acetone mixture, tetrahydrofuran, diglyme, methylene chloride or chloroform with 1 mol equivalent of a peroxocarboxylic acid, preferably m-chloroperbenzoic acid added. The reaction temperature is between 0 and 50 ° C, preferably at room temperature.

In the event that one carries the 1-H-1,2,4-triazoles with peroxo groups Reacts compounds with the addition of a salt-forming agent, proceeds one as follows:

• a) 1 to 10 molar equivalents of 1-H-1,2,4-triazole IV are in an inert Solvents such as diglyme, tetrahydrofuran or diethyl ether with a organometallic compound of an alkali metal suspension or Metallized hydride, then with 1 mol equivalent of dibenzoyl peroxide transferred. The mixture is stirred at room temperature for several days.
• b) 1 to 3 molar equivalents of 1-H-1,2,4-triazole IV in water with a Metal hydroxide, a carbonate or a hydroxarbonate, then mixed with 1 molar equivalent of peroxcarboxylic acid and over Stirred at night. Instead of peroxcarboxylic acid, you can also do that Use alkali or alkaline earth metal salt of peroxocarboxylic acid and z. B. in add solid form.

As salt-forming agents are organometallic compounds such. B. Metal alkyls such as n-butyllithium, tert-butyllithium and methyl lithium, Metallaryls such as phenyllithium, alkali metal suspensions such as sodium in Toluene or potassium in toluene, hydrides, e.g. B. alkali hydrides such as lithium hydride, Sodium hydride and potassium hydride, alkaline earth hydrides such as calcium hydride, preferably sodium hydride, hydroxides, e.g. B. alkali metal hydroxides such as Lithium hydroxide, sodium hydroxide and potassium hydroxide, alkaline earth hydroxide such as calcium hydroxide and magnesium hydroxide, carbonates, e.g. B. alkali carbonates such as lithium carbonate, sodium carbonate and potassium carbonate, alkaline earth carbonates such as calcium carbonate and magnesium carbonate, hydrogen carbonate, e.g. B. sodium bicarbonate.

These reactions can preferably also be carried out in the presence of a solvent be performed. When using organometallic compounds or hydrides are suitable ethers such as diethyl ether, methyl butyl ether, Tetrahydrofuran and dioxane, glycol ethers such as diglyme, triglyme, aliphatic Hydrocarbons such as pentane, hexane, petroleum ether, cyclohexane, aromatic Hydrocarbons such as benzene, toluene and the xylenes or their Mixtures.

Suitable when using hydroxides, carbonates or hydrogen carbonates water, alcohols such as methanol, ethanol, n-propanol, iso-propanol and the butanols, ketones, such as acetone and diethyl ketone or mixtures thereof, prefers water.

Hydrogen peroxide are suitable as compounds containing peroxo groups or organic peroxides, e.g. B. dialkyl peroxides, alkylaryl peroxides, diaryl peroxides, Diacyl peroxides such as diacetyl peroxide, dipropionyl peroxide and Dibenzoyl peroxide, preferably dibenzoyl peroxide; Peroxyacids e.g. B. peroxosulfonic acids such as p-toluene peroxosulfonic acid, toluene peroxosulfonic acid, p-Bromotoluene peroxosulfonic acid and methyl peroxosulfonic acid, preferred p-toluenesulfonic acid, peroxocarboxylic acids such as peroxoacetic acid, peroxobenzoic acid, m-chloroperbenzoic acid, peroxopropionic acid, peroxobutyric acid, Peroxomaleic acid, monoperoxosuccinic acid and monoperoxophthalic acid, preferably monoperoxophthalic acid.

At least one is normally used to prepare the compounds I. equivalent amounts of a base, based on III, to II and / or III, but can also in excess or, if appropriate, as a solvent use. Suitable bases are, for example, hydroxides of Alkali and alkaline earth metals such as sodium hydroxide, potassium hydroxide and Calcium hydroxide, alcoholates of alkali and alkaline earth metals such as  Sodium methylate, sodium methylate, calcium methoxide or potassium tert-butoxide; Alkali or alkaline earth metal hydrides such as sodium hydride, Potassium hydride or calcium hydride; Alkali or alkaline earth carbonates such as Sodium carbonate, potassium carbonate or calcium carbonate; aliphatic amines such as dimethylamine, triethylamine or diisopropylamine; heterocyclic amines such as piperidine, piperazine or pyrrolidine; aromatic amines such as pyridine or pyrrole and optionally also alkyl lithium compound such as n-butyllithium.

According to the method described above, the starting materials II are used and III usually in a stoichiometric ratio. An excess of the one or the other can be quite advantageous in individual cases be.

The reaction is conveniently carried out in a solvent or diluent carried out. For example, are suitable for this aliphatic hydrocarbons such as n-pentane, n-hexane, the hexane isomer mixture and petroleum ether; aromatic hydrocarbons such as benzene, Toluene, the xylenes and isomer mixtures, gasoline; Alcohols like Methanol, ethanol, n-propanol and isopropanol; Ethers such as diethyl ether, Di-n-butyl ether, methyl tert-butyl ether, tetrahydrofuran and dioxane; Ketones such as acetone, methyl ethyl ketone and methyl isopropyl ketone; Nitriles like Acetonitrile and propionitrile; aprotic dipolar solvents such as Dimethylformamide, dimethyl sulfoxide or pyridine. Mixtures of these Substances can be used as solvents and thinners.

The reactions usually proceed above -20 ° C with sufficient Speeds. In general, 120 ° C do not have to be exceeded. As they develop heat in some cases, it can develop from Be advantageous to provide cooling options.

The reaction mixtures are worked up in a conventional manner, for. B. by Mix with water, separate the phases and column chromatography. The new compounds of formula I fall partly in the form of colorless or Slightly brownish-colored, viscous oils that develop through prolonged heating under reduced pressure to moderately elevated temperature ("distillation") rid of the last volatile parts and on them Let way clean. Obtaining the compounds of formula I in crystalline form, so its purification by recrystallization respectively.

The individual substituents of the formula I have the following meanings:

X, YO, S, SO, SO₂, CH₂, preferably O and S, particularly preferably O
R¹, R² are hydrogen, C₁-C₃-alkyl such as methyl, ethyl, propyl, i-propyl, preferably hydrogen and C₁-C₂-alkyl, particularly preferably hydrogen and methyl,
R³, R⁴, R⁵ are hydrogen, halogen, particularly preferably hydrogen, fluorine, chlorine and bromine;
C₁-C₄ alkyl, preferably C₁-C₃ alkyl, particularly preferably methyl, ethyl and i-propyl;
C₁-C₄ alkoxy such as methoxy, ethoxy, propoxy, butoxy, preferably methoxy and ethoxy;
C₁-C₄ haloalkyl, e.g. B. fluoro and chloroalkyl, preferably C₁-C₂ fluoroalkyl, particularly preferably trifluoromethyl;
C₁-C₄ haloalkoxy, preferably C₁-C₃ fluoroalkoxy, particularly preferably difluoromethoxy, trifluoromethoxy, 1,1,2,2-tetrafluoroethoxy;
n the numbers 0, 1, 2, preferably 0 and 1, particularly preferably 0.

The compounds according to the invention can have one or more centers of asymmetry contain. This excludes all possible stereoisomers such as Diastereomers, enantiomers and mixtures of diastereomers and enantiomers a.

The substituted N-hydroxytriazoles of the general formula I are suitable pests from the class of insects, acarids and nematodes fight effectively. They can be used in crop protection as well as on hygiene, Storage protection and veterinary sector as pesticides be used.

Harmful insects belong to the order of the butterflies (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus,  Eupoecilia ambiguella, Evetria bouliana, Feltia subterramea, 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, Malacosome neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma suacia, Phalera bucephala, Phthorimaea operculella, 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 canadensis.

From the order of the beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, anthonomus grandis, anthonomus pomorum, atomaria linearis, 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, Ortiorrhynchus ovatus, Phaedon cochleariae, Phillotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta nemorum, Phyllotetra 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, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.

From the order of the thrips (Thysanoptera), for example Frankliniealla fusca, Frankliniella 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 sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaois, 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 (Homotera), for example Acyrthosiphon 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 cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Sappahis mala, Sppahis 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, Aceta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locuste migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca americana, Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.  

The arachnoid class includes arachnids (Acarina), for example Amblyomma americanum, Amglyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentor silvarum, Eotetranychus carpini, Eriphyes sheldoni, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata, Otobins megnini, Paratetranychus 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.

The class of nematodes includes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cysts forming nematodes, e.g. B. Globodera rostochiensis, Heterodera avenae, Hetrodera glycinae, Heterodera schachtii, Heterodera trifolii, stick and Leaf flakes, e.g. B. Belonolaimus longicaudatus, Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elongatus, Radopholus similis, Rotylenchus robustus, Trichodorus primitivus, Tylenchorhynchus 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, sprinkles, granules by spraying, Nebulization, dusting, scattering or pouring can be used. The application forms depend entirely on the purposes; they should in any case the finest possible distribution of the active ingredients according to the invention guarantee.

For the production of directly sprayable solutions, emulsions, pastes or oil dispersions come 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, tetra hydronaphthalene, 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, in Consider.  

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, alkylarylsulfonates, Alkyl sulfates, alkyl sulfonates, alkali and alkaline earth salts dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, fatty acid alkali and alkaline earth salts, salts of sulfated hexadecanols, Heptadecanols, octadecanols, salts of sulfated fatty alcohol glycol ether, Condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or Naphthalenesulfonic 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 ether, ethoxylated polyoxypropylene, Lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite waste liquor and methyl cellulose.

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

Examples of formulations are:

• I. 5 parts by weight of compound no. 1 with 95 parts by weight of finely divided Kaolin mixed intimately. You get one in this way Dusts containing 3% by weight of the active ingredient.
• II. 30 parts by weight of compound no. 2 are mixed with 92 parts by weight of powdered silica gel and 8 parts by weight Paraffin oil that is sprayed onto the surface of this silica gel was mixed intimately. You get one in this way Preparation of the active ingredient with good adhesiveness.  
• III. 10 parts by weight of compound no. 19 are dissolved in a mixture, that from 90 parts by weight of xylene, 6 parts by weight of the adduct from 8 to 10 moles of ethylene oxide to 1 mole of oleic acid-N-monoethanolamide, 2 parts by weight of calcium salt of dodecylbenzene sulfonic acid and 2 parts by weight of the adduct of 40 moles There is ethylene oxide in 1 mol of castor oil.
• IV. 20 parts by weight of compound no. 5 are dissolved in a mixture, made from 60 parts by weight of cyclohexanone, 30 parts by weight of 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.
• V. 80 parts by weight of compound no. 13 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.

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 formulations generally contain between 0.1 and 95% by weight Active ingredient, preferably between 0.5 and 90 wt .-%.

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 10, preferably 0.05 to 2.0 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.

Preparation of compounds 1 1- {2- [4- (3-chloro) phenoxyphenoxy] ethoxy} -1,2,4-triazole (Example No. 19 in the table below)

To a suspension of 0.31 g (12.4 mmol) sodium hydride in 3 cm³ A solution of 0.96 g is added dropwise to dimethylformamide while cooling with ice (11.3 mmol) 1-hydroxy-1,2,4-triazole in 10 cm³ dimethylformamide. To 30 minutes of stirring, a solution of 3.9 g (11.3 mmol) of 2- [4- (3-chloro) phenoxy-phenoxy] ethyl methyl sulfonate in 20 cm³ dimethylformamide at 60 ° C added dropwise, then 3 hours at 80 ° C and another 14 h at room temperature touched. Then volatile constituents are removed, the Residue taken up in about 100 cm³ of ethyl acetate, with water washed, dried over sodium sulfate and concentrated. It remains yellowish oil back.

Yield: 2.9 g (77% of the arithmetically possible amount).
Infrared absorptions [cm ^-1 ]: 1502, 1472, 1273, 1222, 1194, 1004, 907, 840, 680.
1 H-NMR spectrum (300 MHz in CDCl₃; δ values in ppm against tetramethylsilane): 4.23 (2 H, m, c), 4.71 (2 H, m, c), 6.80-7, 28 (8 H, m), 7.8 (1 H, s), 8.11 (1 H, s).

table

Substituted N-hydroxytriazoles I

Preparation of 1-hydroxy-1,2,4-triazole

103.5 g (1.5 mol) of 1-H-1,2,4-triazole were dissolved in 1344 g (12 mol) of 50% aqueous potassium hydroxide dissolved. 340 g (3 mol) 30% H₂O₂, 555 g (3.75 mol) phthalic anhydride was added in portions and stirred for 2 hours at room temperature (20 to 30 ° C). Subsequently was acidified to a pH <1.5 with approx. 35% sulfuric acid, the precipitate formed is suctioned off and the filtrate by quantitative HPLC measurement examined. 19 g (15%) of N-hydroxy-1,2,4-triazole were obtained, that was worked up as usual; Mp: 132 ° C.

Examples of use

In the following examples, the compounds or agents containing them with regard to their action on pests with the Compound A known below from GB-A 21 15 812.

The concentrations at which the compounds tested are 100% The respective minimum concentrations cause mortality or inhibition. At least 2 attempts were made at each concentration carried out.

The purity of the active ingredients is <95%. The wording was a 10 wt .-% emulsion concentrate selected, which by emulsifying the Active ingredient in a mixture of 70 wt .-% cyclohexanone, 20 wt .-% Nekanil LN® (Lutensol AP6, wetting agent with emulsifying and dispersing effect based on ethoxylated alkylphenols) and 10% by weight Emulphor EL® (Emulan El®), emulsifier based on ethoxylated fatty alcohols). The concentrations given in the examples were by dilution of the formulated active ingredient obtained with water.

Example A Dysdercus intermedius (cotton bug); ovicidal effect

Stick-on labels were attached to the upper edge with pieces of adhesive tape (approx. 0.8 cm). The eggs were shaken 24 hours before the start of the experiment Immerse in the receptacle attached to the adhesive tape edge. The Eggs were placed in the aqueous preparation for about 5 seconds dipped, then allowed to drain on filter paper. In doing so the eggs are not laid on the paper.

The trimmed labels were with the adhesive strips facing up placed in vessels, each with a to prevent dehydration Half a cotton roll soaked in water. After covering the Vessels with glass plates were waited for until the larvae in a control experiment (hatched without active ingredient (about 8 days) and then rated.

At an active substance concentration of 1000 ppm, the comparison bond was A ineffective while compounds 1, 2, 6, 13 and 108 had mortality caused by 100%.

Claims (6)

1. Substituted N-hydroxytriazoles of the general formula I in which the substituents have the following meaning:
X, YO, S, SO, SO₂, CH₂,
R¹, R² are hydrogen, C₁-C₃-alkyl,
R³, R⁴, R⁵ hydrogen, halogen C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkyl, C₁-C₄-haloalkoxy,
n 0, 1, 2. 2. A process for the preparation of the substituted N-hydroxytriazoles of the formula I according to claim 1, characterized in that an appropriately substituted compound II wherein A is a nucleophilically displaceable leaving group, with an N-hydroxytriazole of the formula III in the presence of a base or directly with the alcoholate. 3. Pesticide containing a substituted N-hydroxytriazole according to claim 1 in addition to the usual carriers. 4. pesticide according to claim 3, characterized in that it is 0.1 to 95 wt .-% of a substituted N-hydroxytriazole Claim 1 contains.   5. A method for controlling pests, characterized in that the pests and / or those to be kept free from pests Areas and / or spaces with an effective amount for pests Substituted N-hydroxytriazole of the general formula I according to Claim 1 treated. 6. Substituted N-hydroxytriazoles of the formula I according to claim 1, in which X and Y are oxygen and n is zero.