JP2002526469A - Pest control tris-oxime compound - Google Patents

Abstract

(57) Abstract: In the present invention, R ₂ is hydrogen, methyl or ethyl, and R ₃ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkenyl. , A C ₂ -C ₄ alkynyl or halomethyl, wherein n is 1 or 2, About. The novel compounds have plant protection properties and are suitable for protecting plants against contamination by phytopathogenic microorganisms.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to a compound of the formula (I)

[0002]

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Wherein R ₂ is hydrogen, methyl or ethyl; R ₃ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkenyl, C _2- C ₄ alkynyl or halomethyl; n is 1 or 2; Novel pesticidally, especially fungicidal fungi
gicidally) active tris-oxime compounds.

[0004] Formula I represents racemic and diastereomeric compounds.
and all stereoisomers, such as mixtures, eg E / Z mixtures, and mixtures thereof.

[0005] 1,2-dioxime ether derivatives having bactericidal / fungal activity are described, for example, in WO9
5/18789.

The compounds according to the invention have a particularly good fungicidal activity, especially in cereals, thereby making them very suitable for practical use in agriculture and horticulture. It shows a characteristic.

Furthermore, the present invention relates to the preparation of these compounds, to agrochemical compositions comprising at least one of these compounds as active ingredient and to the attack by harmful microorganisms, in particular fungi. To the use of the active ingredient or the composition for protecting plants.

[0008] The general terms used herein have the following meanings.

C ₁ -C ₄ alkyl may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl by itself or as a structural element of another group such as alkoxy. is there.

Alkenyl is straight-chain or branched, for example vinyl, allyl, methallyl, 1-methylvinyl or but-2-en-1-yl.

Alkynyl is straight-chain or branched, for example ethynyl, propargyl, but-1
-In-1-yl and but-1-in-3-yl. Ethynyl and propargyl are preferred.

Halogen or halo is fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine.

The halomethyl can contain the same or different halogen atoms, examples are fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, difluorochloromethyl, dichlorofluoromethyl, Trifluoromethyl is preferred.

Compounds of formula I wherein R ₂ is methyl and R ₃ is fluoro, chloro or bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, ethynyl or trifluoromethyl are preferred.

Particularly preferred are the compounds of Table 1, in particular 1 to 8 and 10.

The compounds of formula I can be prepared as follows.

[0017]

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A compound of formula II wherein U is a leaving group, for example chlorine, bromine, iodine, mesyloxy or tosyloxy, a compound of formula III wherein the substituents are as defined in formula I, The reaction is preferably carried out in an organic solvent in the presence of a base.

The compounds of the formulas II and III are known or can be prepared by known methods.

The compounds of the formula I are used in the agricultural and related fields in plant diseases
It can be used proactively and / or curatively as an active ingredient in the control of diseases. The compounds of the formula I according to the invention are distinguished by having good activity even at low concentrations, by being well tolerated by plants and by being environmentally friendly. They are very advantageous, especially systemic
c) It has properties and can be used for the protection of a large number of cultivated plants. The compounds of formula I inhibit or inhibit the pests present on plants or plant parts (fruits, flowers, leaves, stems, tubers or roots) of various crops of useful plants.
While growing or destroying, the parts of the plant that grow later are phytopathogenic microorgangans.
ismus), especially against fungi and molds.

Compound I is used in seeds [fruits, tubers, kernels (gr)
ains)] and as a dressing in the treatment of plant cuttings, fungi and fungi.
us infections as well as protection against phytopathogenic fungi present in the soil.

Compound I is, for example, a phytopathogenic fungus or fungi belonging to the following classes: Fungi imperfecti (for example, Botrytis sp. (Botry)
tis), Pyricularia, Helminthosporium, Fusarium
), The genus Septoria, the genus Cercospo (Cercospo)
ra) and Alternaria spp .; Basidiomycetes (Basi)
dimycetes) (eg, Rhizoctonia)
, Hemileia, Puccinia);
Ascomycetes (eg, Ventur)
ia) and Erysiphe, Podosfaera (Podos)
phaera), Monilinia, Uncinula (Unc)
inula) and oomycetes (eg, Phytophthora, Pythium, Plasmopara).

Within the scope of the present invention, target crops for plant protection are, for example, the following plant species: cereals (wheat, barley, rye, oat, rice, corn, sorghum and related crops) ; Beet (sugar beet)
t) and feeder beet; pomes, stona fruit, and soft fruit (apple, pears, plum, peach, almond, cherry, strawberry,
Leguminous plants (raspberries and blackberries); leguminous plants
) (Beans, beans, lentils, peas (p
eas), soybeans); oils and fats plants (oilseed rape, mustard, poppy, olives,
Sunflower, coconut, castor plant, cocoa beans, peanut; cucumber plants (marrows, cucumber, melon); (Orange, lemon, grapefruit, mandarin); vegetables (spinach, lettuce, asparagus, cabbage, carrot, onion, tomato, potato, shii pepper); laucaceae (avocado, cinnamon, camphor) and tobacco and nuts nuts), coffee,
Includes plants such as eggplant, sugar cane, tea, pepper, grapes (vines), hops, bananas, as well as natural rubber plants and ornamental plants.

The compounds I are usually used in the form of a composition and can be applied to the area or the plant to be treated simultaneously with or subsequent to the further active ingredient. These additional active ingredients include, for example, fertilizers, micronutrients (micronu
It can be tri-donors or other preparations that affect plant growth. Common use of selective herbicides and insecticides, fungicides, bactericides, nematicides, molluscicides, or some mixtures of these preparations, if desired in compounding techniques Additional carriers, surfactants or other application-promoting aids
adjuvants).

Suitable carriers and auxiliaries can be solid or liquid, and are those substances commonly used in compounding techniques, such as natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, Thickeners, binders or fertilizers.

A preferred method of applying the compounds of the formula I or the agrochemical compositions comprising at least one of these compounds is by applying to the foliage of plants (foliar application). is there. The frequency and rate of application depends on the risk of infestation by the pathogen in question. However, the compounds of the formula I can be passed through the soil when the plant site is impregnated with a liquid formulation or when the active ingredient is incorporated into the soil in solid form, for example in granular form (soil application). It can also penetrate plants through roots (systemic action). In the case of paddy rice crops, such granules may be used in flooded rice fields.
Can be applied in metered amounts. However, the compounds of the formula I can be used for seed treatment by impregnating the seeds or tubers with a liquid formulation of the active ingredient or by coating the seeds or tubers with a solid formulation.
It can also be applied (coated) to the ed grains.

The compounds of the formula I are used in unmodified form or, preferably, with auxiliaries customary in compounding techniques. To that end, they are prepared in a known manner, for example by emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions. emulsions), wettable powders, soluble powders
wders, dusts or granules, for example by encapsulation in, for example, a polymeric material. Depending on the nature of the composition, spraying, atomizing, dusting, dusting (scat)
The method of application, such as tering, coating or pouring, is chosen according to the intended purpose and the prevailing environment.

Advantageous rates of application are generally from 1 g to 1 g
2 kg of active ingredient (ai) / ha (ha), preferably 10 g to 1 kg
a. i. / Ha, especially 20 g to 600 ga. i. / Ha. Active ingredient 10m when used as seed dressings
A rate of g to 1 g / kg of seed is advantageously used.

Formulations, ie, formulations, compositions, preparations or mixtures comprising a compound of formula I (active ingredient) and optionally a solid or liquid auxiliary, comprise the active ingredient in an extended amount such as a solvent, solid carrier. It is prepared in a known manner by homogeneously mixing and / or grinding with extenders and, optionally, surfactant compounds (surfactants).

The agrochemical composition comprises from 0.1 to 99% by weight, in particular from 0.1 to 95% by weight, of a compound of the formula I, from 99.9 to 1% by weight, in particular from 99.8 to 5% by weight, of solid or liquid auxiliaries. % By weight and from 0 to 25% by weight of surfactant, in particular from 0.1 to 25% by weight.

The compounds of formula I can be mixed with other fungicides in some cases to produce unexpected synergistic effects.

Particularly preferred mixing partners are azoles such as azaconazole (azaco
nazole), bitertanol, propiconazole, difenoconazole
zole), diconiconazole, cyproconazole, epoxyconazole (epoxyconaz)
ole), fluquinconazole, flusilazole, flutriafol
, Hexaconazole, imazalil
il), imibenconazole, ipconazole, tebuconazole,
Tetraconazole), fenbuconazole (f
enbuconazole, metconazole, microbutanil, perfurazoate (perfur)
azoate), penconazole, bromuconazole, pyrifenox
, Prochloraz, triadimefon (triadim)
efon), triadimenol, triflumizole, or triticonaz
ole); pyrimidinyl carbinols such as ancimidol (ancym)
idol), fenarimol, or nuarimol
imol); 2-aminopyrimidines, such as bupirima
te), dimethirimol or ethilimol (ethimol)
rimol); morpholines such as dodemorph, fenpropidin, fenpropimorph (fenprr)
opimorph), spiroxamine or tridemorph; anilinopyrimidines such as cyprodinil (
cyprodinil, pyrimethanil or mepanipyrim; pyrroles, such as fenpiclonil or fludioxonil
; Phenyl amides such as benalaxyl (benalaxyl), furalaxyl (furalaxyl), metalaxyl (metalaxyl), R- metalaxyl (R-metalaxyl), Ofuureisu (ofurace) or oxadixyl (oxadixyl); benzimidazoles, for example, benomyl (Benomyl ), Carbendazim, debacarb, fubadizole or thiabendazole; dicarboximides, such as
Clozolinate, diclozolin
oline), iprozine (iprodine), microzoline (mycloz)
olicine), procymidone or vinclozolin (
carboxamides, such as carboxin (car)
boxin), fenfuram, flutolanil (fluto)
ranil), mepronil, oxycarboxine (oxy)
carboxin or thifluzamide; guanidines, such as guazatine, dodine or iminoctadine; strobilurin (str)
obirurines), for example, azoxystrobin
in), kresoximmethyl, methinostrobin, SSF-129, methyl 2-[(
2-trifluoromethyl) -pyrid-6-yloxymethyl] -3-methoxyacrylate or 2- [α {[(α-methyl-3-trifluoromethyl-benzyl) imino] -oxy} -o-tolyl] -Glyoxylic acid methyl ester-O-methyl oxime (trifloxystrobin)
Dithiocarbamates, such as ferbam, mancozeb (
mancozeb, maneb, metiram, propineb, propineb, thiram, zineb
) Or ziram; N-halomethylthiodicarboximides such as captafol, captan, dichlofluanide, fluoromide
), Phorpet or trifluanid
); Copper compounds, for example, Bordeaux mixture, copper hydroxide, copper oxychloride, copper sulfate, cuprous oxide, mancopper
r) or oxine-copper; nitrophenol derivatives such as dinocap or nitrotar-isopropyl (
Nitrothal-isopropyl; organophosphorus derivatives such as edifenphos, iprobenphos
s), isoprothiolane, phosdiphen (p
hosdiphen), pyrazophos or toclofos-methyl; as well as other compounds of various structures, such as, for example, acibenzolar-S-met.
hyl), anilazine, blasticidin-S (blas)
ticidin-S), quinomethionate, chloroneb, chlorothalonil
il), cymoxanil, dichlone
, Diclomezine, dichlorane
, Dietofencarb, Dimethomorph (dim
ethomorph, dithianon, etridiazole, famoxadone, fenamidone, fentin, ferimzone, fluamin, fluazin, fluazim
ide), fosetyl-aluminum,
Hymexazole, kasugamycin, metasulfocarb, pencycuron,
Phthalide, polyoxins, probenazole, propamocarb
rb), pyroquilon, quinoxyphen (quinox)
yfen), quintozene, sulfur, triazoxide (t
riazoxide, tricyclazole, triforine, validamycin
, (S) -5-methyl-2-methylthio-5-phenyl-3-phenyl-amino-3,5-dihydroimidazol-4-one (RPA407213), 3,5-
Dichloro-N- (3-chloro-1-ethyl-1-methyl-2-oxopropyl)
-4-methylbenzamide (RH-7281), N-allyl-4,5-dimethyl-2-trimethylsilylthiophene-3-carboxamide (MON65500)
, 4-chloro-4-cyano-N, N-dimethyl-5-p-tolylimidazole-
1-sulfone-amide (IKF-916), N- (1-cyano-1,2-dimethylpropyl) -2- (2,4-dichlorophenoxy) -propionamide (AC
382042) or iprovalicarb (SZX7
22).

[0033] 1. Production Examples Example P-1: Compound No. Manufacture of 17

[0034]

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[0035] 0.2 g of a 60% dispersion of sodium hydride in mineral oil is washed with hexane and 5 ml of N, N-dimethylformamide are added thereto. 1.5 g of ethyl 2- (bromomethylphenyl) glyosylate O-methyloxime was added to the suspension.
And 1.2 g of 1- (4-bromophenyl) -propane-1,2-dione-1- (O-methyloxime) -2-oxime are added. The reaction mixture is heated to 50 ° C. and stirred at room temperature for 1 hour. Ice water is then added and extraction is carried out twice with in each case 50 ml of ethyl acetate. The combined organic extracts are washed with water and dried over sodium sulfate, and the solvent is distilled off under reduced pressure. The residue was taken up in ethyl acetate / hexane (1: 5% by volume)
Chromatography on silica gel using 〜1: 4% by volume). 1.3 g of the desired product are obtained in the form of white crystals, mp 103-104 ° C.

The compounds in the following table can be obtained in a similar manner.

[0037]

[Table 1]

[0038] 2. Formulation Examples Formulation examples for similar purposes for pesticidal use are described, for example, in WO 97/33890.

[0039] 3. Biological Examples The compounds in the table show good activity in the following pathosystems.

[0040] Example B-1: after 6 days of action a) Residual protective action against Pukushinia graminis (Puccinia g raminis) in wheat (residual-protection action) seeding (Sowing), wheat plants, wettable powder of the active ingredient An aqueous spray mixture (0.02% active ingredient) prepared from the formulation was added to the drip point
Spray until t) and infect 24 hours later with a uredospore suspension of the fungus. 48 hours incubation (conditions: 95-100 at 20 °)
(% RH) period, the plants are placed in a 22 ° greenhouse. Fungus and mold contamination (fung)
us infestation is assessed 12 days after infection. In this test, compounds 1, 3, 5, 7, 8, and 10 in Table 1 showed 80% or more potency.

B) Systemic action 5 days after sowing, the wheat plants are watered with an aqueous spray mixture (0.006% active based on soil volume) prepared from a wettable powder formulation of the active.
). Care is taken that the spray mixture does not come into contact with the plant parts on the soil. 48
After an hour, the plants are infected with a uredospore suspension of the fungus. After a period of 48 hours of incubation (conditions: 95-100% relative humidity at 20 °), plants are placed in a 22 ° greenhouse. Bacterial and mold contamination is assessed 12 days after infection.

Example B-2: Action on Phyto phthora infestans in tomato a) Residual protection action After a three week cultivation period, tomato plants were prepared from a wettable powder formulation of the active ingredient. The aqueous spray mixture (0.02% of active ingredient) is sprayed to the point of dripping and, after 24 hours, infected with the sporangia suspension of the fungus. Fungal and fungal contamination was assessed 5 days after infection, during which time 90-100% relative humidity and a temperature of 20 ° were maintained.

B) Systemic action After the cultivation period of 3 weeks, the tomato plants are sowed with an aqueous spray mixture (0.006% of active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. . Care is taken that the spray mixture does not come into contact with the plant parts on the soil. After 48 hours, the plants are infected with a sporangial suspension of the fungus. Fungal and fungal contamination was assessed 5 days after infection, during which time 90-100% relative humidity and a temperature of 20 ° were maintained.

Example B-3: Action on Plasmopara viticola in grapes (vines) Prepared from a wettable powder formulation of the active ingredient in grape seedlings of the 4-5 leaf stage. The aqueous spray mixture (active ingredient 0.02%) is sprayed to the point of dripping and after 24 hours the fungus is infected with a sporangia suspension of the fungus. Fungal contamination was evaluated 6 days after infection, during which time 95-100% relative humidity and 20 ° C temperature were maintained.

In this test, compounds 3 to 8 and 10 in Table 1 showed 90% or more potency.

Example B-4: Residual protective action against Venturia inaequalis in apples. Apple cuttings with new shoots of 10-20 cm.
The aqueous spray mixture prepared from the wettable powder formulation of the active ingredient (active ingredient 0.02%) is sprayed to the dropping point, and after 24 hours, the conidium suspension of the fungus and mold is sprayed. Infect with liquid. The plants are incubated at 90-100% relative humidity for 5 days and placed in a greenhouse at 20-24 ° for another 10 days. Bacterial and mold contamination is assessed 12 days after infection.

Example B-5: Action against Erysiphe graminis in barley a) Residual protective action An aqueous spray mixture prepared from a wettable powder formulation of the active ingredient on barley plants having a height of about 8 cm ( The active ingredient (0.02%) is sprayed to the dropping point and after 3-4 hours the conidia of the fungus are dusted. The infected plants are placed in a 22 ゜ greenhouse. Bacterial and mold contamination is assessed 12 days after infection. In this test, compound 2 of Table 1
, 5 and 10 showed 90% or more efficacy.

B) Systemic action A barley plant of about 8 cm in height is sprayed with an aqueous spray mixture (0.002% of active ingredient, based on the volume of the soil) prepared from a wettable powder formulation of the active ingredient. Care is taken that the spray mixture does not come into contact with the plant parts on the soil. After 48 hours, the plant
Dust the conidia of the mold. The infected plants are placed in a 22 ゜ greenhouse. Bacterial and mold contamination is assessed 12 days after infection.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, TZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL , IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (71) Applicant D-51368 Leverkusen, Germany F-term (Reference) 4H006 AA01 AA03 AB03 BW13 BW19 BW21 BW31 QN30 4H011 AA01 BB06

Claims (5)

[Claims] 1. A compound of the formula I Wherein R ₂ is hydrogen, methyl or ethyl; R ₃ is hydrogen, halogen, cyano, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₂ -C ₄ alkenyl, C ₂ -C ₄ alkynyl Or halomethyl, wherein n is 1 or 2. _{2. The} compound according to claim 1, wherein R ₂ is methyl and R ₃ is fluoro, chloro or bromo, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, ethynyl or trifluoromethyl. 3. A composition for controlling fungi, comprising an effective amount of the compound according to claim 1 as an active ingredient together with a suitable carrier substance. 4. A method for controlling and preventing the contamination of plants by phytopathogenic fungi, comprising applying the compound according to claim 1 to plants, parts thereof or their environment. (5) U is a compound of formula II is a leaving of the group R _2, R ₃ and n is reacted with a compound of formula III is as defined in formula I, process for preparing a compound of formula I according to claim 1 .