RU2127256C1 - Substituted oxime ethers and a fungicide, insecticide, arachnoicide agent - Google Patents

Abstract

FIELD: organic chemistry, insecticides. SUBSTANCE: invention relates to oxime ethers of the general formula (I)

where R¹ is C_1-6-alkyl, C_3-6-alkenyl, C_1-6- -halogenalkyl, C_1-4-alkoxy-C_1-6-alkyl, C_1-6-alkoxycarbonylalkyl, C_3-6-cycloalkylalkyl, phenylalkyl, phenylhydroxyalkyl being phenyl can be substituted with halogen; cyanoalkyl, phenyl- -C_3-6-alkenyl being phenyl can be substituted with halogen, C_1-2-halogenalkyl; furan-2-yl-C_1-6-alkyl; R² and R³ - H, alkyl, alkoxy-group, halogen, cyano- or nitro-group; R⁴ is H, phenyl, alkyl, C_3-6-cycloalkyl, halogenalkyl; R⁵ and R⁶ - Hor alkyl; X means -CH or nitrogen. Compounds of the formula (I) show fungicide, insecticide, archnoicide activity and effective action against broad spectrum of plant pathogenic fungi and can be used as leaf and soil fungicides. EFFECT: improved method of synthesis, enhanced effectiveness of compounds. 7 cl, 18 tbl, 448 ex

Description

в которой
R¹ обозначает C₁-C₆-алкил, C₃-C₆-алкенил, C₃-C₄-алкинил, C₁-C₆-галогеналкил, C₃-C₆-галогеналкенил, C₁-C₄-алкокси-C₁-C₆-алкил,
C₁-C₆-алкоксикарбонил-C₁-C₆-алкил, C₃-C₆-циклоалкил, C₃-C₆-циклоалкил-C₁-C₆-алкил, фенил-C₁-C₆-алкил, фенилокси-C₁-C₆-алкил, причем фенил может быть замещен галогеном; циан-C₁-C₆-алкил, фенил-C₃-C₆-алкенил, причем фенил может быть замещен галогеном, C₁-C₂-галогеналкилом; фуран-2-ил-C₁-C₆-алкил;
R² и R³ являются одинаковыми или различными и обозначают водород, C₁-C₄-алкил, C₁-C₄-алкоксигруппу, галоген, циано или нитрогруппу;
R⁴ обозначает водород, C₁-C₆-алкил, C₃-C₆-циклоалкил, галоген-C₁-C₇-алкил, фенил;
R⁵ и R⁶ являются одинаковыми или различными и обозначают водород или C₁-C₄-алкил; и
X обозначает - CH или азот.The invention relates to new substituted oxime ethers of the general formula I

wherein
R ¹ is C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ haloalkenyl, C ₁ -C ₄ alkoxy -C ₁ -C ₆ -alkyl,
C ₁ -C ₆ alkoxycarbonyl-C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl-C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, phenyloxy-C ₁ -C ₆ alkyl, wherein phenyl may be substituted with halogen; cyan-C ₁ -C ₆ -alkyl, phenyl-C ₃ -C ₆ -alkenyl, wherein phenyl may be substituted with halogen, C ₁ -C ₂ -haloalkyl; furan-2-yl-C ₁ -C ₆ alkyl;
R ² and R ³ are the same or different and are hydrogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, halogen, cyano or nitro;
R ⁴ is hydrogen, C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, halogen-C ₁ -C ₇ alkyl, phenyl;
R ⁵ and R ⁶ are the same or different and are hydrogen or C ₁ -C ₄ alkyl; and
X is CH or nitrogen.

Preferred oxime ethers of formula I are selected from the group where R ¹ is methyl, R ² is methyl at position 2, R ⁴ and R ⁶ are methyl, R ³ and R ⁵ are hydrogen, X is nitrogen, and the oxyminoethyl radical is in position 4
or substituted oxime ethers of the formula I, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ and R ⁶ are methyl, R ³ and R ⁵ are hydrogen, X is CH, and the oximine radical is at position 4 , or
substituted oxime ethers of the formula I, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ is cyclopropyl, R ⁶ is methyl, R ³ and R ^{5 are} hydrogen, X is nitrogen, and the oxyminoethyl radical is at position 4 , or
substituted oxime ethers of formula I, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ is trifluoromethyl, R ⁶ is methyl, R ³ and R ⁵ are hydrogen, X is nitrogen, and the oxyminoethyl radical is at position 4 .

 Substituted oxime ethers of the formula I according to the invention exhibit fungicidal, insecticidal and arachnocidal activity.

 The invention also relates to a fungicidal, insecticidal, arachnocidal agent comprising an active substance and inert additives, which contains as an active substance a compound of formula (I) in an effective amount.

 The compounds of formula I and compositions based on them according to the invention have improved properties and a wider spectrum of action for plant protection compared to known analogous compounds.

 In particular, the use of oxime ethers is known, such as, for example, 2- (2'-methylphenoxymethyl) phenylglyoxylic acid methyl ester or 2- [2'-methyl-4 '- methyl ester methyl ester methoxyiminoeth-1 ″ -yl) phenoxymethyl] phenylglyoxylic acid as fungicides (EP N 253213; EP N 398692).

где Z означает метоксигруппу, в качестве фунгицидноактивных веществ.In addition, in EP N 386561 fungicidal agents containing compounds of formula IA are described,

where Z is a methoxy group, as fungicidal substances.

The radicals given in general formulas I can have, for example, the following meaning:
R ¹ may be, for example, C ₁ -C ₆ alkyl, predominantly C ₁ -C ₄ alkyl (e.g. methyl, ethyl, n- or isopropyl, n-, iso-, sec. Or tert-butyl , n-, iso, sec. - or neopentyl, hexyl), C ₃ -C ₆ alkenyl (e.g. allyl, 2-butenyl, 3-butenyl, 1-methyl-2-propenyl, 2-methyl-2- propenyl), C ₃ -C ₄ alkynyl (e.g. propargyl, 2-butynyl), C ₁ -C ₆ haloalkyl (e.g. 2-fluoroethyl), C ₃ -C ₆ -haloalkenyl (e.g. 3-chloroallyl), C ₁ -C ₄ alkoxy-C ₁ -C ₆ alkyl (e.g. 2-methoxyethyl, 3-ethoxypropyl), C ₃ -C ₆ -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexy l), C ₃ -C ₆ cycloalkyl-C ₁ -C ₄ -alkyl (e.g. cyclopropylmethyl, cyclohexylmethyl), cyan-C ₁ -C ₆ -alkyl (e.g. cyanmethyl, 3-cyanopropyl), C ₁ -C ₆ -alkoxycarbonyl-C ₁ -C ₆ -alkyl (e.g. ethoxycarbonylmethyl, tert.-butoxycarbonylmethyl, tert-butoxycarbonylpropyl), phenyl-C ₁ -C ₆ -alkyl (e.g. benzyl, 2-phenylethyl, 3-phenylpropyl, 4- phenylbutyl), phenoxy-C ₁ -C ₆ -alkyl (e.g. phenoxymethyl, phenoxyethyl, phenoxypropyl, phenoxybutyl), wherein phenyl may be substituted with halogen, phenyl-C ₃ -C ₆ alkenyl (e.g. 4-phenyl-2-butenyl , 4-phenyl-3-butenyl), wherein phenyl may b substituted with one or more radicals, for example from 1 to 5, in particular from 1 to 3 radicals from the group: halogen, C ₁ -C ₂ haloalkyl (for example, trifluoromethyl, trichloromethyl); or furan-2-yl-C ₁ -C ₆ alkyl;
R ² and R ³ may be the same or different and are hydrogen, C ₁ -C ₄ alkyl (e.g. methyl, ethyl, n- or isopropyl, butyl), C ₁ -C ₄ alkoxy (e.g. methoxy, ethoxy, n- or isopropoxy, butoxy), halogen (e.g. fluorine, chlorine, bromine, iodine), cyano or nitro;
R ⁴ may be, for example, C ₁ -C ₆ -alkyl, (C ₁ -C ₄ -alkyl) (for example, methyl, ethyl, n- or isopropyl, n-, iso-, sec- or tert-butyl , n-iso, sec., tert. - or neopentyl, hexyl), C ₁ -C ₇ haloalkyl (e.g. trifluoromethyl, trichloromethyl, chloromethyl, 2-chloroethyl, 3-chloropropyl, 3-bromopropyl, 4-chlorobutyl 4-bromobutyl, 5-chloropentyl, 5-bromopentyl, 6-chlorohexyl, 6-bromohexyl), C ₃ -C ₆ -cycloalkyl (e.g. cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl), phenyl;
R ⁵ and R ⁶ may be the same or different and are hydrogen or C ₁ -C ₄ alkyl (e.g. methyl, ethyl, n- or isopropyl, butyl). Preferred are compounds of formula I, where R ⁵ is hydrogen and R ⁶ is methyl.

The radical —C (R ⁴ ) = NOR ¹ may be on the phenyl radical relative to —O — CH ₂ in the second, or third, or, preferably, fourth position.

New compounds of the general formula I can be prepared with respect to C = C or C = N double bonds in the form of E / Z isomeric mixtures, which can be separated into individual isomers in the usual way, for example, by crystallization or chromatography. Both individual isomeric compounds and mixtures thereof are encompassed by the invention and are useful as fungicides and pesticides. In the case of the group —C (CONR ⁵ R ⁶ ) = X — OCH ₃ , those compounds are preferred in which the groups CONR ⁵ R ⁶ and OCH ₃ with respect to the double bond C = X have the configuration E. In the case of the group —C (R ⁴ ) = N-OR ¹ , those compounds are preferred in which R ⁴ and OR ¹ are stable with respect to the C = N double bond and, therefore, with small substituents, for example methyl, the C = N double bond has the configuration E .

The preparation of new compounds of the formula I can be carried out, for example, as follows: a substituted oxime ether of the general formula II, where L is a C ₁ -C ₄ alkoxy group, a hydroxyl group or a halogen such as chlorine or bromine, is treated with primary or secondary amine of the formula HNR ⁵ R ⁶ in accordance with the above scheme A (see the scheme at the end of the text).

The compounds of formula II, where L is an alkoxy group C ₁ -C ₄ , are known from EP N 386561 or can be obtained similarly to the method described there. From them, the corresponding carboxylic acids N (L = OH) can easily be obtained in the usual way (see, for example, Houben Weyl, Bd E 5, S. 223-254; Org. Reactions 24, (1976), S. 187-224 ) They can then be converted to activated derivatives of acids, such as, for example, imidazolides of acid II, where L = imidazol-1-yl or acid halides II, where L = Cl, Br (Houben Weyl, Bd VIII, S. 463). The resulting compounds of formula II are reacted with a primary or secondary amine HNR ⁵ R ⁶ to give the corresponding amide of formula I (Houben Weyl, Bd E 5, S. 941-977, S. 983-991; Houben Weyl, Bd VIII S. 654 ff) .

R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X have the above meanings.

Compounds of formula IA in which Z is OR ⁷ are known from European patent application 386561 or can be prepared by the methods described therein.

Production Example 1
2- [2'-methyl-4 '- (methoxyiminoeth-1''- yl) -phenoxymethyl] phenylglyoxylic acid methylamide
a) 225.3 g (1.5 mol) of 4-hydroxy-3-methylacetophenone are dissolved in 600 ml of dry methanol. 150.3 g (1.8 mol) of methoxyamine hydrochloride and 100 g of molecular sieve are added. The mixture was stirred for 12 hours at room temperature (20 ^° C.). The molecular sieve is filtered off. The filtrate was concentrated. The residue was taken up in dichloromethane. The organic phase is washed with water, dried and concentrated. The resulting solid was washed with pentane and then dried. 252 g (94%) of 4-hydroxy-2-methylacetophenone-O-methyloxy is obtained as a colorless crystalline solid (melting point: 96-98 ^° C.).

b) 89.6 g (0.5 mol) of 4-hydroxy-3-methylacetophenone-O-methyloxyme are placed under nitrogen in 300 ml of dry methanol. 90 g (0.5 mol) of a 30% (weight percent) sodium methanolate solution are added dropwise. After 2 hours, methanol was distilled off. The residue was dissolved in 700 ml of dimethylformamide. Add 15 g of potassium iodide. Then, at room temperature, in a nitrogen atmosphere, a solution of 151.6 g (0.53 mol) of 2-bromomethyl methylglyoxime phenylglyoxylic acid methyl ester in 300 ml of methanol is added dropwise. After about 10 hours of stirring at room temperature, the solution was cooled to about 10 ^° C. and water was added dropwise. The resulting precipitate was filtered off, washed with water and pentane and dried. 153.7 g (80%) of 2- [2'-methyl-4 '- (methoxyiminoeth-1''- yl) -phenoxymethyl] phenylglyoxylic acid methyl ester methyl ester is obtained as a colorless crystalline solid (melting point) : 138-140 ^o C).

c) 4.8 g (0.012 mol) of 2- [2'-methyl-4 '- (methoxyiminoeth-1''yl) phenoxymethyl] phenylglyoxylic acid methyl ester O-methylglyoxime is dissolved in 32 ml of tetrahydrofuran and mixed with 3.6 g (0.047 mol) of a 40% aqueous methylamine solution. Then the reaction mixture was stirred for 6 hours at 40 ^o C. Then the mixture was concentrated. The residue was taken up with methyl tert-butyl ether. The organic phase is washed with water, dried and concentrated again. The remaining crude product is purified by chromatography through a column of silica gel (cyclohexane / ethyl acetate, 1: 1). 3.2 g (67%) of 2- [2'-methyl-4 '- (methoxyiminoeth-1''- yl) phenoxymethyl] phenylglyoxylic acid methylamide O-methyloxymethyl amide are obtained in the form of colorless crystals (melting point: 104-105 ^o C, compound I.007).

Production Example 2
Α- [2- [2′-methyl-4 '- (methoxyiminoeth-1''- yl) phenoxymethyl] phenyl] -β- methoxyacrylic acid methylamide
a) Methyl ester of α- (2-bromomethylphenyl) -β-methoxyacrylic acid and 4-hydroxy-3-methylacetophenone-O-methyloxime are converted analogously to variant b) (example 1) into α- [2- [2 ′ methyl 4 '- (methoxyiminoeth-1''- yl) phenoxymethyl] phenyl] β-methoxyacrylic acid. The compound is obtained as a colorless solid (melting point: 118-120 ^° C.).

b) 3 g (0.0078 mol) of α- [2- [2′-methyl-4′- (methoxyiminoeth-1 '' yl) phenoxymethyl] phenyl] -β-methoxyacrylic acid methyl ester are dissolved in 15 ml dry pyridine. 5.2 g (0.039 mol) of anhydrous lithium iodide are added and stirred for 8 hours at 130 ^° C. The reaction mixture is concentrated. The residue is taken up with water. The aqueous phase is first washed with methyl tert-butyl ether and then acidified with hydrochloric acid. The aqueous phase is then extracted with methyl tert.-butyl ether. The simple methyl tert phase. -butyl ether is washed with water, dried over sodium sulfate and concentrated. 2.1 g of α- [2- [2'-methyl-4 '- (methoxyiminoeth-1''- yl) phenoxymethyl] phenyl] -β-methoxyacrylic acid are obtained in the form of a dark resin, which is used without further purification subsequent reactions.

c) 2.1 g (0.0056 mol) of α- [2- [2'-methyl-4 '- (methoxyiminoeth-1''- yl) -phenoxymethyl] phenyl] -β-methoxyacrylic acid and 0.53 g of pyridine is placed in 10 ml of dry diethyl ether. At a temperature of 0-5 ^° C., 0.8 g (0.0067 mol) of thionyl chloride are added dropwise and stirred for 10 hours at room temperature. Then filtered off. The filtrate was concentrated. Obtain 2 g of acid chloride of α- [2- [2'-methyl-4 '- (methoxyiminoeth-1 "-yl) -phenoxymethyl] -phenyl] -β-methoxyacrylic acid as a dark oil, which is used without further purification for subsequent reactions .

d) 1 g (0.0026 mol) of α- [2- [2'-methyl-4'- (methoxyiminoeth-1 "-yl) phenoxymethyl] phenyl] -β-methoxyacrylic acid chloride is placed in 10 ml of dichloromethane. At 0-5 ^° C., a solution of 1 g (0.032 mol) of methylamine in 10 ml of dichloromethane is added dropwise, stirred for 10 hours at room temperature, the reaction mixture is collected with 20 ml of dichloromethane, washed with water, dried and concentrated. The remaining crude product chromatographic purification through a silica gel column (n-hexane / acetone, 2: 1) yields 0.5 g (50%) of methylamide α- [2- [2'-methyl-4 '- (metho siiminoet-1 '' - yl) phenoxymethyl] phenyl] -β- metoksiakrilovoy acid as colorless crystals (melting point: 96-98 ^o C, compound I. 006).

Accordingly, it is possible to obtain compounds I indicated in the following table. I, in which Z is NR ⁵ R ⁶ . Compound IA, in which Z denotes OR ⁷ , can be obtained according to EP N 386561. They are also shown in table. 1.

The following groups of compounds 1, 2, 5, 11, 18-22 corresponding to compounds of the general formula I in which Z is NR ⁵ R ⁶ are of particular importance in connection with their biological activity against pests (plant pathogenic fungi, as well as insects, arachnids and nematodes).

In addition, groups of compounds 3, 4, 12-17, 23-27, corresponding to the general formula IA, in which Z is OR ⁷ , also have biological activity against animal pests (insects, arachnids and nematodes).

The following are compounds having the general formulas I.1 - I.5 with different positions of the radicals in the phenyl core with the values of R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X indicated in the table. A - E.

2. Соединения общей формулы I.2, в которых заместители R¹, R², R³, R⁴ и X имеют соответствующие значения, указанные в табл. B

3. Соединения общей формулы I.3, в которых заместители R¹, R², R³ и X имеют соответствующие значения, указанные в табл. A

4. Соединения общей формулы I.4, в которых заместители R¹, R², R³, R⁴ и X имеют соответствующие значения, указанные в табл. B

5. Соединения общей формулы I.5, в которых заместители R¹, R², R³, R⁴, R⁵, R⁶ и X имеют соответствующие значения, указанные в табл. C

6. Соединения общей формулы I.2, в которых R⁴ обозначает циклопропил и заместители R¹, R², R³ и X имеют значения, указанные в табл. D.1. The compounds of General formula I.1, in which the substituents R ¹ , R ² , R ³ , R ⁴ and X have the corresponding meanings indicated in the table. A

2. Compounds of General formula I.2, in which the substituents R ¹ , R ² , R ³ , R ⁴ and X have the corresponding meanings indicated in the table. B

3. Compounds of General formula I.3, in which the substituents R ¹ , R ² , R ³ and X have the corresponding meanings indicated in the table. A

4. The compounds of General formula I.4, in which the substituents R ¹ , R ² , R ³ , R ⁴ and X have the corresponding meanings indicated in the table. B

5. Compounds of General formula I.5, in which the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ and X have the corresponding meanings indicated in the table. C

6. Compounds of general formula I.2, in which R ⁴ is cyclopropyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

7. Compounds of general formula I.2, in which R ⁴ is cyclopentyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

8. The compounds of General formula I.2, in which R ⁴ denotes cyclohexyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

9. The compounds of General formula I.2, in which R ⁴ denotes CF ₃ and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

10. The compounds of General formula I.2, in which R ⁴ denotes CH ₂ Cl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

11. The compounds of General formula I.2, in which R ⁴ denotes CH ₂ CH ₂ Cl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

12. The compounds of general formula I.4, in which R ⁴ is cyclopropyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

13. The compounds of general formula I.4, in which R ⁴ is cyclopentyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

14. The compounds of general formula I.4, in which R ⁴ is cyclohexyl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

15. Compounds of general formula I.4, in which R ⁴ is CF ₃ and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

16. The compounds of general formula I.4, in which R ⁴ is CH ₂ Cl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

17. The compounds of general formula I.4, in which R ⁴ is CH ₂ CH ₂ Cl and the substituents R ¹ , R ² , R ³ and X have the meanings indicated in the table. D.

18. The compounds of General formula I.2, in which R ⁴ denotes cyclopropyl, = X- denotes = N - and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

19. The compounds of general formula I.2, in which R ⁴ is cyclopentyl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

20. The compounds of General formula I.2, in which R ⁴ denotes cyclohexyl, = X- denotes = N - and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

21. The compounds of General formula I. 2, in which R ⁴ denotes CF ₃ , = X- denotes = N - and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

22. The compounds of general formula I.2, in which R ⁴ is CH ₂ CH ₂ Cl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

23. The compounds of general formula I.4, in which R ⁴ is cyclopropyl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

24. The compounds of general formula I.4, in which R ⁴ is cyclopentyl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

25. The compounds of general formula I.4, in which R ⁴ is cyclohexyl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

26. The compounds of general formula I. 4, in which R ⁴ is CF ₃ , = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

27. The compounds of general formula I.4, in which R ⁴ is CH ₂ CH ₂ Cl, = X- is = N- and the substituents R ¹ , R ² and R ³ have the meanings indicated in the table. E.

 The new compounds of formula I exhibit excellent action against a wide range of plant pathogenic fungi, in particular from the class of ascomycetes and basidiomycetes, and can be used as leaf and soil fungicides. In part, they have noteworthy high systemic mobility and effectiveness in soil and, in particular, also leaf application.

 They are of particular importance for controlling many fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, cereals, cotton, soy, coffee tree, sugarcane, grape, fruit and ornamental plants and vegetable plants, such as cucumbers, beans and pumpkin, as well as on the seeds of these plants.

They are especially suitable for controlling the following plant diseases:
Erysiphe graminis (powdery mildew) in cereals,
Erysiphe cichoracearum and Shaerotheca fuliginea on pumpkin plants,
Podospheare leucotricha on apple trees,
Uncinula necator on grapes,
Puccinia - Varieties on Crops,
Rhizoctonia - varieties on cotton and grain,
Ustilago - Varieties on cereals and sugarcane,
Venturia inaequalis (scab) on apple trees,
Helminthosporium - varieties on cereals,
Septoria nodorum on wheat,
Botrytis cinerea (gray mold) on strawberries, grapes,
Cercospora arachidicola on peanuts,
Pseudocercosporella herpotrichoides on wheat, barley,
Pyricularia oryzae on rice,
Phytophtora infestans on potatoes and tomatoes,
Furasium- and Verticillium - varieties on various plants,
Plasmopara viticola on grapes,
Alternaria - Varieties on vegetables and fruits.

 Compounds I are used by treating fungi or plants, seed, protected against fungal damage, or soil with a fungicidal amount of active substances. Application is carried out before or after infection of materials, plants or seeds with fungi.

 Compounds I can be added to conventional formulations, such as, for example, solutions, emulsions, suspensions, dust preparations, powder, pastes and granules. Forms of application are determined by the purpose of application; in each case, they must ensure a fine and uniform distribution of the ortho-substituted benzyl ester of cyclopropanecarboxylic acid. The compositions are prepared in a known manner, for example, by mixing the active substance with solvents and / or excipients, if necessary using emulsifying and dispersing agents, and besides water, other organic solvents, such as auxiliary solvents, can also be used as diluents. For this purpose, mainly auxiliary materials are considered: solvents, such as aromatic hydrocarbons (e.g. xylene), chlorinated aromatic hydrocarbons (e.g. chlorobenzenes), paraffins (e.g. oil fractions), alcohols (e.g. methanol, butanol) , ketones (e.g. cyclohexanone), amines (e.g. ethanolamine, dimethylformamide) and water; fillers, such as natural ground rocks (e.g. kaolin, alumina, talc, chalk) and synthetic finely ground rocks (e.g. finely divided silicic acid, silicates); emulsifiers, such as non-ionic and anionic emulsifiers (for example, polyoxyethylene ether and fatty alcohol, alkyl sulfonates and arylsulfonates) and dispersants, such as spent lignin-sulfite liquor and methyl cellulose.

 Fungicidal agents generally contain from 0.1 to 95, preferably from 0.5 to 90% by weight of the active substance.

 Consumption rates, depending on the desired effect, range from 0.01 to 3 kg of active substance per ha.

 When processing the seed, an active substance of usually from 0.001 to 50 g, preferably from 0.01 to 10 g, per kilogram of seed is usually required.

 The agents according to the invention can also be used in the form of fungicides together with other active substances, for example, herbicides, insecticides, growth regulators, fungicides or also with fertilizers.

 Moreover, when mixed with fungicides, in many cases an extension of the spectrum of action of fungicides is obtained.

 In addition, the compounds of formula IA are suitable for controlling pests of the class of insects, arachnids and nematodes. They can be used to protect plants, as well as in the field of hygiene, protection of food stocks and veterinary medicine for pest control.

 Pests include butterflies / Lepidoptera /, for example, Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticuli rifumirumumifuridae, Cheimatidae, Cheimatidae unipunkta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grndiosella, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiquella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholita heliella teliella teliella teliella tibeta Hibernia defoliaria, hyphantria cunea, hyponomeuta malinellus, keifferia lycopersicella, lambdina fiscellaria, laphygmy exigua, leucoptera coffeella etria clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis, Panolis flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea plyplooplispriella pyllida plyoplella citella perellum citella francaella Perculella, Phyllocnistisifella citrella citella perellum Scrobipalpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viridana, Tricoplusia ni, Zeiraphera canadensis.

 From the order of beetles (coleoptera), for example, Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonimus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruus lechruus bruus lechruus bruus lechruus bruus lechruus bruus lechruus bruchus , Cassida nebulosa, Cerotoma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrynchus napi, Chaetochema fibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica longicornis, Diabrotica 12-punctata, Dicbrotica 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 aenueus, Melolontha hippocastani, Onlemachrjörnjörjörjörjörjörjörjörmöloryrjörljörjörjörjörjörjörjörmölorytrjor otreta chrysocephala, Phyllophaga sp., Phyllopertha horticola, Phyllotreta striolata, Popillia japonica, Sitona lineatus, Sitophilus granaria.

 From a diptera squad, for example, Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitus capitata, Chrisomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Gontariniaecaea daeaeeciopeifaeophiopephaeophisensopha , Gasterophilus intestinalis, Glossia morsitans, Haematobia irritans, Haplodiplosis equetris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Oscillaria muscola, Lucilia sericella musca frit, Pegormya hysocyami, Phorbia antiqua, Phobia brassicae, Phorbia coarctata, Rhagoletis cerasi, Phagoletis pomonella, Tabanus bovinus, Tipula oleracea, Tipula paludosa.

 From the thrips order (fringed-winged), for example, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi, Thrips tabaci.

 From the order of Hymenoptera, for example, Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, Solenopsis geminata, Solenopsis invicta.

 From the order of bugs (half-winged), for example, Acrosternum hilare, Blussus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Disdercus intermedius, Eurygaster integriceps, Euchistus impictiventris, Leptoglossus phyllopus, Lygus linezarais, Polgis insultis .

 From the order Homoptera Proboscidea, 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, Meguora viciae, Metopolophium dirhodum, Myzodes persicae, Myzus cerasi, Nilaparvata lugens, Pemphigus bursarius, Perkinsella saccharicida, Phoroda mali mali, Phorlla mali malis, Psylla mali malis, Psylla mali malis Schizaphis graminum, Schizoneura lanuginosa, Trialeurodes vaporariorum, Viteus vitifolii.

 From the termite order, for example, Calotermes flavicollis, Leucotermes flavipes, Retuculitermes lucifugus, Termes natalensis.

 From the order of Orthoptera, for example, Acheta domestica, Blatta orientalis, Blatella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus birittatus, Melanoplus femur-rubrum, Melanoperopusus Melanoplus frusculus mexicanus Schistocerca peregrina, Stauronotus maroccanus, Tachycines asynamorus.

 From the order of arachnids, for example, Amblyomma americanum, Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Brevipalpus phoenicis, Bryobia praetiosa, Dermacentorischomdes, Oromissiforidiifomidiifomidiomidisomidomidiomidisfomidiomidisfomldiomidomidomidomidisfomidomidiforidov, , Otobins megnini, Paratetranychus pilosus, Permanyssus gallinae, Phyllocaptrata oleivora, Polyphagatarsonemus latus, Psoroptes ovis, Rhipicephalus appendiculatus, Rhipicephalus evertsi, Saccoptes scabiei, Tetranychus.

 From the class of nematodes, for example, root bile roundworms, for example, Meloidogyne halpa, Meloidogyne incognita, Meloidogine javanica, nematodes forming a cyst, for example, Globodera rostochiensis, Heterodera avenae, Heterodera glycinae, Heterodera schatii, leaf, for example , 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.

 Active substances can be used in the form of formulations, or in forms prepared from these formulations, ready for use, for example, in the form of directly sprayed solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dust preparations, dispersible preparations, granules by spraying dusting, spraying, scattering or watering. The forms of application depend on the purpose of the application; in each case, they must ensure the distribution of the active substances proposed in the invention, if possible with a very thin layer.

 The concentration of the active substance in ready-to-use formulations can vary over a wide range.

 They are generally in the range of 0.0001 to 10%, preferably in the range of 0.01 to 1%.

 Active substances can also be used with great success by the method of ultra-low volume (ULV), and it is possible to obtain compositions with more than 95 wt. % active substance or even active substance without additives.

 The consumption rate of the active substance for pest control in open ground conditions reaches from 0.01 to 2.0, preferably from 0.2 to 1.0 kg / ha.

 To obtain directly sprayed solutions, emulsions, pastes or oil dispersions, mineral oil fractions with a medium to high boiling point are used, such as kerosene or diesel oil, tar tar oils, as well as oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, for example benzene, toluene, xylene, paraffin, tetrahydronaphthalene; alkyl naphthalenes or their derivatives; methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone; highly polar solvents, for example dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water.

 Aqueous use forms can be prepared from emulsion concentrates, pastes, powders (wettable powder, oil dispersions) by adding water. To obtain emulsions, pastes or oil dispersions, it is possible to homogenize the substances, in their original form or dissolved in an oil or solvent, using wetting agents, adhesive additives, dispersants or emulsifiers. However, concentrates consisting of an active substance, a wetting agent, adhesive additives, a dispersant or emulsifier and, respectively, a solvent or oil, suitable for dilution with water, can also be obtained.

 Surfactants are salts of alkali, alkaline earth metals, ammonium salt of ligninsulfonic acid, naphthalene sulfonic acid, phenolsulfonic acid, dibutylnaphthalene sulfonic acid, alkylaryl sulfonates, alkyl sulfates, alkyl sulfonates, fatty alcohol sulfates and alkali metal salts of alkaline salts glycol ether and fatty alcohol, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde , Condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenyl polyglycol ether, tributylphenyl polyglycol ether, alkyl aryl polyhydric alcohols, isotridecyl alcohol, ethylene oxide condensates of fatty alcohol, ethoxylated castor oil, polyoxyethylene alkyl ether, ethoxylated polyoxypropylene, polyglycol ether acetal lauryl water alcohol, sorbitol ester, spent ligninsulfite liquor and methyl cellulose.

 Powders, granules and pulverulent preparations can be obtained by mixing or grinding the active substances with a solid filler.

 The compositions contain the active substance, mainly in the range from 0.01 to 95 wt. %, preferably from 0.1 to 90 wt.%. The active substances are used with a purity of from 90 to 100%, preferably from 95 to 100% (according to NMR spectrum).

Examples of formulations are:
Granules, for example, granules in a shell, impregnating and homogeneous granules. They can be obtained by binding the active substances to solid excipients. Solid fillers are, for example, natural asphalt, such as silica gel, silicic acids, silicates, talc, kaolin, alumina, limestone, lime, chalk, bolus, loess, clay, dolomite, diatomaceous earth, calcium and magnesium sulfate, magnesium oxide milled synthetic materials, fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea and plant products, such as grain flour, bark flour, wood flour and nutshell flour, cellulose powder and other solid fillers.

 Various types of oils, herbicides, fungicides, other pesticides, bactericides also immediately before use can be added to the active substances. These agents can be mixed with the agents of the invention in a weight ratio of 1:10 to 10: 1.

 The agents of the invention may also be in these forms of application together with other active substances, such as, for example, herbicides, insecticides, growth regulators and fungicides, or mixed with fertilizers. When mixed with fungicides, in many cases an increase in the spectrum of fungicidal action is obtained.

 Examples of the use of active substances for action against harmful fungi.

и сложный метиловый эфир О-метилоксима 2-[2'-метил-4'- (метоксииминоэт-1''-ил)-феноксиметил] фенилглиоксиловой кислоты (B) формулы, описанный в EP 386561

A.1. Действие против Plasmopara viticola
Листья горшечного винограда сорта "Muller Thurgau" обрабатывают водным раствором для опрыскивания, содержащим 80% активного вещества и 20% эмульгатора в сухом веществе. Для анализа длительности действия активных веществ растения после высушивания нанесенного слоя помещают в теплицу на 8 дней. Лишь после этого листья инфицируют взвесью зооспор Plasmopara viticola (виноградные споры). Затем виноград помещают сначала на 48 часов в камеру, насыщенную водяным паром, при температуре 24^oC и затем на 5 дней в теплицу при температуре в пределах от 20 до 30^oC. По истечении этого времени для ускорения разрыва спорангиеносца растения вторично помещают во влажную камеру на 16 часов. Затем следует оценка размера разрыва грибка на обратной стороне листьев (см. табл.2)
A.2. Действие против бурой ржавчины на пшенице
Листья выращенных в горшках сеянцев пшеницы сорта "Канцлер" опыляют спорами бурой ржавчины (Puccinia recondita). Затем горшки помещают в камеру с высокой влажностью воздуха (90-95%) на 24 часа при температуре от 20 до 22^oC. В течение этого времени споры прорастают и проростки проникают в ткань листьев. Затем инфицированные растения опрыскивают водным раствором, содержащим 80% активного вещества и 20% эмульгатора в сухом веществе, до мокрого состояния. После высыхания нанесенного слоя опытные растения ставят в теплицу при температуре от 20 до 22^oC и относительной влажности воздуха от 65 до 70%. Через 8 дней определяют состояние развития ржавчинных грибков на листьях (см. табл.3)
A.3. Действие против ржавчины на фасоли
Листья фасоли обыкновенной кустовой сорта "Фори" опрыскивают водной споровой суспензией фасолевой ржавчины с обратной стороны листа равномерным слоем. Затем растения выдерживают в течение 24 часов в климатической камере с высокой влажностью воздуха при температуре 19^oC и затем ставят в теплицу при температуре 22-25^oC. Через 2-3 дня осуществляют обработку активными веществами путем распыления на нижнюю (базальную) половину верхней стороны листа. Оценка состояния развития грибков на листьях осуществляется через 10-12 дней после опрыскивания. Благодаря временному и пространственному разделению обработки листьев спорами и обработки листьев активными веществами исключается непосредственный контакт между грибком и активным веществом; поэтому впитывание активного вещества и перемещение активного вещества в листе должно предшествовать действию фунгицида (системное передвижение). Проверка различных зон листьев позволяет установить трансламинарное или апикальное движение испытуемых активных веществ в листе.The following compounds were used as comparative active substances: O-methyloxime 2- (2'-methylphenoxymethyl) phenylglyoxylic acid methyl ester (A) of the formula described in EP 253213

and 2- [2'-methyl-4'- (methoxyiminoeth-1 '' - yl) -phenoxymethyl] phenylglyoxylic acid methyl ester O-methyl oxime (B) of the formula described in EP 386561

A.1. Action against Plasmopara viticola
Muller Thurgau potted grape leaves are treated with an aqueous spray solution containing 80% active substance and 20% emulsifier in dry matter. To analyze the duration of action of the active substances, the plants after drying the applied layer are placed in a greenhouse for 8 days. Only after this leaves are infected with a suspension of Plasmopara viticola zoospores (grape spores). Then the grapes are first placed for 48 hours in a chamber saturated with water vapor at a temperature of 24 ^o C and then for 5 days in a greenhouse at a temperature in the range from 20 to 30 ^o C. After this time, to accelerate the rupture of the sporangios, plants are re-placed in wet camera for 16 hours. This is followed by an estimate of the size of the fungal rupture on the back of the leaves (see Table 2)
A.2. Action against brown rust on wheat
The leaves of the Chancellor cultivated wheat seedlings are pollinated with brown rust spores (Puccinia recondita). Then the pots are placed in a chamber with high humidity (90-95%) for 24 hours at a temperature of from 20 to 22 ^o C. During this time, the spores germinate and the seedlings penetrate the leaf tissue. Then, infected plants are sprayed with an aqueous solution containing 80% of the active substance and 20% of the emulsifier in the dry substance, to a wet state. After drying of the applied layer, the experimental plants are placed in a greenhouse at a temperature of from 20 to 22 ^o C and a relative humidity of 65 to 70%. After 8 days, the state of development of rust fungi on the leaves is determined (see table 3)
A.3. Anti-rust action on beans
Bean leaves of ordinary bush varieties "Fori" are sprayed with an aqueous spore suspension of bean rust on the back side of the sheet in a uniform layer. Then the plants are kept for 24 hours in a climate chamber with high humidity at a temperature of 19 ^o C and then put in a greenhouse at a temperature of 22-25 ^o C. After 2-3 days, the active substances are treated by spraying on the lower (basal) half of the upper side of the sheet. Assessment of the development of fungi on the leaves is carried out 10-12 days after spraying. Due to the temporal and spatial separation of leaf treatment with spores and leaf treatment with active substances, direct contact between the fungus and the active substance is excluded; therefore, absorption of the active substance and movement of the active substance in the sheet should precede the action of the fungicide (systemic movement). Checking the different areas of the leaves allows you to establish the translaminar or apical movement of the tested active substances in the leaf.

 The result of the experiment shows that after treatment with a solution containing 50 ppm of the active substance, the active substances I.003, I.007 and I.014 on the underside of the leaves and partially also on the untreated part of the bean leaves showed a fungicidal effect, while known compounds A and B did not show a fungicidal effect.

 In the table. 4 presents the results of example A.3.

 The results of these tests clearly show that the compounds in accordance with patent application serial N 08/091254 have certain advantages and improved action in the fight against undesirable mushrooms.

Application examples for action against pests
The action of the compounds of general formula IA against pests from the class of insects, arachnids and nematodes can be shown in the following experiments:
Active substances prepare
a) in the form of a 0.1% solution in acetone or
b) in the form of a 10% emulsion in a mixture of 70 wt.% cyclohexanol, 20 wt.% Necanil ^® LN (Lutenzene ^® AP6, a wetting agent with emulsifying and dispersing action based on ethoxylated alkyl phenols) and 10 wt.% Emulsor ^® EL ( emulan ^® EL, emulsifier based on ethoxylated fatty alcohols)
and diluted in accordance with the required concentration of acetone in case a) or water in case b).

 After the end of the experiments, the lowest concentration is determined at which the compound, compared with the untreated control tests, still causes 80% inhibition of development or mortality (threshold of action or minimum concentration).

B.1. Aphis fabae (black louse), contact action
Heavily affected bush beans (Vicia faba) are treated with the aqueous composition of the active substance. After 24 hours, determine the percentage of mortality.

 In this test, compounds I.007, I.011, I.015, I.003, I.001, I.017, I.058, I.086, I.096 and I.029 showed action thresholds from 200 to 1000 parts per million.

B.2. Nephotettix cincticeps (green rice cicadas), contact action
Round filters are treated with the aqueous composition of the active substance and then covered with 5 adult cicadas. After 24 hours, determine the percentage of mortality.

 In this test, compounds I.007, I.011, I.014, I.015, I.003, I.002, I. 004, I.017, I.117, I.307, I.192, I. 193, I.195 and I.201 showed an action threshold of 0.4 to 0.1 mg.

B. 3. Prodenia litura (Egyptian cotton worm), cultivation experience
Five larvae in the L3 developmental stage (10-12 mm) are placed in a standard nutrient medium (3.1 l of water, 80 g of agar, 137 g of brewer's yeast, 515 g of cornmeal, 130 g of wheat seedlings, as well as usual supplements and vitamins ( 20 g of Wesson's salt, 5 g of nipagin, 5 g of sorbine, 10 g of cellulose, 18 g of ascorbic acid, 1 g of lutavit ^® pale (vitamin), 5 ml of an alcoholic solution of biotin), previously moistened with an aqueous composition of the active substance.

 Observation continues until the hatching of the butterflies in the control experiment without the active substance.

 In this test, compounds I.003, I.014, I.015, I.017, I.057, I.064, I.068, I. 076, I.100, I.108, I.109, I. 112, I.119 and I.079 showed an action threshold of 200 to 0.1 ppm.

B.4. Agrotis ypsilon (soil larva), contact action
For 3 seconds, the leaves of corn are immersed in the aqueous composition of the active substance and, after the droplets have drained, they are placed in a Petri dish (diameter 12 cm) on a round filter. 5 larvae of 3 and 4 stages of development (approximately 15 mm in length) are placed in each cup. After 24 and 48 hours, the effect is determined by the% leaf conservation from eating and% mortality.

 In this experiment, compounds I.060, I.070, I.086, I.090, I.096, I.117, I.121, I. 129, I.140, I.177, I.307, I. 189, I.190, I.191, I.192, I.193, I.195, I.201 and I.213 showed a threshold of action of 10 to 1000 ppm.

B.5. Sitophilus granaria (weevil), contact action
The bottom of the test vessel is wetted with an acetone solution of the active substance and after evaporation of the solvent, 50 beetles are placed. After 4 hours, the beetles are placed in raw cardboard cups. These cups are then placed in a vessel for experiment. After 24 hours, mortality is determined, and beetles that cannot leave the cup are considered dead or severely affected.

 In this experiment, compound I.115 showed a threshold of action of 1 mg.

B.6. Musca domestica (housefly), contact action
The bottom of the test vessel is wetted with an acetone solution of the active substance and 10 flies are placed in the vessel after evaporation of the solvent. After 4 hours, determine the percentage of mortality.

 In this experiment, compounds I.064, I.071, I.077, I.080, I.083, I.085, I.098, I. 100, I.103, I.106, I.111, I. 115, I.117, I.126, I.127, I.130, I.133, I.309 and I.184 showed an action threshold of 0.01 to 2 mg.

B.7. Musca domestica (housefly), cultivation experience
25 ml of dry feed mixture (1 kg of bran, 250 g of yeast powder, 35 g of fish meal) are mixed with the active substance and 25 ml of a solution of milk with sugar (1 l of milk, 42 g of sugar) and then 20 stage 1 larvae are placed on this mixture development. After hatching, the larvae in the control experiment determine the percentage of mortality.

 In this experiment, compound I.064 showed a threshold of 4 ppm.

B.8. Prodenia litura (Egyptian cotton worm), control action
Round filters (diameter 9 cm) are treated with 1 cm ^{3 of the} aqueous composition of the active substance and placed in a plastic Petri dish (diameter 94 mm). Then 5 Prodenia L3 larvae are placed under development and the Petri dish is closed. The test lasts 24 hours.

 In this experiment, compounds I.098, I.100, I.102, I.106, I.111, I.115 and I.184 showed an action threshold of 0.1 to 1 mg.

B.9. Prodenia litura (Egyptian Cotton Worm)
5 larvae of the L3 developmental stage (10-12 mm) are placed in a standard nutrient medium (3.1 l of water, 80 g of agar, 137 g of brewer's yeast, 515 g of cornmeal, 130 g of wheat seedlings, as well as usual supplements and vitamins (20 g of Wesson salt, 5 g of nipagin, 5 g of sorbine, 10 g of cellulose, 18 g of ascorbic acid, 1 g of lutavit ^® blend (vitamin), 5 ml of an alcoholic solution of biotin)), previously moistened with an aqueous composition of the active substance. Observation continues until the hatching of the butterflies in the control experiment without the active substance.

 In this experiment, compounds I.128, I.272, I.292, I.293, I.307 and I.310 show an action threshold of 1 to 1000 ppm.

B.10. Plutella maculipennis (cabbage moth), contact action
The leaves of young cabbage plants are moistened with an aqueous composition of the active substance and then placed on a moistened filter. Then, 10 larvae of 4 stages of development are placed on the treated leaves. After 48 hours, the mortality rate is determined.

 In this experiment, compounds I.064, I.065, I.068, I.079, I.081, I.084, I.086, I.088, I.090, I.117 and I.130 showed an action threshold 200 to 1000 ppm.

B.11. Aedes aegypti (yellow fever midge), cultivation experience
Plastic cups with a capacity of 250 ml (diameter 8 cm) are filled with 200 ml of tap water at a water temperature of 23 ^o C and 30-40 larvae of Aedes 3-4 stages of development are placed in them. The test substance is added to the vessel in the form of an aqueous emulsion and in the suspension after 24 hours the mortality in the vessels is determined. Then cultivation continues until the hatching of midges. Room temperature reaches 25 ^o C.

 In this experiment, compound I.128 showed a threshold of action of 0.1 ppm.

1. Action against Plasmopara viticola (downy mildew of grapes)
Grapes in pots (cultivar "Muller-Thurgau") were intensively sprayed until drops with a prepared solution of the active substance. After 8 days, the plant was sprayed with a suspension of zoospores of Plasmopara viticola fungi and then kept for 5 days at 20-30 ^o C at high humidity. After this time, the plant was left for 16 hours in a humid chamber to accelerate the formation of zoosporangia. Then, the degree of damage on the underside of the sheet was determined by visual means (see table. 5).

2. Action against Pyricularia oryzae (def.)
Leaves from “Tail-Nong 67” cultivated rice seedlings grown in pots were sprayed intensively until droplets appeared with a composition containing the active substance in the amount of 10%, 63% cyclohexanone and 27% emulsifier. The next day, the plant was inoculated with an aqueous suspension of spores of Pyricularia oryzae. After that, the test plant was placed in a chamber with an artificial climate at 22-24 ^o C and a relative humidity of 95-99% for 6 days. Then, the percentage of damage on the underside of the sheet was visually determined (see Table 6).

An example proving the action against fungi
The fungicidal effect of the compounds of the general formula I is proved by the following experiments.

Active substances are prepared in the form of a 20% emulsion consisting of a mixture of 70 wt.% Cyclohexanone, 20 wt.% Nekanil ^® (Lutensol ^® AP6, a wetting agent with an emulsifier and dispersant based on alkyl phenol) and 10 wt. % Wettol ^® EM (non-ionic emulsifier based on ethoxylated recinole oil), and accordingly the emulsion is diluted with water to the desired concentration.

Action against Plasmopara viticola (Rebenpersonospora)
Grapes planted in a pot (Mueller Thurgau variety) were sprayed with a prepared solution of the active substance until drops formed. After 8 days, the plants were sprayed with a solution of spores of the Plasmopara viticola fungus and the plants were kept for 5 days at a temperature of 20-30 ^o C at high humidity. Before control, the plants were kept for 16 hours at high humidity. The control was carried out visually (see table. 7).

Action against Puccinia recondita (red rust of wheat)
Leaves of wheat germ (Kanzler cultivar) were sprinkled with spores of red rust Puccinia recondita. Treated in this way, the plants were kept for 24 hours at a temperature of 20-22 ^o C and a relatively high humidity of 90-95%, and then were treated with an aqueous solution of the emulsion. After the next 8 days of exposure at a temperature of 20-22 ^o C and humidity of 65-70%, the development of fungi was monitored. The control was carried out visually (see table. 8).

 The fungicidal effect of the compounds of formula I in accordance with the invention is illustrated by the following experiments.

Using active ingredients, a 20% emulsion was prepared in a mixture of 70 wt.% Cyclohexanone, 20 wt.% Nekanil ^® (Lutensol ^® AP6, a surfactant with emulsifying and dispersing action based on ethoxylated alkyl phenols) and 10 wt.% Emulphor ^® EL (Emulan ^® EL, an emulsifier based on ethoxylated fatty alcohols) and diluted with water to the desired concentration.

 Effect on Plasmopara viticola (downy mildew).

Potted grape plants of the Muller Thurgau variety were sprayed until the liquid drained with compositions of active ingredients. After 8 days, the plants were sprayed with a zoospore suspension of Plasmopara viticola mold and kept for 5 days at 20-30 ^o C and high relative humidity. Subsequently, the plants were kept at high relative humidity for 16 hours and evaluated. Evaluation was performed visually (see table. 9).

Effect on Puccinia recondita (rough rust of cereals)
Kanzler wheat seedlings were pollinated with wheat rust spores (Puccinia recondita). Thus treated plants were incubated for 24 hours at 20-22 ^o C and a relative humidity of 90-95%, and then treated with aqueous compositions of active components. After the next 8 days at 20-22 ^o C and a relative humidity of 65-70%, the degree of mold growth was determined. The results were evaluated visually; they are presented in table. ten.

 The test results of the compounds of formula I according to this invention and the compounds of formula Ia from US A5166399 are shown in table. eleven.

Using the compounds, a 20% emulsion was prepared in a mixture containing 70 wt. % cyclohexanone, 20 wt.% Nekanil ^® LN (Lutensol ^® AP6, a surfactant with emulsifying and dispersing effects based on ethoxylated alkyl phenols) and 10 wt.% Emulphor ^® EL (Emulan ^® EL, emulsifier based on ethoxylated fatty alcohols). The concentrations given in the examples were achieved by diluting the composition of the compounds with water.

 The biological effect of the compounds of table 11 was tested as follows.

A. Puccinia recondita
Kanzler wheat seedlings were pollinated with wheat rust spores (Puccinia recondita). Thus treated plants were incubated for 24 hours at 20-22 ^o C and a relative humidity of 90-95%, and then treated with aqueous compositions containing 250 parts per million active components. After the next 8 days at 20-22 ^o C and a relative humidity of 65-70%, the degree of mold growth was determined. The results were evaluated visually; they are presented in table. 12.

B. Erysiphe graminus var. tritici
The seedlings of wheat seeds of the Fruhgold variety were initially treated with aqueous compositions of active ingredients. After approximately 24 hours, the plants were pollinated with wheat powdery mildew spores (Erysiphe graminus var. Tritici). Thus treated plants were incubated for 7 days at 20-22 ^o C and a relative humidity of 75-80%. Then, the degree of mold growth was determined. The results were evaluated visually; they are presented in table. 13.

C. Pyricularia oryzae
The seedlings of rice of the "Tai Nong 67" variety were sprayed to drip the liquid with aqueous compositions containing 250 parts per million parts of active ingredients. After 24 hours, the plants were sprayed with an aqueous suspension of spores of the fungus Pyricularia oryzae and kept for 6 days at 22-24 ^o C and a relative humidity of 95-99%. The results were evaluated visually; they are presented in table. fourteen.

Examples of action against pests
The action of the compounds of general formula I against pests of the class of insects, arachnids and nematodes is shown using the following experimental data. The limits of action of individual substances are given in the tables.

Rice Cicadas (Nephotettix cincticeps)
Cottonworm (Prodenia litura), contact experiments
Leaf aphid (Aphis fabae).

 For these types of pests, accurate test data are given in sections B.1, B.2 and B.8.

Spider mite (Tetranychus urticae)
Description of the tests and the result of the experiments are given in table. 15. The second and third columns of Table 15 relate to the threshold of action, namely, to the minimum concentration at which at least 60% damage to the corresponding pest is achieved with respect to which the test compound is applied.

25A - Tetranychus urticae, bean spider mite
Type of experiments - contact action, spraying
Conducting experiments
Bush beans grown in a pot with a fully developed pair of leaves were sprayed in the cabin with an aqueous solution of the active substance until drops formed. Then the plants with the help of the guide bus were moved to the rotating pan of the cab and sprayed from all sides using three differently arranged nozzles of 30 cm ³ of the active substance solution. The irrigation process lasted approximately 20 seconds. Plants should have been severely affected by ticks and eggs.

 Control was carried out after 5 days using a binocular lens. It was determined whether all stages develop uniformly. During the experiment, the plants were in the usual conditions of a greenhouse.

Score -% defeat
Defeat:
100% lack of live caterpillars and eggs
80%: ≤ 4 live caterpillars and eggs
60%: 5-10 live caterpillars and eggs
0%>: 10 live caterpillars and eggs
Initial concentration: 0.04%
Standard: Plictran (Cyhexatin)

Claims (7)

1. Substituted simple oxime ethers of General formula I

wherein R ¹ is C ₁ -C ₆ alkyl, C ₃ -C ₆ alkenyl, C ₃ -C ₄ alkynyl, C ₁ -C ₆ haloalkyl, C ₃ -C ₆ haloalkenyl, C ₁ -C ₄ -alkoxy-C ₁ -C ₆ -alkyl,
C ₁ -C ₆ alkoxycarbonyl-C ₁ -C ₆ -alkyl, C ₃ -C ₆ -cycloalkyl, C ₃ -C ₆ -cycloalkyl,
C ₁ -C ₆ -alkyl, phenyl-C ₁ -C ₆ -alkyl, phenyloxy-C ₁ -C ₆ -alkyl, moreover, phenyl can be substituted by halogen, cyan-C ₁ -C ₆ -alkyl, phenyl-C ₃ - C ₆ alkenyl, wherein phenyl may be substituted with halogen, C ₁ -C ₂ haloalkyl, furan-2-yl C ₁ -C ₆ alkyl;
R ² and R ³ are the same or different and are hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -alkoxy, halogen, cyano or nitro;
R ⁴ is hydrogen, phenyl, C ₁ -C ₆ alkyl, C ₃ -C ₆ cycloalkyl, halogen-C ₁ -C ₇ alkyl;
R ⁵ and R ⁶ are the same or different and are hydrogen or C ₁ -C ₄ alkyl;
X is —CH or nitrogen. 2. The substituted oxime ethers of formula I according to claim 1, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ and R ^{6 are} methyl, R ³ and R ⁵ are hydrogen, X is nitrogen and the oxyminoethyl radical is in position 4. 3. The substituted oxime ethers of formula I according to claim 1, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ and R ⁶ are methyl, R ³ and R ⁵ are hydrogen, X is —CH and an oxyminoethyl radical is in position 4. 4. The substituted oxime ethers of formula I according to claim 1, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ is cyclopropyl, R ⁶ is methyl, R ³ and R ⁵ are hydrogen, X is nitrogen, oximine the radical is in position 4. 5. The substituted oxime ethers of formula I according to claim 1, where R ¹ is methyl, R ² is methyl at position 2, R ⁴ is trifluoromethyl, R ⁶ is methyl, R ³ and R ⁵ is hydrogen, X is nitrogen, oximine the radical is in position 4.  6. Substituted simple oxime ethers of the formula I according to claim 1, exhibiting fungicidal, insecticidal, arachnocidal activity.  7. Fungicidal, insecticidal, arachnocidal agent comprising an active substance and inert additives, characterized in that as an active substance it contains a compound of formula I according to claim 1 in an effective amount. Priority on points:
07/15/92. - according to claim 1, in addition to R ⁴ - cycloalkyl, halogenated, PP.2, 3, 6, 7;
03/31/93 - according to claim 1, where R ⁴ - cycloalkyl, halogenated, PP.4, 5.

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