CS274476B2 - Fungicide and insecticide and method of active substances production - Google Patents

Abstract

Heterocyclically substituted methyl alpha -arylacrylates of the general formula <IMAGE> in which R represents alkyl, alkenyl, haloalkyl, cycloalkyl, alkoxy, alkylcarbonyl, alkoxycarbonyl, halogen or aryl, where the aromatic ring is optionally substituted, Het represents a radical optionally substituted five-membered heterocyclyl having 1 to 3 hetero atoms, A represents ethenylene, ethylene, methyleneoxy or methylenethio, and fungicides and pesticides containing these compounds.

Description

The present invention relates to a fungicidal and insecticidal composition comprising, as active ingredient, novel heterocyclically substituted o-arylacrylic acid methyl esters. Said novel compounds have valuable fungicidal and insecticidal effects. The invention further relates to a process for the preparation of these novel active compounds.

It is already known to use methyl esters of acrylic acid, such as o- [2- (benzoxazol-2'-yloxy) phenyl] -3-methoxyacrylic acid methyl ester (cf. EP 2 5 6 667) as an insecticide. However, its insecticidal effect is not satisfactory.

It has now been found that heterocyclically substituted methyl esters of arylacrylic acid of formula I

in which

E represents a C1-C4 alkyl group, a cyclopropyl group or a phenyl group optionally substituted by a halogen atom, a C1-C4 alkyl group, a cyano group, a methoxy group or a nitro group,

Het means a residue of pyrrole, pyrazole, isoxazole, oxadiazole or thiadiazole, and

A represents an ethenylene group, an ethylene group or a methyleneoxy group, having an excellent fungicidal and insecticidal action which is superior to that of the known methyl esters of acrylic acid.

For example, the radicals of formula I may have the following meanings:

The substituent H may be a (C 1 -C 4) alkyl group (for example methyl, ethyl, n-propyl or isopropyl, n-butyl, isobutyl, sec-butyl or tert-butyl), cyclopropyl or phenyl optionally substituted by halogen (such as fluorine, chlorine or bromine), C1-C4 alkyl (e.g. methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl) , sec-butyl or tert-butyl), cyano, methoxy or nitro.

Het may be, for example, pyrrolyl, pyrazolyl, isoxazolyl, oxadiazolyl or thiadiazolyl.

The substituent A may be an ethenylene group (-CH = CH-), an ethylene group - (CH 2 -CH 8 -) or a methyleneoxy (-CH ₂ -O-) group.

Accordingly, it is an object of the present invention to provide a fungicidal and insecticidal composition which comprises, in addition to an inert carrier, an effective amount of at least one heterocyclically substituted β-arylacrylic acid methyl ester of the aforementioned general formula (I).

These novel compounds of formula I may be prepared, for example, by one of the following processes:

Compounds of formula (Ia) (R and Het are as defined above, A stands for ethenylene) and compounds of formula (Ib (R and Het are as defined above and A stands for methyleneoxy) 3e are obtained from heterocyclically substituted derivatives of methyl esters. -hydroxyacrylic acids of formula V, which may be present in equilibrium with the formyl derivatives of formula VI, by reaction with an alkylating agent (e.g.

CS 274 476 B2 with di-ethylsulfate, methyl iodide) in the presence of a base (e.g. potassium carbonate, sodium carbonate) in a diluent, e.g. acetone. The process is illustrated by the following reaction scheme in which L represents a leaving group (for example, a methylsulfate group or an iodide residue):

M

CH-OH

H (VI)

CH-OCH ₃ (Ia: A = -CH = CH-) (Ib: A = -CH ₂ -O-)

Heterocyclic-substituted C-aryl- [3-hydroxyecrylic acid methyl esters of formula V wherein A is ethenylene or methyleneoxy are prepared from heterocyclically substituted phenylacetic acid methyl esters of formula II by reaction with methyl formate using a base (e.g. sodium hydride, lithium diisopropylamide, sodium methoxide) in an inert solvent such as diethyl ether or tetrahydrofuran (cf. Ann. Chem. 424 (1921) 214) as illustrated in the following reaction scheme:

(II)

(IN)

CH-OH (A = -CH = CH- or -CH 6 -O-)

Heterocyclic substituted phenylacetic acid methyl esters of formula IIIa (A = ethylene), which are required as starting materials, are prepared from 2-formylphenylacetic acid methyl ester of formula III by reaction 8 with a methanephosphonic acid ester of formula IV (R and Het as defined above, r 'is methyl or ethyl). This reaction is carried out in a manner known per se (cf., for example, J. Am. Chem. Soc. 83 (1961) 1733). The starting materials are usually used in stoechio3

CS 274 476 B2 metric ratio. An excess of up to 10% (by weight) of one of the two reactants relative to the stoichiometric amount is possible. The reaction is conveniently carried out in an inert solvent or diluent (e.g. diethyl ether, tetrahydrofuran, methyl tert-butyl ether, ethylene glycol dimethyl ether, toluene, dimethylsulfoxide) in the presence of an equivalent amount of a base (e.g. sodium hydride, sodium amide, potassium t-butoxide, sodium methoxide). hutyllithium, phenyllithium, sodium bis-trimethylsilylamide, sodium methylsulfinylamide). The reactions generally take place in the temperature range from -70 ° C to +30 ° C. Since the reactions may in some cases take place with the release of heat, it may be advantageous for the reaction mixture to cool during the reaction. This process is illustrated by the following reaction scheme:

(IV)>

O * 1

R-Het-CH ₂ -P- (OR ¹ ) ₂

(Ila)

2-Formylphenylacetic acid methyl ester of formula III is obtained by esterifying 2-formylphenylacetic acid of formula VII with methanol under standard conditions. 2-Formylphenyl acetic acid of formula VII is prepared in a simple manner by ozonolysis of trimethylsilylenethanol of formula VIII obtained from 2-indanone of formula IX (cf. Tetrahedron Lett. 25 (1984) 3659; Tetrahedron 43 (1987) 2075).

(IX)

(VII)

H

COOCH-j

Heterocyclic substituted methanephosphonic acid esters of formula IV (R and Eet have the meanings given above and R ¹ is methyl or ethyl)

CS 274 475 B2 are obtained by reacting five-membered heteroaromatic methyl halogeno derivatives of the general formula R-Het-CH, -Z (X) (Z = chloro, bromo) with phosphorous phosphoric acid ester or triethyl phosphoric acid of general formula P (OR) j (cf. llethoden) der organischen Chemie, vol 12/1, p. 433, Thieme, Stuttgart 1963).

The heterocyclic substituted methyl esters of phenylacetic acid of general formula IIb (A represents methyleneoxy), which are required as starting materials, are prepared by reacting five-membered heteroaromatic methyl halogeno derivatives of formula X (X = chloro, bromo) with ortho-hydroxyphenylacetic acid methyl ester of formula XI

The reaction may be carried out by reacting in a reaction a stoichiometric amount of the starting materials of formulas X and XI in an inert solvent or diluent (e.g. acetone, acetonitrile, dimethylsulfoxide, dioxane, dimethylformamide, N-methylpyrrolidone, N, N -diethylpropyleneurea, pyridine). adding an equivalent amount of a base (e.g., sodium carbonate or potassium carbonate).

Alternatively, the methyl ortho-hydroxyphenylacetic acid of formula XI can be reacted first with a base (e.g. sodium hydroxide, potassium hydroxide) to convert it to the corresponding sodium phenoxide or potassium phenoxide and react with the pollen in an inert solvent. or a diluent (e.g., dimethylformamide) with five-membered heteroaromatic methyl halide derivatives of formula X to form heterocyclic substituted phenylacetic acid methyl esters of formula IIb.

A second procedure is available for the preparation of the novel compounds of formula (Ia) (R and Het have the meanings given above and E represents an ethenylene group). In this procedure, the five-membered heteroaromatic aldehydes of formula XII (R and Het are as defined above) are reacted with 2- [β-methoxy-t-methoxycarbonylvinyl) benzylphosphonic acid dimethyl ester of formula XIII (cf. J. Am. Chem. Soc. 83 (1961), 1733. This second process is illustrated by the following reaction scheme;

(XII)

R-Het-C

CH-OCH (XIII)

GS 274 476 B2

-> R

Het = CH = CH

V7

CHnOOC-C

J «

CH-OCHj (la)

The 2- (-methoxy-methoxycarbonylvinyl) benzylphosphonic acid dimethyl ester of the formula XIII is a known compound (cf. DE 3,519,280 and DE 3,545,318).

The novel compounds of formula 1c (B and Het are as defined above, A is an ethylene group) are obtained by selective reduction of the novel compounds of the formula Ia (R and Het are as defined above and A is an ethenylene group). The reduction is usually carried out catalytically with hydrogen (cf. Methoden der organischen Chemie, vol. 5 / 2b, p. 264, Thieroe, Stuttgart 1951). The procedure is illustrated by the following scheme:

(la) (Ib)

For the preparation of the novel compounds of formula (I) as defined above, five-membered heteroaromatic methyl halide derivatives of formula (X) and five-membered heteroaromatic aldehydes of formula (XII) in the form of starting materials are required. These compounds are known in the art or can be prepared according to known procedures. Appropriate manufacturing processes are described, for example, in: J, Chem. Soc. (C) 1970, 2563; Synth. Commun. 13 (1953) 741; J. Org. Chem. 50 (1985) 5272; Acta Chem. Scand. 24 (1970) 99; Acta Chem. Scand. 26 (1972) 1851; J. Chem. Soc. 1961, 2733; Liebigs Ann. Chem. 1985, 1377; J. Heterocyclic Chem. 23 (1986) 1535; Synthesis 1982, 318; Eur. J. Med. Chem. 19 (1984) 285; Chem. Pharm. Bull. 34 (1986) 2840; Liebigs Ann. Chem. 717 (1968) 148; Heterocycles 26 (1987) 947; Tetrahedron 43 (1987) 235; J. Chem. Soc., Perkin Trans. I, 1976, 570; Chem. Ber. 106 (1973) 3345; J. Org. Chem. 43 (1978) 3736; J. Org. Chem. 43 (1978) 3742; J. Indian Chem. Soc. 64 (1907) 314; Chem. Ber. 121 (1988) 723; LE 3,118,258; Chem. Ber. 101 (1968) 3872.

The novel compounds of formula (I) as defined above may exist in the form of E- and 2-isomers on the double hip (methyl ester group / 5-methoxyacrylic group and side chain when A is ethenylene). Stereoisomers can be separated, for example, by column chromatography or based on different solubilities, into pure forms. Isomerically pure compounds can be converted to the opposite isomers by known methods. The present invention includes both isomerically pure compounds and mixtures thereof. When using the novel compounds as fungicides and insecticides, both mixtures of diastereomers and uniform isomeric compounds are suitable. Mixtures formed during the synthesis are also suitable for this purpose.

The following examples illustrate the synthesis of new compounds.

Example Ί

<4-2- [2 '- (β-Cyclopropylisoxazol-5-yl) ethen-1-yl] phenyl-4-methoxyacrylic acid methyl ester

CS 274 476 B2 o

H-C-CH

α) To a solution of 36.5 g (0.28 mol) of 2-indanone and 32.4 g (0.30 mol) of trimethylchlorosilane in 300 ml of tetrahydrofuran is added 30.3 g (0.30 mol) at room temperature with stirring. triethylamine. The reaction mixture is stirred for a further 3 hours at room temperature (20 ° C), then the precipitate formed is filtered off with suction and the filtrate is concentrated. The residue was purified by distillation (53 ° C, 30 Pa). 40.6 g (2% of theory) of 2-trimethylsilyloxy-1H-indene are thus obtained in the form of a colorless liquid.

b) 40.0 g (0.20 mol) of 2-trimethyl-3-yloxy-1H-indene are dissolved in a mixture of 500 ml of methanol and 50 ml of methylene chloride and 14.0 g of the resulting solution are added at -70 DEG C. over 5 hours. (0.30 mol) of ozone. After removal of excess ozone by nitrogen, 150 mL (2.0 mol) of dimethylsulfide was added and the reaction mixture was stirred overnight at room temperature. The solution was then concentrated and the residue was taken up in sodium bicarbonate solution. The aqueous phase is washed with diethyl ether and pK adjusted to 2 by addition of dilute hydrochloric acid. Extraction is then carried out with diethyl ether, the combined organic phase is dried over magnesium sulphate and concentrated. 24.1 g (75% of theory) of 2-formylphenylacetic acid are obtained in the form of colorless crystals (m.p. 103-105 ° C).

c) 24.0 g (0.15 mol) of 2-formylphenylacetic acid and 0.1 g of p-toluenesulfonic acid are refluxed in 250 ml of methanol for 2 hours. The reaction solution is then concentrated, the concentrated residue is taken up in diethyl ether and the diethyl ether solution is washed with dilute hydrochloric acid. The organic phase is separated, dried over magnesium sulphate and concentrated. The residue was purified by distillation (50 ° C, 40 Pa). 19.3 g (74.5% of theory) of 2-formylphenylacetic acid methyl ester are obtained in the form of a colorless liquid.

d) To a solution of 15.6 g (0.06 mol) of 3-cyclopropylisoxazol-5-ylmethanfoaphthonic acid diethyl ester in 50 mL of tetrahydrofuran at room temperature (20 ° C) was added 43.3 mL of a 1.5 M solution of n-butyllithium in hexane dropwise. (0.065 mol). The reaction mixture was stirred for 20 minutes at 20 ° C and then a solution of 10.7 g (0.06 mol) of 2-formylphenylacetic acid methyl ester in tetrahydrofuran was added dropwise. The reaction mixture was stirred overnight, then poured into ice water and extracted with methyl tert. butyl ether. The organic phase is washed with water, dried over magnesium sulphate and concentrated. The residue was chromatographed on silica gel using cyclohexane / ethyl acetate 8: 2 as eluent. There were obtained 8.0 g (47% of theory) of methyl? - ^[2 - (3_cyklopropylisoxazol-5-yl) ethene-i-yl] phenylacetic acid as a colorless oil.

1 H-NMR (CDCl 3): 0.87 (m, 2H); 1.03 (m, 2H); 3.68 (s, 3H); 3.77 (s,

2H); 5.93 (s, 1H); 6.80 (d, IH); 7.25 - 7.62 (m, 4H); 7.52 (d, IH).

e) To a suspension consisting of 0.76 g (0.03 mol) of sodium hydride in 30 ml of dimethylethe.ru is added dropwise a mixture of 6.0 g (0.02 mol) of methyl 2- [2 ^of - (3- cyclopropylisoxazol-5-yl) ethhen-1'-yl] phenylacetic acid, 2.8 g (0.05 mol) of methyl formate and 50 ml of diethyl ether. The reaction mixture was stirred at room temperature for 12 hours and then hydrolyzed with ice water. The aqueous phase is adjusted to pH 4 by addition of dilute hydrochloric acid and then extracted with diethyl ether. The combined ether phase was dried over sodium sulfate

CS 274 476 B2 in the form of an early magnesium fever and thicken. 5.4 g (82% of theory) of <4-2- [2 ^z - (3-cyclopropylisoxazol-5-yl) ethen-1'-yl] phenyl-4-hydroxyacrylic acid methyl ester are obtained as a colorless oil.

f) 5.4 g (0.02 mol) of the acrylic acid methyl ester obtained according to e), 2.4 g (0.02 mol) of potassium carbonate and 2.2 g (0.02 mol) of dimethyl sulphate are stirred in 60 g. ml of acetone at room temperature for 12 hours. The precipitate is filtered off, the filtrate is concentrated and the residue is taken up in diethyl ether. The organic phase is washed with dilute ammonium hydroxide solution, dried over magnesium sulphate and concentrated. The residue was purified by chromatography on silica gel using cyclohexane / ethyl acetate 8: 2 as eluent. The oil obtained is overlaid with diisopropyl ether and crystallizes on trituration. It is obtained

4.5 g (80% of theory) of e-2- [2 ^of - (3-cyclopropylisoxazol-5-yl) ethen-1'-yl] phenyl-β-methoxyacrylic acid methyl ester as colorless crystals (m.p. 109-111) ° C, Compound No. 122).

Example 2

Methyl ster <£ -2- [2 ^/ - (Np-chlorfenylpyrrol-3-yl) ethene-1'-yl] -phenyl-0-methoxyacrylate

CH = CH

I p-ci-ci

C - OOCCH ₃ - 1

CH - OCH ₃

E. A suspension of 1.1 g (0.04 mol) sodium hydride in 50 ml of dimethylformamide is added dropwise at 0 ° C to a solution of 13.7 g (0.04 mol) of dimethyl smear (2-N-methoxy-t-methoxycarbonylvinyl) benzylphosphonic acid of acid and 9.0 β (0.04 mol) of N? -chlorophenylpyrrol-3-ylcarboxaldehyde in 100 ml of dimethylformamide with stirring. The reaction mixture was stirred at 0 ° C for 1 hour and then at room temperature for 12 hours. The mixture was then hydrolyzed with ice water and extracted with diethyl ether. The organic phase is dried over magnesium sulfate. Crystallization occurs when the ether phase is concentrated. 5.4 g (31% of theory) of the title compound are obtained in the form of colorless crystals (m.p. 146 DEG-147 DEG C., compound x and &gt;

C · O, «

Example 3

Methyl ester U-2 - \ _ ^of 2 - (Np-chlorfenylpyrrol-3-yl) eth-1-yl ^a] -phenyl- / J-methoxyacrylate

4.2 g (0.01 mol) of methyl 2-dz P ^z - (N-p-chlorophenyl-3-yl) ^{ethene-1-a-yl]} -phenyl - ^ - methoxyacrylate (cf. Example 2) are dissolved in 100 ml of tetrahydrofuran and the solution was hydrogenated in the presence of 1.0 g of palladium on carbon (10%) at a hydrogen pressure of 50 psi and at 0 ° C. After uptake of 220 ml of hydrogen, the mixture was filtered and the organic phase was concentrated. The residue is chromatographed on silica gel using toluene as the eluent. The oil thus obtained is coated with diisopropyl ether and triturated to crystallize. 1.9 g (45% of theory) of the title compound are obtained as colorless crystals (m.p. 115 DEG-116 DEG C., compound 14).

The following compounds can be prepared accordingly:

Table 1

CS 274 476 B2

_CH-OCH3

Compounds of formula I:

The first configuration refers to the methoxymethacrylic acid methyl ester residue, the second refers to the ethenylene group in the compounds of formula Ia (A - ethenylene residue).

compound R position R Het-A- melting point (° C)

No to Het (.isomer)

4-C1-C4L by 4

CH = CH 4 -NNO ₂ -C ₆ H ₄

i 42-143 (A, B)

I4 4-Cl-CgH ₄ 11i I6 (3)

CH = CH86 4-CH _{3 4} 1 -OgH

120-122 (3)

Q7 4_ci-C ₆ H ₄

141-143 (2)

121 (CH ₃ ) ₂ CH 3

90-91 (2)

CH = CH122 cyclo-C ₃ H ₅ 3 i 09-1Il (S, E)

CH = CHCS 274,476 B2

E position S to Het

4-Cl-C'Hi-och _3- c ₆ h ₄

4-CH ₃ -C ₆ H ₄

4-CN-C ₆ H ₄

2, ° —Eg — C ^ E ₃ 3 (ch ₃ ) ₂ ch

4-Cl-C ₆ H ₄

4-Cl-C ₆ H ₄

2-FC ₆ H ₄ 1

-fc ₆ h ₄

4-E-C, 11. o 4

Het -A-

CH = CHCH = CHH = CHJH = CH-

CH = CH melting point (° C (isower)

161-163 (E, E)

130-132 (E, E)

138-140 (E, S)

163-165 (E, E)

126-128 (E, E)

91-92

152-153 (E, E)

111-113 (E, E)

91-92

138-139 (E, E): h = ch138 (E, E)

CS 274 476 B2 compound

δ.

S position B Het-Ana Het melting point (° C) (isomer)

27 '

3-Cl-C ₆ H ₄

272

4-CH ₃ -C ₆ H ₄

273

4-C ₄ H ₉ -C ₆ H ₄

274

2,6-F ₂ -C H _{3 NO}

275

3,4-Cl ₂ -C ₆ H ₃ 1

276

4 ₇ FC _Ó H ₄

277

4- ^C 6 ^H 4

278

CH-,

279 ^C 6 ^U 5

280

2-Cl-6-FC ₆ H ₃ 3

281

CH ₃ 3

CH = CH141-142 (K, 2)

CH = CH-

124-125 (1, 2)

05 0505-106 (2, 21

CH = CH 116-117 (2, E)

147-149 (E)

I15-117 (2)

138-140 (Ε, 2) / - - n.

55-i Pi;

CH117-119 (2, E) oil (E, 2)

oil (El

1

CS 274 476 B2 Compound ΙΪ

C.

position R to Het

Het-Melting point (° C) (isomer)

282 4-GH ₃ -C ₆ H ₄ . 5

147 (E, E)

CH = CH283 C ₆ H ₅ 5

144 (E, E)

CH = CHTable 2

NaI spectrum data for selected compounds of Table 1.

The chemical shift (δ) is reported in ppm relative to tetramethylenesilane. As the solvent used in deuterochloroform (CDC1 _3).

Compound No. 8

3.70 (s, 3H), 3.80 (s, SU, 6.53 (d, 1H), 6.80 (d, 1H), 6.95 (d, 1H), 7.00 (d, 1H) 1H), 7.10 (s, 1H), 7.15-7.70 (m, SH), 7.63 (s, 1H).

Compound No. 14

2.76 (m, 4H), 3.73 (a, 3H), 3.86 (s, 3H), 6.21 (d, 1H), 6.82 (s, 1H), 6.98 (d 1 H, 7.11-7.42 (m, 8H), 7.63 (s, 1H).

Compound 2. 122

0.82 (m, 2H), 1.00 (m, 2H), 2.00 (m, 1H), 3.68 (s, 3H), 3.80 (s, 3H), 5.88 (s 1 H, 6.84 (d, 1H), 7.17-7.68 (m, 4H), 7.28 (d, 1H), 7.65 (s, 1H).

Compound No. 3.70 (s, 3H),

123

3.62 (s, 3H);

6.50 (s, 1H);

6.92 (d, 1H), 7.19-7.79 (m, SH), 7.63 (s

The novel compounds exhibit, in general, excellent activity against a wide range of phytopathogenic fungi, in particular from the class of Ascomycetes and Basidiomycetes. The compounds are systemically active in part and can be used as foliar and soil fungicides.

Of particular interest are the novel fungicidally active compounds for controlling a variety of fungi on various crop plants or their seeds, in particular wheat, rye, barley, oats, rice, corn, grasses, cotton, soy, coffee, sugarcane, fruit trees and ornamental plants. in horticulture, vineyards, as well as in vegetables - such as cucumbers, beans and pumpkin plants.

The novel compounds are particularly suitable for controlling the following plant diseases: powdery mildew (Erysiphe graminis) on cereals, powdery mildew (Erysiphe cichoracearum and Si> haeroteca fuliginea) on pumpkin plants, Podosphaera leucotricha on apple trees,

Uncinula necator on grapevine, Puccin.ia species on cereals, Rhizoctonia species on cotton and grasses, various types of Ustilago on cereals and sugar cane, scab of apple trees (Venturia inaequalis) on apple trees, various Helminthosporium on cereals,

Septoria nodorum on wheat, Gray mold (Botrytis cinerea) on strawberry and vine,

Oercor.pora arachidicola on peanuts,

Pseudocercosporella herpotrichoide3 on wheat and barley, en 274 476 B2

Pyricularia oryzae on rice, potato blight (Phytophthora infestans) on potatoes and tomatoes, various Fusarium and Verticillium species on different plants, vine peronospore (Plasmopara viticola), different Alternaria species on vegetables and fruits.

The active compounds according to the invention are applied by spraying or dusting the plants with the active compounds or by treating the seeds with the active compounds. The application is carried out before or after infection of the plants or seeds by the fungus.

The novel compounds can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use forms depend entirely on the intended use. These forms are intended in each case to ensure a fine and uniform distribution of the active ingredient. The compositions are prepared in a manner known per se, for example by mixing the active ingredient with solvents and / or carriers, optionally with emulsifiers and dispersants, where further organic solvents can also be used as co-solvents when water is used as a diluent. Basically, the following substances are suitable as auxiliaries: solvents such as aromatics (for example xylene), chlorinated aromatics (for example chlorobenzenes), paraffinic hydrocarbons (for example petroleum fractions, alcohols (for example methanol, butanol), ketones (for example cyclohexanone), amines (e.g., athanolamine, dimethylformamide) and water; carriers such as natural stone meal (e.g. kaolin, alumina, talc, chalk) and synthetic stone meal (e.g. vyaocedisperse silica, silicates); emulsifiers such as non-ionic and anionic emulsifiers (e.g. polyoxyethylene fatty esters) alcohols, alkylsulfonates and arylsulfonates) and dispersants such as colloquine, sulfite waste liquors and methylcellulose.

Fungicidal compositions generally contain between 0.1 and 95% by weight of active ingredient, preferably between 0.5 and 90% by weight of active ingredient.

Depending on the desired fungicidal effect, the application rate is between 0.02 and 3 kg of active substance or more per ha. The novel compounds can also be used in the protection of materials, for example against the fungus Paecilomyces variotii.

The compositions or preparations prepared therefrom for direct use, such as solutions, emulsions, suspensions, powders, dusts, pastes or granules, are applied in a known manner, for example by spraying, fogging, dusting, sprinkling, pickling or potting.

Examples of such means are:

Example I parts by weight of compound No. 8 are mixed with 10 parts by weight of N-methyl-6-pyrrolidone to give a solution which is suitable for application in the form of minimal drops.

Example II parts by weight of compound No. 14 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the addition product, 8 to 10 moles of ethylene oxide with 1 mol of N-monoethanolamide oleic acid, 5 parts by weight of calcium dodecylbenzenesulfonic acid and 5 parts. % by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. The solution is poured into water and finely divided to give an aqueous dispersion.

Example III parts of limestone compound No. 122 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutyl alcohol, 20 parts by weight of the addition product of 40 moles of ethylene oxide with 1 mole of castor oil. The solution is poured into water and finely divided to give an aqueous dispersion.

Example 274 parts by weight of Compound (8) is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction boiling at 210 to 280 ° C and 10 parts by mass of 40 mol ethylene oxide with 1 mol ricin oils. The solution is poured into water and finely divided to give an aqueous dispersion.

EXAMPLE In parts by weight of Compound No. 14, 3 parts by weight of diisobutylnaphthalene-.alpha.-sulfonic acid sodium salt, 10 parts by weight of ligninsulfonic acid sodium salt from sulphite waste liquors and 7 parts by weight of silica gel are mixed, and after good homogenization ground in a hammer mill. . By finely distributing the mixture in water, a spray suspension is obtained.

Example V1 parts by weight of Compound No. 122 are intimately mixed with 97 parts by weight of finely dispersed kaolin. In this way, a dust is obtained which contains 3% by weight of active ingredient.

Example VII parts by weight of Compound (8) is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. In this way, an effective formulation with good adhesion is obtained.

Example VIII parts by weight of Compound (14) are intimately mixed with 10 parts by weight of the sodium salt of the condensation product of phenolsulfonic acid, urea and formaldehyde, 2 parts by weight of silica gel and 48 parts by weight of water. A stable aqueous dispersion is obtained. Dilution with water gives an aqueous dispersion.

EXAMPLE IX parts by weight of Compound No. 122 are intimately mixed with 2 parts by weight of dodecylbenzenesulfonic acid calcium salt, 8 parts by weight of polyalcol ethers of fatty alcohols, 2 parts by weight of phenolsulfonic acid, urea and formaldehyde condensation sodium salt and 68 parts by weight of paraffinic mineral oil. A stable oil dispersion is obtained.

In these dosage forms, the active compounds according to the invention may also be present together with other active compounds, such as, for example, herbicides, insecticides, growth regulators and fungicides, or else together in a mixture with a fertilizer, whereby such mixtures are applied together. When mixed with fungicides, in many cases the spread of fungicidal effects is achieved.

The following list of fungicides with which the compounds of the invention may be combined is intended to illustrate, but not limit, such combinations.

Fungicides which may be combined with the compounds of the invention include, for example: sulfur, dithiocarbemates and derivatives thereof, such as ferric dimethyldithiocarbamate, zinc imethyldithiocarbamate, zinc ethylenebis-dithiocarbamate, manganese ethylene bis-dithiocarbamate, Manganese-zinc bis-dithiocarbamate, tetramethylthiuramdi sulfide,

CS 274 476 B2 zinc ammoniacal complex, zinc β-ethylene bis-dithiocarbarate, zinc ammoniacal complex N, N-propylene bis-dithiocarbamate,

Zinc,, Ν-propylene-β-dithiocarbaraate,

ΪΤ, β-β-propylene-bis- (thiocarbamoyl) di sulfide;

nitroderivatives such as d init po- (1-r-thylheptyl) phenyl crotonate,

2 sec. Butyl 4,6-dinitrophenyl 3,3-dimethylacrylate

2 sec. butyl 4,6-dinitrophenylisopropyl carbonate, 5-nitroisophthalic acid diisopropyl ester;

heterooyclic compounds such as

2-Heptadecyl-2-imidazoline acetate

2,4-dichloro-6- (o-chloroanilino) -s-triazine,

0,0-diethylphthalimido phosphonothioate,

5-amino-1- [bis- (dimethylamino) phosphinyl] -3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithioanthraquinone,

2-thio-1,3-dithio [4,5-b] quinoxaline, 1- (butylcarbamoyl) -2-benzimidazolecarbamic acid methyl ester,

2-methoxycarbonylaminobenzimidazole,

2- (2-furyl) benzimidazole

2- (thiazol-4-yl) benzimidazole

N- (1,1,2,2-tetrachloroethylthio) tetrahydrophthalimide,

N-Trichloromethylthiotetrahydrophthalimide

N-Trichloromethylthiophthalimide

Sulfuric acid N-dichlorofluoromethylthio-N, N-dimethyl-1 H -phenyldiamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-rhodanomethylthiobenzthiazole, 1,4-dichloro-2,5-dimethoxybenzene,

4- (2-chlorophenylhydroazano) -3-methyl-5-isoxazolone, pyridine-2-thio-1-oxide,

6-hydroxyquinoline or its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiine-4,4-dioxide,

2-methyl-5,6-dihydro-4H-pyrene-3-carboxanilide

2-methylfurene-3-carboxanilide,

2,5-dimethylfuran-3-carboxanilide

2,4.5-trimethyifuran-3-carboxanilide, 2,5-dimethylfuran-3-carboxylic acid cyclohexylamide,

H-cyclohexyl-H-methoxy-2,5-dimethylfuran-3-carboxamide

2-Methylbenzylide,

2-iodobenzanilide,

H-formyl-N-morpholine-2,2,2-trichlorethylacetal, piperazine-1,4-diyl-bis- (1- (2,2,2-trichloroethyl) formamide),

1- (3,4-dichloroanilino) -1-formylamino-2,2-trichloroethane,

2,6-dirnethyl-H-tridecylmorpholine or its 30 ΙΪ,

2,6-di-ethyl-N-cyclododecylmorpholine or its salts, [1- (p-tert-butylphenyl) -2-methylpropyl] -cis-2,6-dimethylmorpholine,

II- [3- (p-tert-butylphenyl) -2-methylpropyl] piperidine,

- [2- (2,4-dichlorophenyl) -4-ethyl-1,3-dioxolan-2-ylethyl] -1H-1,2,4-triazole,

1- [2- (2,4-dichlorophenyl) -4-n-propyl-1,3-dioxolan-2-ylethyl] -1- -1,2,4-triazole, N- (n-propyl) - N- (2,4,6-trichlorfenoxyethyl) -N ^/ -imidazolylmočovinu,

1- (4-chlorophenoxy) -3,3-dimethyl-1- (1H-1,2,4-triazol-1-yl) -2-butanone, 1- (4-chlorophenoxy) -3,3-dimethyl- 1- (1H-1,2,4-triazol-1-yl) -2-butanol, N- (2-chlorophenyl) - (E - (4-chlorophenyl) -5-pyrimidinemethanol, <5 EN 274 476 B2

5-Butyl-2-dimethyl-amino-4-hydroxy-6-methyl-pyrimidine, bis- (p-chlorophenyl) -3-pyridine-methanol; , 2-bis (3-ethoxycarbonyl-2-thioui'eido) benzene, 2-bis (3-'J ^'<: TBO: íykarbonyl-2-thioureido) _benzene), and various fungicides, such as dodeeylguanidinacetát,

3- (3- (3,5-dimethyl-2-oxycyclohexyl) -2-hydroxyethyl] glutarimide, hexachlorobenzene,

D, L-methyl-N- (2,6-dimethylphenyl) -N-fur-2-oylalaninet, D, L-N- (2,6-dimethylphenyl) -N- (2'-methoxyacetyl) alanine methyl ester,

N- (2,6-dimethylphenyl) -N-chloroethyl-D, L-2-aminobutyrolactone, methyl ster L, L-lT- (2,6-dimethylphenyl) -N- (phenylacetyl) alanine,

5-methyl-5-vinyl-3- (3,5-chlorophenyl) -2,4-dioxo-1,3-oxazolidine,

3- [3,5-dichlorophenyl- (5-methyl-5-methoxymethyl) -1,3-oxazolidine-2,4-dione,

3- (3,5-dichlorophenyl) -1-isopropylcarbamoylhydantoin,

N- (3,5-d-chlorophenyl) -1,2-diinethylcyclopropane-1,2-dicarboximide,

2-cyano- (1 H - ethylsminocarbonyl) -2-methoxyimino) acetamide,

- [2- (2,4-Dichlorophenyl) pentyl] -1- 1,2,4-triazole,

2,4-difluoro-cis- (1'-1,2,4-triazolyl-1-methyl) benzhydryl alcohol,

H- (3-chloro-2,6-dinitro-4-trifluoromethylphenyl) -5-trifluoromethyl-3-chloro-2-aminopyridine, 1- (bis- (4-fluorophenyl) methylsilyl) methyl-1H-1,2, 4-triazole.

Examples illustrating biological activity:

In the tests described below, et-2- (6-chloropyrazin-2-oxy) phenyl-3-methoxyacrylic acid methyl ester, referred to as compound G, known from EP 260 794, was used as reference active substance (standard).

Example B1

Activity against peronospora of grapevine (Plasmopara viticola)

The vine leaves of Mtíller Thurgau in pots are sprayed with an aqueous spray suspension which contains 80% active ingredient and 20% emulsifier in the dry matter. In order to assess the duration of action of the active substances, the plants are exposed to a greenhouse for 8 days after the spray coating has dried. Only then the vine leaves are infected with a suspension of grapevine peronospores (Plasmopara viticola). Then the vine plants are first placed in a chamber with a steam saturated atmosphere at 24 ° C for 48 hours and then in a greenhouse at a temperature between 20 and 30 ° C for 5 days. After this time, the plants are again placed in a chamber filled with water vapor atmosphere for 16 hours to accelerate the development of sporangia carriers. The degree of fungal infestation on the undersides of the leaves is then evaluated.

The result of the experiment demonstrates that the active substances No. 14, 86, 87, 122, 123, 124, 125, 126, 220, 270, 276, 277, 276, 279 and 280 have 0.0125% by weight (% by weight) when used. ) spray suspensions had a better fungicidal effect (95% effect) than the known comparative active substance C (effect 60%).

Example B2 '

Effectiveness against Septoria nodorum

Foliargold wheat plants are sprayed in a single leaf stage with an aqueous active ingredient containing 80% active ingredient and 20% emulsifier in the dry state until the droplets are dripped. 20 hours after the spray coating has dried, the plants are inoculated with an aqueous suspension of Septoria nodorum spores until droplets are formed and then placed in an air-conditioned room at temperatures between 17 and 19 ° C and a relative humidity of approximately 90 to 95% for 1 week. · The rate of disease symptoms is then determined.

The result of the experiment shows that active substances No. 8, 14, 66, 87, 121, 205, 246, 268, 269,

272, 276, 277, 280, 281 and 282, when applied in the form of 0.05% (w / w) spray

CS 274 476 B2 (Limonius californicus), Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hippocastani, Melolontha melolontha, Onlema oryzinka, Ortiorrhynchus sulcatus, , Phyllotreata chrysocephala, Phyllophaga spec., Phyllopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Shitona lineatus.

From the order of the diptera (Diptera), for example, species such as mosquito (Aedes aegypti), Aedes vexans, Anastrepha ludens, anofeles (Anopheles maculipennis), fruit propeller (Ceratifcis capitata), Chrysomya bezziana, Chrysomia homyaivorel Contaniria sorghicola), Cordylobia anthropophaga, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Sunflower (Fannia canicularis), Gasterophilus intesinalis, Glossina morsitans) ), Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia sereata, Lycoria pectoralia, May bitter beetle , house fly (Musea domestica), house fly (Muscina stabulans), sheep (Oestrus ovis), Oscinella frit, beetle (Pegomya hysocyami), Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, cherry propeller (Rhagoletis cerasi), propeller (Rhagoletis pomonella), Tabanus bovinus, Tipula olaracea, Tipula palulaosa.

Among the order of the Thysanoptera, there may be mentioned, for example, species such as thrips (Frankliniella fusea), thrips (Frankliniella occidentalis), thrips (Krankliniella tri tici), Scirtothrips citri, thrips (Thrips oryzae), thrips (Thrips) Thrips tabaci).

From the order of the Hymenoptera, for example, species such as the rapeseed (Athalia rosae), Atta cephalotes, Atta sexdens, Atta texana, plum (Hoplocampa minuta), apple moss (Hoplocampa testudinea), Monomorium pharaonis, ant (So lenopsis geminata), ant (Solenopsis invicta).

Among the order of the Heteroptera can be mentioned, for example, species such as Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Euchistus iapictiventris, Leptoglossus klusolaris pratensis), Nezara viridula, Píma quadrata, Solubea insularis, Thyanta perditor.

The nematode class includes, for example, root-forming nematodes such as Meloidogyne hapla, Meloidogyne ineognita, Meloidogyne javanica, and nematode-forming nematodes such as Globodera rostochiensis, Heterodera avenae, Hetrodera hina Heterodera triflolii, stem-forming nematodes, forming nodules on stems and leaves, such as Belonolaimus longicaudatus Ditylenchus destructor, Ditylenchus dipsaci, Heliocotylenchus multicinctus, Longidorus elengatus, Prophetususchuschus, Primus spp. Pratylenchus penetrans, Paratylenchus curvitatus, Partylenchu3 goodeyi.

When used to control pests, the concentrations of the active substances in the preparations to be applied may vary within wide limits.

These concentrations are generally between 0.0001 and 10%, preferably between 0.001 and 0.1%.

The active compounds can also be used with good success in the so-called ULV (Ultra-Low-Volume) procedure, whereby it is possible to apply preparations with a concentration of more than 95% by weight of the active compound or even the active compound alone without additives.

The application rate of the active compound for controlling pests is from 0.01 to 10, preferably 0.1 to 1.0 kg, of active compound per ha, depending on the conditions in the open soil.

CS 274 476 B2, 6 suspension very good fungicidal effect (95% effect).

Example B3

Activity against brown blotches of barley (Pyrenophora teres)

Igri barley plants are sprayed at the two-leaf stage with aqueous suspensions containing 80% active ingredient and 20% emulsifier in the dry state until the drops are dripped. After 24 hours, the plants were inoculated with a barley spotted fungus suspension (Pyrenophora teres) and placed in an air-conditioned room with high relative humidity at 18 ° C for 48 hours. The plants are then cultured in a greenhouse at 20-22 ° C and 70% relative humidity for an additional 5 days. The degree of attack is then determined.

The result of the experiment shows that active ingredients Nos. 86, 87, 125, 126, 246, 277, 278 and 280 when applied as a 0.0125% (by weight) spray suspension have a better fungicidal effect (95% effect) than the known active ingredients. substance C (effect 55%) ·

In addition, the novel compounds are suitable for controlling insect, spider mite and nematode pests. Furthermore, the compounds can be used in plant protection as well as in the field of hygiene, stock protection and in the veterinary sector as a pest control agent.

Harmful insects include the order of the butterflies (Lepidoptera) such as ypsilon (Agrotis ypsilon), field bug (Agrotis segetum), Alabama argillacea, Anticarsia gemmatalis, apple moth (Argyresthia conjugella), bark beetle (Autographa gamma) , Cacoecia murinana, Capun reticulana, Cheimatobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini) (Evetria bouliana), Eeltia subterranea, Galleria mellonella, Grapholita funebrana, Grapholita molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, Hellula undalis, Hibemia defoliaria, Hypanersia cunea, Hypusomeuta malia Laphygma exigua, Leucoptera coffeella, Le ucoptera scitella, Lifchocolletis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkra, (Mamestra brassicae), Orgyia pseudotsugata, Ostrinia nubilalis, Panoli flamea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala) scarbra, Plutellaxylostella, Pseudopulsia includens, Phyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerelella, Sparganothis pilleriana, Spodoptera littoralis, Spodoptera spp. ), Trichoplusia ni., Zeiraphera canadensis.

Among the order of the beetles (Coleoptera) we can name, for example, species such as the tree bark (Agrilus sinuatus), the black bark beetle (Agriotes lineatus), the black bark beetle (Agriotes obscurus), the summer fly (Amphimallus solstitialis), Anisandrue dispar, Apple Blossom (Anthonomus pomorum), Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bay Bean (Bruchus rufimanus), Peacock Frog (Bruchus pisorum), Water-lily (Bruchus lentis), Zosel Cassida nebulosa), Cerotoma trifurcata, Cryutrhynchus assimilis, Ceuthorrhynchus napi, Chaetochema tibialis, Conoderus vespertinus, Diaperotica, Diaperotisia, Criotisbis , Epithrix hirtipennis, Eutinobothrua brasiliensis, Hylo Pine bius abietig'i, Hypera brunneipennis, Mypera postica, Spruce Engraver (Ips typographus), cockerel (Leme bilineata ^- ', cockerel (Lema melanopus), Colorado potato beetle (Leptinotarsa decemlineata')

CS 274 476 B2

2- (R-methoxy-β-methoxy-6-methoxycarbonylvinyl) -4'-chloro-stilbene (Compound A) and methyl <? - ['2- (benzoxazol-2'-yloxy' · phenyl) methyl ester were used as reference active substances (standard). .alpha.-methoxyacrylic acid (compound B) known from EP 178 826 and EP 256 667. Example B4

Effectiveness against Prodenia litura

Test method: lending effect

Test performance:

The experiments were carried out in 250 ml plastic beakers. In this process, two caterpillars are used in each container and feeds are provided with pieces of maize plants which have been immersed in an aqueous active ingredient preparation for 5 seconds and which serve as food. The active substance content is given in ppm. After 24 hours, mortality was assessed and expressed as%.

The results are shown in the following table:

active substance no. ppm Prodenia litura mortality in% 8 40 100 ALIGN! 123 200 80 AND 1000 0 (B) 1000 80

Example B5

Activity against house fly (Musea domestica)

Test method: contact permanent effect

Test performance:

Both parts of a 10 cm glass dish are wetted with a total of 1 ml of acetonic drug solution. The active substance content of the solution is given in ppm. After evaporation of the solvent, 10 specimens of housefly are placed in the dishes, the dish is closed and after 4 hours the animals in the supine position are counted and the degree of mortality in% is determined.

The results are shown in the following table:

active substance No. Musea domestica ppm mortality in%

2 100

2 100

A 2 0

B 4 80

Example B6

Efficacy against Plutella maculipennis

Test method: contact effect

Test performance:

The young cabbage leaves are immersed for 3 seconds in the aqueous preparation of the test substance (active substance content is given in ppm) and placed on a 9 cm round filter paper moistened with 0.5 ml of water and placed in a 10 cm diameter glass dish. The leaf is then filled with 10 caterpillars, which are in the 4th larval stage, and the glass dish is closed. After 48 hours, the% mortality was assessed.

The results are shown in the following table:

i 9

CS 274 476 B2

active substance no. Plutella maculipennis ppm mortality in% 8 100 ALIGN! 100 ALIGN! 14 1000 100 ALIGN! 123 200 100 ALIGN! AND 1000 0 (B) 200 0 1000 80

Example B7

Effectiveness against Ornithodorus moubata

Test method: contact effect

Test performance:

Use young ticks drunk with blood (diameter 1.5 to 2 mm). These animals are collected by means of a suction tube, the active animals being expelled from the remnants of the skin by a strong light source. 5 ticks are immersed in an aqueous preparation of the active substance in the paper bag for 5 seconds (the active substance content is given in ppm). The bags are then freely suspended and after 48 hours the activity is determined. The bags are kept in the presence of a strong light source (60 W bulb); live animals attempt to escape and are easy to detect. The test temperature is about 25 ° C. Mortality is determined in%.

The test results are shown in the following table: Active ingredient No. Ornithodorus moubata

ppm mortality in% 8 400 80 14 1000 0 121 1000 80 125 1000 60 279 1000 60 AND 1000 0 (B) 1000 0

Example B8

Activity against spider mite (Tetranychus telarius)

Test method: contact effect

Test performance:

The potted bean plants grown in pots are sprayed at the stage of the second pair of leaves with an aqueous preparation of the active ingredient until the drops are dripped. The plants are sprayed on all sides with a total of 50 ml of spray suspension. Said plants are strongly attacked by spider mite and containing a large number of laid eggs.

The potency is determined after five days using a microscope. In doing so, care shall be taken that all developmental stages of the animals are equally represented. The plants are kept in a greenhouse under normal conditions for 5 days. The test results are shown in the following table:

active substance no. ppm mortality in% ---------------- ———————————————------------------- —---- 121 100 ALIGN! 100 ALIGN! 125 40 80 126 400 100 ALIGN!

CS 274 476-2

279

Β

100 ALIGN!

1000

00

Claims (2)

A fungicidal and insecticidal composition, characterized in that it contains at least one heterocyclically substituted arylacrylic acid methyl ester of the general formula I as an active ingredient. CH-OCH3 in which R is C 1 -C 4 alkyl, cyclopropyl or phenyl optionally substituted by halogen, C 1 -C 4 alkyl, cyano, methoxy or nitro; Her is the radical of pyrrole, pyrazole, isoxazole, oxadiazole or thiadiazole, and A is ethenylene, ethylene or methyleneoxy. A process for the preparation of heterocyclically substituted λ-arylacrylic acid methyl esters of general formula (Ia) in which A represents an ethenylene group -CH = CH- or compounds of the general formula (Ib) in which A represents a methyleneoxy group -CH 2 -O- (Ia). Ib), whereby R and Het have the meanings given in item 1 as in item 1, characterized in that a methyl ester of a heterocyclically substituted C 3 -aryl- / 3-hydroxyacrylic acid of the general formula V, which can be present in equilibrium with a formyl derivative of the general formula VI CS 274 476 B2 where R and Het have the meanings given in 1 a A is ethenylene or methyleneoxy, with an alkylating agent, for example dimethyl sulfate or methyl iodide, in the presence of a base and a diluent.