DE4024094A1 - New 2-substd. benzyl cyclopropane carboxylate ester derivs. - Google Patents

Abstract

Substd. benzyl cyclopropane carboxylate esters of formula (I) are new: Where X = CH or N; A = a gp. (i)-(iv) R1 = CN, 2-8C alkyl, CF3, 3-8C alkenyl, Me3Si, 1-4C alkoxycarbonyl, phenyl (1-6C) alkyl or phenyl (3-6C) alkenyl (in which the aromatic rings can be substd. by 1-5 halo or 1-3 of 1-6C alkyl (opt. partially or fully halogenated) or 1-6C alkoxy); or R1 is phenyl substd. by EtO; 2- or 3- Br; 2- or 4- CF3; 2,4- or 2,6-F2; 2-F-6-Cl; 2,4- or 2,6-Me2, or 2,3,6-Cl3; R2 = H or halo; R3 = phenyl (opt. substd. by 1-5 halo or 1-3 of 1-6C alkyl (opt. partially or fully halogenated) or 1-6C alkoxy); R4 = Me or halogen; Proviso: X = CH if R1 = CF3 or Me3Si. More specifically A = A' with R1 = CN, 2-4C alkyl, CF3, 3-4C alkenyl, Me3Si, 1-2C alkoxycarbonyl, phenyl (1-4C) alkyl or phenyl (3-4C) alkenyl (opt. ring substd. by halo or Me); or phenyl substd. by 2-Br; 2,4- or 2,6-F2; 2-F-6-Cl or 2,3,6-Cl3.

Description

The present invention relates to new ortho-substituted benzyl esters of cyclopropanecarboxylic acids of the general formula I

in the X for nitrogen or = CH- and A for one of the following cyclo propane residue stands:

where the substituents have the following meaning:

R¹ cyano, C₂-C₈-alkyl, trifluoromethyl, C₃-C₈-alkenyl, trimethylsilyl, C₁-C₄-alkoxycarbonyl, phenyl-C₁-C₆-alkyl or phenyl-C₃-C₆-alkenyl, where the aromatic each 1-5 halogen atoms or can carry up to 3 of the following substituents:
C₁-C₆-alkyl, partially or fully halogenated C₁-C₆-alkyl or C₁-C₆-alkoxy, ethoxyphenyl, 2-bromophenyl, 3-bromophenyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2,4-difluorophenyl, 2,6- Difluorophenyl, 2-fluoro-6-chlorophenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl or 2,3,6-trichlorophenyl:
R² is hydrogen or halogen;
R³ is phenyl which can carry 1-5 halogen atoms or up to 3 of the following substituents: C₁-C₆-alkyl, partially or completely halogenated C₁-C₆-alkyl or C₁-C₆-alkoxy;
R⁴ is methyl or halogen;
Hal halogen;
with the proviso that X is = CH- when R¹ is trifluoromethyl or tri methylsilyl.

In addition, the invention relates to a method for producing this Ver compounds, their use as fungicides and their use in combating pest control, fungicidal and pest control agents containing these compounds as active substances.

EP-A 3 10 954 and EP-A 3 54 571 are also fungicidal, among others effective ortho-substituted benzyl esters of cyclopropanecarboxylic acids from Type of compounds I known, the cyclopropane ring is unsubstituted or a methyl, dichloro or variously substituted phenyl radical wearing. Furthermore, EP-A 3 54 571 u. a. 2- [1- (trifluoromethyl) cyclo propyl-carbonyloxymethyl] phenyl and 2- [1- (trimethylsilyl) cyclopropyl carbonyloxymethyl] -phenyl-glyoxylsäuremethylester-O-methyloxim known. An insecticidal effect is not from the publications mentioned known.

The invention lay new ortho-substituted benzyl esters of cyclopropane carboxylic acids as a task.

Accordingly, the ortho-substituted benzyl esters defined at the outset of cyclopropanecarboxylic acids of the formula I found.

Specifically, the substituents in the verb according to the invention I mean the following:

R1 - cyano;
- Branched or unbranched C₂-C₈-alkyl, especially C₂-C₆-alkyl such as methyl, ethyl, isopropyl, n-butyl, tert-butyl, n-pentyl, isopentyl and neopentyl;
- Branched or unbranched C₃-C₈ alkenyl, especially C₃-C₆ alkenyl such as prop-2-enyl, 1-methyl-2-propenyl, but-2-enyl, 3-methyl-but-2-enyl or 2-methyl -prop-2-enyl;
- C₁-C₄ alkoxycarbonyl, especially methoxycarbonyl and ethoxy carbonyl;
- Phenyl-C₁-C₆-alkyl or phenyl-C₃-C₆-alkenyl, especially phenyl-C₁-C₄-alkyl or phenyl-C₃-C₄-alkenyl such as benzyl, 2-phenylethyl, 3-phenyl-n-propyl, 4- Phenyl-n-butyl, 3-phenylallyl and 4-phenyl-2-butenyl,
where the aromatic can each carry 1-5 halogen atoms such as fluorine, chlorine and bromine or up to 3 of the following substituents:

• - Branched or unbranched C₁-C₆ alkyl, in particular C₁-C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl,
• - partially or fully halogenated, branched or unbranched C₁-C₆ alkyl, especially C₁-C₄ alkyl such as Di fluoromethyl, trifluoromethyl, trichloromethyl, pentafluoroethyl and 2-chloro-1,1,2-trifluoroethyl,
• - Branched or unbranched C₁-C₆ alkoxy, in particular C₁-C₄ alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy;

- ethoxyphenyl such as 2-, 3- or 4-ethoxyphenyl;
- 2- or 3-bromophenyl;
- 2- or 4-trifluoromethylphenyl;
- 2,4- or 2,6-difluorophenyl;
- 2-fluoro-6-chlorophenyl;
- 2,4- or 2,6-dimethylphenyl;
- 2,3,6-trichlorophenyl;
- trimethylsilyl or trifluoromethyl;
R² - hydrogen or halogen such as fluorine, chlorine and bromine;
R³ - phenyl which can carry 1-5 halogen atoms such as fluorine, chlorine and bromine or up to 3 of the following substituents

• - Branched or unbranched C₁-C₆ alkyl, in particular C₁-C₄-alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl,
• - partially or fully halogenated, branched or unbranched C₁-C₆-alkyl, especially C₁-C₄-alkyl such as Difluoromethyl, trifluoromethyl, chloromethyl, trichloromethyl, Pentafluoroethyl and 2-chloro-1,1,2-trifluoroethyl,
• - Branched or unbranched C₁-C₆ alkoxy, in particular C₁-C₄ alkoxy such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy and tert-butoxy;

preferred groups are 2-, 3- and 4-fluorophenyl, 2-, 3- and 4-chlorophenyl, 2-, 3- and 4-bromophenyl, 2-, 3- and 4-methylphenyl, 4-tert-butylphenyl , 2-, 3- and 4-trifluoromethylphenyl, 2-, 3- and 4-methoxyphenyl, 2-, 3- and 4-ethoxyphenyl, 2,4-di fluorophenyl, 2,6-difluorophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-dichlorophenyl, 2-fluoro-6-chlorophenyl, 2,3,6-trichlorophenyl, 2,4-, 3,4- and 2,6-dimethylphenyl, 2,4- , 3,4- and 2,6-dimethoxyphenyl and 3,4-diethoxyphenyl;
R⁴ - methyl and halogen such as fluorine, chlorine and bromine;
Hal - halogen such as fluorine, chlorine and bromine.

Particularly suitable compounds I can be found in Table 1. Prefers Compounds Ia, whose cyclopropane ring is represented by the following radicals R¹ ' is monosubstituted:

- cyano;
- C₂-C₄-alkyl such as ethyl, n-propyl, isopropyl and tert-butyl;
- trifluoromethyl;
- C₃-C₄ alkenyl such as prop-2-enyl and but-2-enyl;
- methoxycarbonyl and ethoxycarbonyl;
- Phenyl-C₁-C₄-alkyl and phenyl-C₃-C₄-alkenyl, where the aromatic can each carry one of the following substituents:
Halogen such as fluorine, chlorine and bromine, or methyl, in particular benzyl, 3-, 4-fluorobenzyl, 3-, 4-chlorobenzyl, 4-bromobenzyl, 3-methylbenzyl, 3- (4-fluorophenyl) propyl, 3- (4th Chlorophenyl) propyl, 3- (4-fluorophenyl) prop-2-enyl and 3- (4-chlorophenyl) prop-2-enyl;
- 2-bromophenyl;
- 2,4- and 2,6-difluorophenyl;
- 2-fluoro-6-chlorophenyl;
- 2,3,6-trichlorophenyl and
Trimethylsilyl.

R¹ 'represents a phenylalkenyl group, the E configuration is at the Double bond particularly preferred.

The compounds I according to the invention can be based on the preparation of the substituent -C (COOCH₃) = X-OCH₃ as ortho to the benzyl moiety E / Z isomer mixtures arise. The isomers can, if desired the usual methods, e.g. B. by crystallization or chromato graphic can be separated. Connections with E configuration are special prefers.

For compounds I whose cyclopropane ring differed in the 2- and 3-position ne substituents are in the 1-position of the cyclopropane ring (which the Benzyl ester group also carries 2 configurations possible. Carries the Cyclopropane ring in the 2-position a methyl group (compounds Ib of Ta belle 2), those compounds are particularly preferred in which the methyl groups trans to the benzyl ester group of the base body is located.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids I are available in various ways, preferably by a cyclopropanecarboxylic acid II in a manner known per se, in an inert th solvent such as ethanol, with a base in the carboxylate anion  and transferred this anion with an ortho-substituted benzyl compound implementation III (see Synthesis 1975, 805):

L represents a nucleophilic leaving group, in particular a sulfonyl Balance such as methanesulfonyl, trifluoromethylsulfonyl, p-toluenesulfonyl, p-bromine phenylsulfonyl or a methylsulfate residue, particularly preferably a halogen atom such as chlorine, bromine or iodine.

Alkali metal hydroxides such as sodium and potassium are particularly suitable as bases hydroxide and triethylamine suitable.

The reaction of the carboxylate anion is expediently taken with the Benzyl compound III in a solvent or diluent such as acetone, Acetonitrile, dimethyl sulfoxide, dioxane, dimethylformamide, N-methylpyrroli don, N, N'-dimethylpropyleneurea and pyridine or, using of a phase transfer catalyst, in a 2-phase system consisting of water and a hydrocarbon such as carbon tetrachloride.

As phase transfer catalysts such. B. Trioctylpropylammonium chloride and cetyltrimethylammonium chloride (see Synthesis 1974, 867).

It is advantageous to set all of the starting compounds to be approximately stoichiometric Ratio, but in some cases an excess of one or other component, approximately up to 10%, may be recommended.

In general, the reaction temperature is between 0 ° C and the boiling point temperature of the solvent, preferably between 20 and 130 ° C.

Since the reaction is not pressure-dependent, it is advantageous to work with Normal pressure.

Like cyclopropanecarboxylic acids II are known or can in themselves known methods are produced [see e.g. B. Synthesis, 738 (1987); Zh. Org. Khim 16: 2086 (1980); J. Am. Chem. Soc. 106: 6642 (1984); Chem. Ber. 116: 3895 (1983); Helv. Chim. Acta 69, 1655 (1986); Chem. Ber. 119: 3694 (1986); Chem. Letters, 475 (1989); J. Organometal. Chem. 46, 73  (1972); Gazz. Chim. Italian 100, 566 (1970); J. Org. Chem. 48, 2472 (1983) and J. Org. Chem. 47, 893 (1982)].

The ortho-substituted benzyl compounds III (X = CH, L = chlorine or Bromine) are also known or can be obtained by known processes are provided (cf. e.g. DE-A 35 19 280, DE-A 35 45 318 and DE-A 35 45 319).

For example, the ortho-substituted benzyl bromide III (X = CH, L = bromine) by bromination of the corresponding ortho-substituted toluene IV can be obtained with N-bromosuccinimide (cf. Angew. Chem. 71, 349 (1959):

The ortho-substituted toluene IV can be prepared by z. B. a Hydroxymethylene derivative Va, which is in equilibrium with the corresponding Formyl derivative Vb is present in the presence of a base such as potassium carbonate alkylated:

Z = methyl sulfate, chloride, bromide, iodide

Examples of alkylating agents are dimethyl sulfate and methyl iodide, chloride and bromide are suitable.

Usually one works in an inert solvent, for example in acetone.

The reaction temperature is generally between 20 and 60 ° C.

The hydroxymethylene derivative Va is, for example, base-catalyzed Reaction of methyl 2-methylphenylacetate with methyl formate ester in an inert solvent such as diethyl ether and tetrahydrofuran available, with the base, e.g. B. sodium hydroxide can be used (see Ann. Chem. 424, 214 (1921)).  

Ortho-substituted benzyl compounds III, where X is nitrogen and L is chlorine or bromine are available in several ways, namely before partially by halogenation of methyl 2-methylphenylglyoxylate-o- methyloxims VI.

For halogenation, chlorine or bromine in an inert solvent, e.g. B. carbon tetrachloride, or halogenating agents such as N-chloro and N-bromine succinimide [cf. Appl. Chem. 71, 349 (1959)] can be used in CCl₄. When using elemental chlorine or bromine, it is recommended that Carry out the reaction photochemically by irradiation with sunlight.

The 2-methylphenylglyoxylic acid methyl ester known from DE-A 36 23 921 o-methyloxime VI is advantageous from the 2-methyl-phenylglyoxylic acid methyl ester available, by reaction with o-methylhydroxylamine hydrochloride or with hydroxylaminohydrochloride, in which case primarily an oxime arises, which then with a methylating agent such as methyl chloride, methyl bromide, methyl iodide and dimethyl sulfate is treated.

A possible process variant for the preparation of the benzyl compound III (Y = nitrogen, L = chlorine, bromine) consists in that from the DE-A 36 23 921 known methyl 2-methyl-phenylglyoxylate VII after to halogenate one of the methods described above and that To convert the product into the corresponding oxime:

Those ortho-substituted benzyl compounds III, the leaving group L a p-toluenesulfonate, p-bromophenylsulfonate, methanesulfonate or trifluoromethanesulfonate is from the benzyl compounds gene III with L = chlorine or bromine, by reaction with p-toluenesulfonic acid, p-bromophenylsulfonic acid, methanesulfonic acid or trifluoromethanesulfonic acid producible.

The reaction is advantageously carried out in a solution or dilution medium, e.g. B. dimethylformamide, in the presence of a base, e.g. B. Potassium carbonate.

The reaction temperature is generally between 20 and 130 ° C.

One variant of the process is that the benzyl compounds III (L = chlorine, bromine) with the alkali metal salts, preferably the sodium or Potassium salts to implement the sulfonic acids in the inert solvent.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids I are suitable themselves as fungicides and to control pests.

The ortho-substituted benzyl esters of cyclopropanecarboxylic acids I are characterized by an excellent effectiveness against a broad Spectrum of phytopathogenic fungi, especially from the class of Ascomycetes and Basidiomycetes, from. Some of them are systemic and can be used as leaf and soil fungicides.

They are particularly important for combating a large number of fungi on various crops such as wheat, rye, barley, oats, rice, Corn, grass, cotton, soybeans, coffee, sugar cane, wine, fruit and Ornamental plants and vegetables such as cucumbers, beans and squashes, as well as on the seeds of these plants.  

They are particularly suitable for combating the following plant diseases:

Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Sphaerotheca fuliginea on pumpkin plants,
Podosphaera leucotricha on apples,
Uncinula necator on vines,
Puccinia species on cereals,
Rhizoctonia species on cotton and lawn,
Unstilago species on cereals and sugar cane,
Venturia inaequalis (scab) on apples,
Helminthosporium species on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, vines,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophthora infestans on potatoes and tomatoes,
Fusarium and Verticillium species on different plants,
Plasmopara viticola on vines,
Alternaria species in vegetables and fruits.

The compounds are applied by taking the mushrooms or the pre-mushroom infect plants, seeds, materials or the soil treated with a fungicidally effective amount of the active ingredients. The application occurs before or after infection of the materials, plants or seeds through the mushrooms.

The otho-substituted benzyl esters of cyclopropanecarboxylic acids I are suitable furthermore to control pests from the insect class arachnids and nematodes. You can in crop protection as well the hygiene, storage protection and veterinary sectors as pest control means are used.

Harmful insects belong to the order of the butterflies (Lepidoptera) for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa Gramme, 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, Eupoecillia 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 pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, 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, Berotoma 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 californicua, 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, Phrobia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.  

From the order of the thrips (Thysanoptera), for example Frankliniella 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 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 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, 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, 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.

From the class of nematodes, for example, root gall nematodes, e.g. B. Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, cysts forming nematodes, e.g. B. Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, Hetrodera triflolii, 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 can be converted into the usual formulations, such as solutions, emulsions, suspensions, dusts, powders, pastes and granules late. The application forms depend on the purposes; they in any case, a fine and even distribution of the ortho-sub ensure substituted benzyl ester of a cyclopropanecarboxylic acid. The Formulations are prepared in a known manner, e.g. B. by Ver stretching the active ingredient with solvents and / or carriers, if desired, using emulsifiers and dispersants means, but in the case of water as a diluent also other orga African solvents can be used as auxiliary solvents.

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 aro Matic hydrocarbons, e.g. B. benzene, toluene, xylene, paraffin, tetra hydronaphthalene, alkylated naphthalenes or their derivatives, methanol, Ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclo hexanol, 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 dispersers sions the substances as such or in an oil or solution medium dissolved, by means of wetting agents, adhesives, dispersants or emulsifiers 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 lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutyl naphthalenesulfonic acid, alkylarylsulfonates, alkyl sulfates, alkyl sulfonates, 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, condensates tion products of naphthalene or naphthalene sulfonic acid with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctyl phenol, octylphenol, nonylphenol, alkylphenol polyglycol ether, tributyl phenyl polyglycol ether, alkylaryl polyether alcohols, isotridecyl alcohol, Fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxy ethylene alkyl ether, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol ester, lignin sulfite liquor and methyl cellulose in Consider.

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

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 such preparations are:

• I. a solution of 90 parts by weight of compound no. 3 and 10 parts by weight Share N-methyl-α-pyrrolidone, which is used in the smallest form Drop is suitable;
• II. A mixture of 20 parts by weight of compound no. 4, 80 parts by weight Xylene, 10 parts by weight of the adduct from 8 to 10 moles of ethylene oxide in 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight Calcium salt of dodecylbenzenesulfonic acid, 5 parts by weight  of the adduct and 40 moles of ethylene oxide with 1 mole of castor oil oil; by finely distributing the solution in water you get one Dispersion.
• III. an aqueous dispersion of 20 parts by weight of compound No. 5, 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight Share the adduct of 40 moles of ethylene oxide with 1 mole Castor oil;
• IV. An aqueous dispersion of 20 parts by weight of compound no. 6, 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction from boiling point 210 to 280 ° C and 10 parts by weight of Addition product of 40 mol ethylene oxide with 1 mol castor oil;
• V. a mixture of 80 parts by weight ground in a hammer mill Compound No. 7, 3 parts by weight of the sodium salt of Diisobutylnaphthalene-α-sulfonic acid, 10 parts by weight of sodium salt of a lignin sulfonic acid from a sulfite waste liquor and 7 parts by weight of powdered silica gel; by fine Ver dividing the mixture into water gives a spray mixture;
• VI. an intimate mixture of 3 parts by weight of compound no. 15 and 97 parts by weight of finely divided kaolin; contains this dust 3% by weight of active ingredient;
• VII. An intimate mixture of 30 parts by weight of compound no. 103, 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; this preparation gives the active ingredient a good one Adherence;
• VIII. A stable aqueous dispersion of 40 parts by weight of the compound No. 109, 10 parts by weight of the sodium salt of a phenosulfonic acid urea-formaldehyde condensate, 2 parts by weight of silica gel and 48 parts by weight of water, which can be further diluted;
• IX. a stable oily dispersion of 20 parts by weight of the compound No. 117, 2 parts by weight of the calcium salt of the dodecylbenzenesulfone acid, 8 parts by weight of fatty alcohol polyglycol ether, 20 parts by weight the sodium salt of a phenolsulfonic acid-urea-formaldehyde Condensates and 68 parts by weight of a paraffinic mineral oil.

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 sul fat, ammonium phosphate, ammonium nitrate, urea and herbal product such as cereal 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.

In general, the compositions contain between 0.0001 and 95, preferably between 0.01 and 90 wt .-% active ingredient.

Formulations with more than 95 wt .-% active ingredient can with good success in Ultra-low-volume processes (ULV) are applied, with even the effect fabric can be used without additives.

The application rates in fungicidal compositions are dependent on the type of the desired Effect between 0.02 and 3 kg of active ingredient per ha. The new compounds can also be used in material protection (wood protection), e.g. B. against Paecilomyces variotii.

In the seed treatment, amounts of active ingredient are generally 0.001 up to 50 g preferably 0.01 to 10 g per kilogram of seed is required.

The amount of active ingredient for controlling insects is under field conditions 0.02 to 10, preferably 0.1 to 2.0 kg / ha.

In these forms of use, the agents according to the invention can also be used are present together with other active ingredients, e.g. B. with herbicides, insects ziden, growth regulators, fungicides or with fertilizers. These Agents can to the agents according to the invention in a weight ratio 1:10 to 10: 1, if necessary also just before use (Tank mix) can be added. When mixed with fungicides or insect ziden you get an increase in effectiveness in many cases spectrum.

The agents or the ready-to-use preparations made from them such as solutions, emulsions, suspensions, powders, dusts, pastes or granules latex are used in a known manner, for example by spraying hen, fogging, dusting, scattering, pickling or pouring.

Manufacturing examples Example 1 (Compound No. 3 in Table 1) Alpha- (2- [1- (n-propyl) cyclopropylcarbonyloxymethyl] phenyl) beta-methoxy acrylic acid methyl ester

A solution of 3.5 g (27 mmol) of 1-n-propyl-cyclopropanecarboxylic acid and 1.5 g (27 mmol) of potassium hydroxide in 75 ml of ethanol was at 20 ° C for 2 hours touched. The precipitated potassium salt was then separated off with Washed 100 ml of diethyl ether and suspended in 50 ml of dimethylformamide. 5.7 g (20 mmol) of alpha (2-bromomethylphenyl) - were added to this suspension. beta-methoxy-acrylic acid methyl ester and then heated to 90 ° C. for 2 hours. After cooling to 20 ° C, the mixture was hydrolyzed with 50 ml of water. Then the product was extracted with diethyl ether and as usual isolated. The purification was carried out chromatographically using silica gel Adsorbent and cyclohexane as eluent. Yield: 66%; Mp: 62-64 ° C.

Preliminary stage 1a 1-Allyl-cyclopropanecarboxylic acid tert-butyl ester

To a mixture of 33.6 ml (0.24 mol) diisopropylamine, 150 ml one 1.5 molar solution of n-butyllithium in n-hexane (0.24 mol butyllithium) and 100 ml of tetrahydrofuran became a solution of 34.1 g at (-70) ° C (0.24 mol) cyclopropanecarboxylic acid tert-butyl ester in 25 ml of tetrahydro furan dropped. After stirring for 3 hours at (-70) ° C, a solution of 27.8 g (0.23 mol) of allyl bromide in 25 ml of tetrahydrofuran were added dropwise. The reaction mixture was then stirred at (-70) ° C. for a further 2 hours and then 12 hours at 20 ° C. After hydrolysis with 50 ml saturated  aqueous ammonium chloride solution and after phase separation organic phase worked up as usual on the product. The The crude product was purified by distillation. Yield: 61%; Sdp .: 86-88 ° C at 30 mbar; colorless oil.

Preliminary stage 1b 1-n-Propyl-cyclopropanecarboxylic acid tert-butyl ester

At 30 ° C and 10 bar hydrogen pressure 25.5 g (0.14 mol) of 1-allyl tert-butyl cyclopropanecarboxylate, dissolved in 150 ml of tetrahydrofuran, with the addition of 6 g of aluminum oxide, which contained 0.5% by weight of palladium, hydrated. After no more hydrogen has been taken up (constant pressure), the solids were filtered off and the filtrate was evaporated to dryness a. The crude product was purified by distillation. Yield 87%; Bp: 89 ° C at 36 mbar; colorless oil.

Preliminary stage 1c 1-n-propyl-cyclopropanecarboxylic acid

A mixture of 21.0 g (0.11 mol) of 1-n-propyl-cyclopropanecarboxylic acid tert-butyl ester and 13.0 g (0.11 mol) of trifluoroacetic acid was 3 hours stirred at reflux temperature and then in 20 ml of dilute sodium hydroxide solution given. After extraction of by-products with diethyl ether, the acidified aqueous phase with dilute hydrochloric acid and again with Extracted diethyl ether. This ether phase was then applied to the Refurbished product. Yield: 95%; colorless oil.  

Example 2 (Compound No. 4 in Table 1) 2- [1- (n-propyl) -cyclopropylcarbonyloxymethyl] phenyl-glyoxylic acid methyl ester-O-methyloxime

A mixture of 2.8 g (22 mmol) of 1-n-propyl-cyclopropanecarboxylic acid (prepared according to Example 1c), 1.3 g (23 mmol) of potassium hydroxide and 50 ml Ethanol was stirred at 20 ° C for 1 hour. Then the failed Potassium salt separated, washed with 50 ml of diethyl ether and in 100 ml of dimethylformamide suspended. 4.3 g were added to this suspension (15 mmol) methyl 2- (bromomethyl) -phenyl-glyoxylate-O-methyloxime and then heated to 100 ° C for 2 hours. After cooling to 20 ° C Mixture with 50 ml of water hydrolyzed and analogous to Example 1 on the Refurbished product. Yield: 38%, m.p .: 56-59 ° C; colorless Crystals.

Example 3 (Compound No. 5 in Table 1) Alpha- {2- [1- (allyl) cyclopropylcarbonylmethyl] phenyl} beta-methoxyacrylic acid methyl ester

A solution of 4.5 g (36 mmol) of 1-allyl-cyclopropanecarboxylic acid and 2.2 g (39 mmol) potassium hydroxide in 50 ml ethanol was stirred at 20 ° C for 2 hours and then narrowed down. After covering with diethyl ether, the precipitated Precipitate separated and washed with diethyl ether. The subsequent one Implementation of the potassium salt of 1-allyl-cyclopropanecarboxylic acid in 50 ml of N-methylpyrrolidone with 8.5 g (30 mmol) of alpha (2-bromomethylphenyl) - beta-methoxyacrylic acid methyl ester and the purification of the The end product was carried out analogously to Example 1. Yield: 40%; colorless oil.  

Preliminary stage 3a 1-allyl-cyclopropanecarboxylic acid

Analogously to Example 1c, 24.0 g (0.13 mol) of 1-allyl-cyclopropanecarboxylic acid tert-butyl ester (prepared according to Example 1a) with 14.9 g (0.13 mol) of trifluoroacetic acid. Yield: 90%; colorless oil.

Example 4 (Compound No. 6 in Table 1) 2- [1- (allyl) -cyclopropylcarbonyloxymethyl] -phenyl-glyoxylic acid methyl ester- O-methyloxime

Analogously to Example 3, 2.3 g (18 mmol) of 1-allylcyclopropanecarboxylic acid (prepared according to Example 1c) with 1.1 g (20 mmol) of potassium hydroxide in the Potassium salt of 1-allyl-cyclopropanoic acid was transferred and this was in 50 ml dimethylformamide with 4.3 g (15 mmol) methyl 2- (bromomethyl) -phenyl-glyoxylate- O-methyloxime implemented. Yield: 84%; colorless oil.  

Example 5 Compound No. 7 in Table 1) Alpha- {2- [1-trifluoromethyl) cyclopropylcarbonyloxymethyl] phenyl} beta methoxyacrylic acid methyl ester

A solution of 10.0 g (55 mmol) of 1-trifluoromethyl-cyclopropanecarboxylic acid ethyl ester and 3.4 g (61 mmol) of potassium hydroxide in 150 ml of ethanol Stirred at 40 ° C for 4 hours and then concentrated. After overlaying with The precipitate was separated off using diethyl ether Washed diethyl ether and suspended in 100 ml of dimethylformamide. To this suspension was added 10.0 g (35 mmol) of alpha (2-bromomethylphenyl) - beta-methoxyacrylic acid methyl ester and then heated to 95 ° C. for 2 hours. After cooling to 20 ° C, the mixture was hydrolyzed with 50 ml of water. Then the product was extracted with diethyl ether and as usual isolated.

The oily crude product was covered with pentane and rubbed on crystallized the vessel wall. Yield: 64%; M.p .: 58-60 ° C; white crystals.

Preliminary stage 5a Cyclopropane-1,1-dicarboxylic acid monoethyl ester

A solution of 53 g (285 mmol) of diethyl cyclopropane-1,1-dicarboxylate and 16.0 g (286 mmol) of potassium hydroxide in 300 ml of ethanol was added for 3 hours Stirred at 20 ° C and then concentrated to dryness. The backlog was in 100 ml of water dissolved, after which by-products with 200 ml of methylene chloride were extracted. After the aqueous phase with dilute hydrochloric acid pH = 2 was acidified, the product was extracted with 200 ml of methyl tert-butyl ether and isoziert it as usual. The cleaning was done distillative. Yield: 83%; Bp: 99-102 ° C at 2.5 mbar; colorless oil.  

Preliminary stage 5b 1-Trifluoromethyl-cyclopropanecarboxylic acid ethyl ester

In a 500 ml stirred autoclave, which is coated with an alloy of 70% nickel, 15% chromium and 15% molybdenum was lined at 31.6 g at (-70) ° C (0.20 mol) monoethyl cyclopropane-1,1-dicarboxylate, 126 g (1.16 mol) Sulfur tetrafluoride, 100 ml dichloromethane and 1.5 g (75 mmol) hydrogen fluoride given. The mixture was heated to 80 ° C. and for 48 hours destroyed the gaseous components after cooling the autoclave to 35 ° C, by introducing into a washing tower filled with potassium hydroxide. The residue was dissolved in 100 ml dichloromethane. After washing the Solution with 100 ml of saturated sodium bicarbonate solution was the dried organic phase with sodium sulfate and potassium fluoride and separated into the individual components by distillation. Yield: 76%; Bp: 141-142 ° C; Oil.

Example 6 (Compound No. 8 in Table 1) Alpha- {2- [1- (trimethylsilyl) cyclopropylcarbonyloxymethyl] phenyl} beta methoxyacrylic acid methyl ester

Analogously to Example 3, 4.5 g (28 mmol) of 1-trimethylsilylcyclopropanecarboxylic acid, dissolved in 80 ml of ethanol, with 1.8 g (32 mmol) of potassium hydroxide converted into the potassium salt of trimethylsilylcyclopropane carboxylic acid and this was mixed at 100 ° C. with 5.7 g (20 mmol) of alpha (2-bromomethylphenyl) beta implemented methoxy-acrylic acid methyl ester. Yield: 62%; colorless oil.  

Preliminary stage 6a 1-trimethylsilyl-cyclopropanoic acid

To a mixture of 42.0 ml (0.30 mol) diisopropylamine, 200 ml one 1.5 molar solution of n-butyllithium in n-hexane (0.30 mol butyllithium) and 150 ml of tetrahydrofuran were 12.9 g (0.15 mol) of cyclopropanecarboxylic acid at (-78) ° C and after stirring for 30 minutes at (-78) ° C 81.3 g (0.75 mol) trimethylchlorosilane was added dropwise. Then you stirred it Reaction mixture for 30 minutes at 0 ° C, added it after heating 20 ° C with 150 ml of methanol and stirred for a further 30 minutes. After hydrolysis the organic phase was separated off with water and concentrated. From the Colorless crystals were obtained in a concentrated solution. Yield: 38%; Mp .: 124-126 ° C.

Example 7 (Compound No. 11 in Table 1) Alpha- {2- [1- (ethoxycarbonyl) cyclopropylcarbonyloxymethyl] phenyl} beta methoxyacrylic acid methyl ester

Analogously to Example 1, 7.9 g (50 mmol) of cyclopropane-1,1-dicarboxylic acid monoethyl ester (prepared according to Example 5a) with 2.8 g (50 mmol) of potassium hydroxide into the potassium salt of the cyclopropane-1,1-dicarboxylic acid monomethyl ester transferred and this was then mixed with 10 g (35 mmol) of alpha [2- (bromomethyl) phenyl] beta-methoxyacrylic acid methyl ester implemented. The The product was cleaned by distillation. Yield: 66%; Bp .: 220 ° C at 0.3 mbar; colorless oil.  

Example 8 (Compound No. 17 in Table 1) Alpha- {2- [1- (2,6-difluorophenyl) cyclopropylcarbonyloxymethyl] phenyl} beta methoxyacrylic acid methyl ester

Analogously to Example 1, 12.8 g (65 mmol) of 1- (2,6-difluorophenyl) cyclopropanecarboxylic acid, dissolved in 60 ml of ethanol, with 4.0 g (71 mmol) of potassium hydroxide in the potassium salt of 2,6-difluorophenyl-cyclopropanecarboxylic acid transferred and this was then at 100 ° C, in 100 ml of N-methylpyrrolidone, with 11.4 g (40 mmol) of alpha (2-bromomethylphenyl) beta methoxyacrylic acid implemented methyl ester. The oily product obtained was with Layered diisopropyl ether and rubbing against the wall of the vessel Brought crystallization. Yield: 86%; M.p .: 108-110 ° C; white crystals.

Preliminary stage 8a 1- (2,6-difluorophenyl) cyclopropyl nitrile

To a mixture of 30.6 g (0.20 mol) of 2,6-difluorobenzyl cyanide and 150.0 g (0.80 mol) of 1,2-dibromoethane became 4.0 g of tetrabutylammonium chloride added and then added dropwise 150 ml of 50% sodium hydroxide solution. To 5 hours stirring at 60 ° C was hydrolyzed with ice water. From the received Mixture, the product was extracted with diethyl ether and in isolated in the usual way. The cleaning was carried out by chromatography Silica gel as adsorbent and cyclohexane as eluent. Yield: 52%; Mp: 56-58 ° C; colorless crystals.  

Preliminary stage 8b 1- (2,6-difluorophenyl) cyclopropanecarboxylic acid

A suspension of 17.9 g (100 mmol) of 1- (2,6-difluorophenyl) cyclopropyl nitrile concentrated in a mixture of 60 ml ice water and 40 ml Sulfuric acid was heated to reflux for 4 hours. After this Cooling to 25 ° C, the resulting precipitate was separated off with Washed water and dried. Yield: 89%; Mp: 150-153 ° C; colorless Crystals.

Example 9 (Compound No. 18 in Table 1) 2- [1- (2,6-difluorophenyl) cyclopropylcarbonyloxymethyl] phenylglyoxylic acid methyl ester - O-methyloxime

Analogously to Example 2, 11.8 g (60 mmol) of 1- (2,6-difluorophenyl) cyclopropanecarboxylic acid (prepared according to Example 8b), dissolved in 60 ml of ethanol, with 3.6 g (64 mmol) of potassium hydroxide in the potassium salt of 2,6-difluorophenyl cyclopropanecarboxylic acid, and this was then at 90 ° C, in 100 ml of N-methylpyrrolidone, with 13.3 g (47 mmol) of 2- (bromomethyl) - phenyl-glyoxylsäuremethylester-O-methyloxim implemented. The oily obtained The product was overlaid with diisopropyl ether and rubbed on the Vessel wall brought to crystallization. Yield: 85%; Mp: 122-123 ° C; white crystals.

Example 10 (Compound No. 29 in Table 1) Alpha- {2- [1- (4-fluorobenzyl) cyclopropylcarbonyloxymethyl] phenyl} beta methoxyacrylic acid methyl ester

Analogously to Example 3, 6.3 g (32 mmol) of 1- (4-fluorobenzyl) cyclopropanecarboxylic acid with 2.0 g (36 mmol) of potassium hydroxide in the potassium salt of Fluorobenzyl-cyclopropanecarboxylic acid was transferred and this was then at 100 ° C with 6.3 g (22 mmol) of methyl (2-bromomethylphenyl) beta-methoxyacrylic acid implemented. Yield: 54%; colorless oil.

Preliminary stage 10a 1- (4-Fluorobenzyl) -cyclopropanecarboxylic acid tert-butyl ester

Analogous to precursor 1a, 34.1 g (0.24 mol) of cyclopropanecarboxylic acid tert.- butyl ester converted into a lithium complex and this was 30.2 g (0.16 mol) of 4-fluorobenzyl bromide reacted. The cleaning was done chromatographically with silica gel as adsorbent and cyclohexane as eluent. Yield: 72%; colorless oil.  

Preliminary stage 10b 1- (4-fluorobenzyl) cyclopropanecarboxylic acid

Analogously to precursor 1c, 25.0 g (0.10 mol) of 1- (4-fluorobenzyl) cyclopropanecarboxylic acid were tert-butyl ester (prepared according to precursor 10a) with 14.3 g (0.13 mol) of trifluoroacetic acid. Yield: 90%; colorless oil.

Example 11 (Compound No. 30 in Table 1) 2- [1- (4-fluorobenzyl) cyclopropylcarbonyloxymethyl] phenyl-glyoxylic acid remethyl ester- O-methyloxime

Analogously to Example 2, 5.8 g (30 mmol) of 1- (4-fluorobenzyl) cyclopropanecarboxylic acid (prepared according to precursor 10a) with 1.8 g (32 mmol) of potassium hydroxide converted into the potassium salt of fluorobenzyl cyclopropanecarboxylic acid and this was then mixed with 6.3 g (22 mmol) of 2- (bromomethyl) - phenylglyoxylsäuremethylester-O-methyloxim implemented. The cleaning was done chromatographically with silica gel as adsorbent and toluene as eluent. Yield: 62%; colorless oil.  

Example 12 (Compound No. 261 in Table 2) Alpha- [2- (1,2-dimethyl-cyclopropylcarbonyloxymethyl) phenyl] beta-methoxyacrylic acid methyl ester

A solution of 3.8 g (27 mmol) of 1,2-dimethyl-cyclopropanecarboxylic acid ethyl ester and 1.6 g (29 mmol) of potassium hydroxide in 50 ml of ethanol Stirred at reflux temperature for 8 hours and then concentrated. After overlaying the precipitate formed in the solution with diethyl ether separated and washed with diethyl ether. The subsequent implementation of the potassium salt of dimethyl-cyclopropanecarboxylic acid obtained in 60 ml N-methylpyrrolidone, at 100 ° C, with 4.2 g (15 mmol) of alpha (2-bromomethylphenyl) - beta-methoxyacrylic acid methyl ester and the cleaning of the end product was carried out analogously to Example 1. Yield: 69%; colorless oil.

Preliminary stage 12a 1,2-dimethyl-3,3-dibromo-1-cyclopropanecarboxylic acid ethyl ester

To a solution of 32 g (0.25 mol) of (E) -2-methyl-2-butenoate in 80 ml of methylene chloride became 1 g (2 mmol) of hexadecyl-tributylphosphonium bromide and 50 ml of 50 wt .-% aqueous sodium hydroxide solution. Subsequently 75.6 g (0.30 mol) of bromoform were added dropwise at 20 ° C. and the reaction mixture The mixture was stirred at 20 ° C. for 24 hours and at 50 ° C. for a further 8 hours. Then 100 ml of water were added to a mixture and the product was extracted Methylene chloride. The organic phase was applied to the product as usual worked up. The crude product was purified by distillation. Yield: 37%; Bp: 102 ° C at 2 mbar; colorless oil.  

Preliminary stage 12b 1,2-dimethyl-cyclopropanecarboxylic acid ethyl ester

Carboxylic acid ethyl ester (prepared according to precursor 12a) in 50 ml of diethyl ether 55 g (0.19 mol) of tributyltin hydride were slowly added dropwise at 20 ° C. After stirring at 20 ° C for 12 hours, the solvent was removed. The mixture was then stirred at 140 ° C. for a further 2 hours then separated them by distillation at about 15 mbar (water jet vacuum). Yield: 76%; Bp: 54-56 ° C at 15 mbar; colorless oil.

Example 13 (Compound No. 263 in Table 2) Alpha- [2- (1,2-dimethyl-3,3-dibromo-cyclopropylcarbonyloxymethyl) -phen-yl] - beta-methoxyacrylic acid methyl ester

A solution of 11.0 g (36 mmol) of 1,2-dimethyl-3,3-dibromo-cyclopropanecarboxylic acid ethyl ester (prepared according to precursor 12a) and 2.2 g (40 mmol) Potassium hydroxide in 100 ml of ethanol was stirred at 60 ° C for 6 hours and then constricted. After covering the solution with diethyl ether, the precipitated one Precipitate separated and washed with diethyl ether. The subsequent one Reaction of the potassium salt of dimethyl dibromo cyclopropanecarboxylic acid in 60 ml N-methylpyrrolidone with 5.1 g (18 mmol) Alpha- (2-bromomethylphenyl) -beta-methoxyacrylic acid methyl ester analogous to Example 1. After hydrolysis of the reaction mixture, the product extracted with methyl tert-butyl ether and isolated analogously to Example 1 and cleaned. Yield: 32%; colorless oil.

The physical data of the end products I can be found in the following Tables 1 to 4, which also list further compounds I which were prepared or can be prepared in the same ways.

Table 2

Table 3

Table 4

Examples of use (fungicidal activity)

Served as reference substances

both known from DE 37 33 870 (compounds No. 71 and 364; both E configuration on the double bond).

Example 14 Efficacy against powdery mildew

Leaves of "Early Gold" wheat seedlings grown in pots were with 0.006 and 0.0015% aqueous active ingredient preparations, the 80% active ingredient (the active ingredients according to table examples 3, 4, 5, 6, 7, 15, 18 and 261) and 20% emulsifier contained in the dry matter, sprayed and 24 hours after the spray coating has dried on with spores of powdery mildew (Erysiphe graminis var. tritici) pollinated. The Test plants were then grown in the greenhouse at temperatures between 20 and 22 ° C and 75 to 80% relative humidity set up. After 7 days, the extent of mildew development judged.

Against a control attempt (no treatment, 70% fungal attack) and the known comparison compounds A (40-50% fungal attack) and B (50% Fungus infestation) showed that the treated plants had only one fungal infestation from 0-15%.

Example 15 Efficacy against wheat brown rust

Leaves of potted wheat seedlings of the "early gold" variety were pollinated with spores of the brown rust (Puccinia redondita). After that the pots were placed in a chamber at 90 to 24 for 20 to 22 ° C 95% relative humidity. During this time, they germinated Spores out and the germ tubes penetrated the leaf tissue. The infected plants were treated with 0.025% aqueous spray mixture, which was 80%  Active ingredient and 20% emulsifier contained in the dry substance, sprayed to runoff and after the spray coating had dried on in the greenhouse at a temperature between 20 and 22 ° C and 65 and 70% relative Humidity set up. After 8 days, the extent of the Rust fungus development on the leaves.

The result shows that the active ingredients 3, 5, 7, 15, 24, 45, 103, 109, 110 and 177 a better one when used as a 0.025% (wt.%) spray mixture Show fungicidal activity (97%) as the known comparison substances A (33%) and B (17%).

Example 16 Efficacy against Pyricularia oryzae (preventive treatment)

Leaves of rice seedlings of the "Bahia" variety grown in pots were with aqueous emulsions containing 80% active ingredient and 20% emulsifier in the Contained dry matter, sprayed to runoff and with 24 hours later an aqueous spore suspension of Pyricularia oryzae. The test plants were then in climatic chambers at temperatures between 20 and 24 ° C and 95-99% relative humidity. The extent of the fungal attack was determined after 6 days.

The result shows that the active ingredients 3, 4, 5, 6, 8, 46, 103, 104, 109, 177, 183 and 261 when used as a 0.05% (wt .-%) aqueous active ingredient preparation have a much better fungicidal activity (98%) than the known comparison substances A (0%) and B (50%).

Examples of use (insecticidal activity)

The insecticidal effects of the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I was shown by the following experiments:

The active ingredients were in the form of a 10% emulsion in a mixture of 70% by weight Cyclohexanol, 20% by weight Nekanil® LN (Lutensol PAP6, 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 according to the desired concentration diluted with water.  

Example 17 Effectiveness against Tetranychus telarius (red spider); Contact effect Trial 17a

Bush beans in pots, forming the second pair of foliage had and which were heavily infested with the spider mites were also different concentrated aqueous preparation of active compound No. 29 sprayed to runoff. To do this, the plants were sprayed on a turntable from all sides with approx. 50 ml of the spray mixture. After 5 days in Greenhouse was the control success in% using a microscope (binocular) detected.

At an active ingredient concentration of 200 ppm, the compound caused No. 29 a mortality rate of 80 to 90%.

Trial 17b (preventive treatment)

Bush beans in pots, forming the second pair of foliage had been with the differently concentrated drug preparations Compound No. 29 sprayed to runoff point analogously to experiment 17a. After 24 hours the plants were covered with leaf pieces that were heavily populated with spider mites were infected.

After 12 days in the greenhouse, the microscope (binocular) was used Control success determined in%.

At an active ingredient concentration of 40 ppm, compound no. 29 caused mortality from 80 to 90%.

Claims (9)

1. Ortho-substituted benzyl esters of cyclopropanecarboxylic acids of the general formula I in which X is nitrogen or = CH and A is one of the following cyclopropane radicals: where the substituents have the following meaning:
R¹ cyano, C₂-C₈-alkyl, trifluoromethyl, C₃-C₈-alkenyl, trimethylsilyl, C₁-C₄-alkoxycarbonyl, phenyl-C₁-C₆-alkyl or phenyl-C₃-C₆-alkenyl, where the aromatics each contain 1-5 halogen atoms or can carry up to 3 of the following substituents:
C₁-C₆-alkyl, partially or completely halogenated C₁-C₆-alkyl or C₁-C₆-alkoxy,
Ethoxyphenyl, 2-bromophenyl, 3-bromophenyl, 2-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2-fluoro-6-chlorophenyl, 2,4-dimethylphenyl, 2,6-dimethylphenyl or 2,3,6-trichlorophenyl;
R² is hydrogen or halogen;
R³ is phenyl which can carry 1-5 halogen atoms or up to 3 of the following substituents: C₁-C₆-alkyl, partially or completely halogenated C₁-C₆-alkyl or C₁-C₆-alkoxy;
R⁴ is methyl or halogen;
Hal halogen;
with the proviso that X is = CH- when R¹ is trifluoromethyl or trimethylsilyl. 2. Ortho-substituted benzyl esters of cyclopropanecarboxylic acids of the general formula Ia in which X represents nitrogen or = CH- and R ^{1 ′ has the} following meaning:
Cyano, C₂-C₄-alkyl, trifluoromethyl, C₃-C₄-alkenyl, trimethylsilyl, C₁-C₂-alkoxycarbonyl, phenyl-C₁-C₄-alkyl or
Phenyl-C₃-C₄-alkenyl, where the aromatic can in each case be simply substituted by halogen or methyl,
2-bromophenyl, 2,4-difluorophenyl, 2,6-difluorophenyl, 2-fluoro-6-chlorophenyl and 2,3,6-trichlorophenyl,
with the proviso that X is = CH- when R ^{1 'is} trimethylsilyl or trifluoromethyl. 3. A process for the preparation of the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I according to claim 1, characterized in that a cyclopropanecarboxylic acid of the formula II A-CO-OH (II) in its alkali metal salt, alkaline earth metal salt, ammonium salt, C₁-C₄ alkylammonium, Di- (C₁-C₄) alkylammonium or tri- (C₁-C₄) alkylammonium salt transferred and this salt, if desired in the presence of a catalyst, with an ortho-substituted benzyl compound of formula III in which L represents a nucleophilically substitutable leaving group. 4. Use of the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I according to claim 1 as a fungicide. 5. Use of the ortho-substituted benzyl esters of cyclopropanecarboxylic acids I according to claim 1 for combating pests. 6. Fungicidal composition containing a liquid or solid carrier and at least one ortho-substituted benzyl ester of cyclopropanecarboxylic acids I according to claim 1. 7. pesticides containing inert carriers and at least one ortho-substituted benzyl ester of cyclopropanecarboxylic acids I according to claim 1. 8. A method of combating fungi, characterized in that a fungicidally effective amount of an ortho-substituted benzyl ester of cyclopropanecarboxylic acids I according to claim 1 on fungi, from fungal attack endangered plants, their habitat or on the seeds of the endangered plants. 9. A method for controlling pests, characterized in that a pesticidally effective amount of an ortho-substituted benzyl ester of cyclopropanecarboxylic acids I according to claim 1 on pests between their living space.