DD149453A5 - SCHAEDLINGSBEKAEMPFUNGSMITTEL - Google Patents

Abstract

The invention relates to pesticidal agents containing novel compounds of the formula I, wherein R & exp1! Halogen, phenyl, C & ind1-14! -Alkyl, C & ind 1-4 -alkoxy, C & ind 1-3 -haloalkoxy, C & ind 1-4 -alkylthio or the CF & ind3! Group; n is 0, 1, 2 or 3; R & exp2! a (formula) group in which X is oxygen or sulfur R & exp3! C & ind1-8! Alkyl which is optionally substituted, C & ind2-6! -Alkenyl, C & ind2-6! Alkynyl, C & ind3-8! -Cycloalkyl which is optionally substituted, phenyl which is optionally substituted, benzyl which is optionally substituted , or an epoxide-containing alkyl radical having up to 4 carbon atoms, or R & exp2! for -CN or a (formula) in which for R & exp4! Hydrogen or C & ind1-4! -Alkyl and for R & exp5! C & ind1-4! Alkyl or phenyl which is optionally substituted, or R & exp4! and R & exp5! optionally together with the amide N-atom form a heterocyclic ring, and azole (formula) or (formula) or imidazol-1-yl (formula) mean, the compounds of formula I also in the form of their salts with inorganic or organic acids or as metal complex compounds may be present as active ingredients.

Description

Berlin, August 29, 1980

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S chew agent Field of application of the invention

The invention relates to pesticides containing new azole-substituted atropic acid derivatives as active ingredients.

Characteristic of the known technical solutions

Benomyl (methyl-1-butylcarbamoyl-Z-benzimidazo-carbamate) is a known fungicide. Its action against various powdery mildews, however, is insufficient.

Z e of the invention

The compounds according to the invention show a surprisingly good action against mildew, in particular against those true mildew strains which are resistant to benzimidazole derivatives.

Explanation of the essence of the invention

The compounds used according to the invention have the general formula I.

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* " Mm ^mm

R is halogen, phenyl, C _1-1 -alkyl, C ₁ -alkoxy, C ₁ , -haloalkoxy, C ₁ -alkylthio or the CF ₁ - group,

η O, 1, 2 or 3,

3 '

R is an R X-C group in which

X oxygen or sulfur,

RC ₁ o-alkyl, which is optionally substituted by halogen, C ₁ , alkoxy or by alkoxycarbonyl having up to 5 carbon atoms or by dialkylamino having up to 8 carbon atoms, C ₀ , .- alkenyl, C _{0 A} - is substituted, group alkynyl, C, g-cycloalkyl, which is optionally substituted by C. _1-alkyl radicals, phenyl, optionally substituted by halogen atoms, C ₁ -alkyl, C ₁ -alkoxy or CF, benzyl, optionally substituted is substituted by halogen, or an epoxide-containing alkyl radical having up to 4 carbon atoms, or

R <^ O

^ ^Ss s. "4

R is -CN or a ^ N-C group in which R is

eerstoff or _C1.-alkyl and RC _1-.-alkyl or phenyl, which is optionally substituted by halogen atoms, CF, radicals, C _1-.-alkyl or C.-alkoxy radicals or by phenoxy or Halögenphenoxyrest, or R and R optionally together with the amide N atom form a heterocyclic ring is, and

Azole 1,2,4-triazol-1-yl-N-N or 1,2,4-triazol-4-yl-N-N

Yl N

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I or imidazol-1-yl

mean.

The compounds of the formula I can also be present in the form of their salts with inorganic or organic acids or as metal complex compounds, preferably copper or zinc complex compounds, the latter being prepared in a customary manner, e.g. B. from CuCl ₂ or ZnCl ₂ and compounds of formula I can be obtained.

1 Preferably in formula I R is halogen, in particular chlorine, η is O or 1, X is oxygen, and azole is the 1,2,4-triazol-yl radical.

The compounds of the formula I are generally obtained as E / Z isomer mixtures which can be separated into the individual isomers by known processes.

The compounds of the formula I can be prepared by reacting compounds of the general formula II

(II)

1 ?

in which R, R "and η have the meaning as in Formql I and Hal is halogen, preferably chlorine or bromine, in particular chlorine, at higher temperatures, preferably at 60

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to 120 ⁰ C in the presence of a hydrogen halide-binding agent, preferably at least a stoichiometric or excess amount of this agent, for example a basic compound such. As potassium carbonate, sodium carbonate, triethylamine or N, N-dimethylaniline, with at least one mole of 1,2,4-triazole or imidazole per mole of compound of formula II.

The reaction is advantageously carried out in inert organic solvents, such as. As acetone, acetonitrile, dimethylformamide or xylene by.

The partially new precursors of formula II can, for. B. according to reaction scheme 1 or, 2 are obtained in the following way:

Reaction Scheme 1

HCOOCH, CH ₀ -C-OCH, -) (OV-C-COOCH,

OH

This type of reaction is described in Liebigs Annalen der Chemie 413 (1917) p. 206.

According to Reaction Scheme 2, chlorinating the compounds of Formula III gives esters of Formula II a. The poorly performing chlorination with PCl ₅ is described for η a 0 in reports Chem. Ges. 51

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(1918) S, 1368. The chlorination with POCl in dimethylformamide (DMF), which proceeds with significantly better yields, is not yet described. Instead of POCl ₃ or PCl ₅ can be z. B. also use thionyl chloride, phosphorus trichloride or phosgene.

Reaction scheme 2

C-COOCH, POC1, / DMF

(III)

C-COOCH

(II a)

Higher esters can be prepared from the methyl esters of the formula IIa by known methods by transesterification.

Another synthetic route for higher esters (II b) or for amides (II c) is outlined in Scheme 3.

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Reaction scheme 3

C-C-Cl

+ HNR ⁴ R ⁵

(II b)

(II C)

The chlorination reaction III j> IV is described for η = O in Reports dtsch. Ehem. Ges. 51 (1918) p. 1368.

The compounds of the formula I according to the invention are distinguished by their excellent fungicidal activity. Already penetrated into the plant tissue fungal pathogens can successfully fight curative, This is particularly important and beneficial in such fungal diseases that can not be effectively combated after infection with the usual fungicides. The V spectrum of the claimed compounds

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fertilize detected ζ. B "oryzae next Pyricularia and various types of rust, especially powdery mildews in the fruit, vegetable, grain and ornamental plants · particular note is the excellent effect of the compounds against powdery mildew species nzimidazolderivate against B _e (z. B. Benomyl, carbendazim) is resistant are·

The compounds of formula I are also suitable for use in technical fields, for example in wood preservatives on the paints sector, as a preservative, z _# B, in cooling lubricants for metalworking.

For use in crop protection, the fungicidal compounds of the formula I can be formulated in a customary manner as dusts, wettable powders, mordants, dispersions, solutions or emulsion concentrates. The content of active compounds of the formula I is generally between 2 and 95 wt .-%, preferably 10 to 90 wt .-%. In addition, the active ingredient formulations mentioned optionally contain the customary adhesives, wetting agents, dispersants, emulsifiers, penetrants, solvents, fillers and carriers "Also mixtures or mixed formulations with other pesticidal active ingredients, such as. As insecticides, acaricides, herbicides or fungicides and fertilizers or growth regulators may be possible.

The invention is illustrated by the following examples:

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A) Precursors for the production examples

1. 2- (4-chlorophenyl) -3-chloroacrylic acid methyl ester

To a sodium suspension prepared from 65.5 g (2.85 g-atom) of sodium and 800 ml of absolute toluene is left a mixture of 504 g (2.73 mol) of p-Chlorphenylessigsäuremethylester, 164 g (2.73 mol) of formic acid methyl ester and Run 30 g of methanol so that the temperature does not rise above 40 C. After completion of the feed is stirred for 4 hours at 40 ⁰ C and 12 hours at room temperature. The precipitated sodium salt of 2- (4-chlorophenyl) -3-hydroxyacrylic acid methyl ester is filtered off with suction, vorvolvaschen with 200 ml of toluene, added to 3 1 of water and acidified with dilute sulfuric acid (pH 2). The 2- (4-chlorophenyl) -3-hydroxyacrylic acid methyl ester is extracted with methylene chloride, the extract is dried and concentrated. This gives 516 g of a semi-crystalline product, which is dissolved without further purification in 600 ml of absolute dimethylformamide. After dropwise addition of 430 g (2.8 mol) of phosphorus oxychloride at 25 ⁰ C is allowed to stir for 1 h and then heated for 1 hr. At 110 ⁰ C After cooling, poured into 4 1 of ice water, extracted with methylene chloride, the extract is dried , the solvent is removed and the residue is distilled off. 406 g (64.4 % of theory) of methyl 2- (4-chlorophenyl) -3-chloroacrylate are obtained,

^K P

l, 8 mbar

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2, 2- (4-chlorophenyl) -3-chloro-acrylic acid isopropyl ester

115 g (0.5 mol) of 2 ~ (4-chlorophenyl) -3-chloro-acrylic acid methyl ester are refluxed with 108 g of isopropanol and 5 g of zirconium (IV) acetylacetonate. "Within 8 hours, 300 ml of alcohol are distilled off and simultaneously replaced fresh isopropanol. Then the reaction mixture is concentrated in a rotary evaporator and the residue is distilled off.

This gives 78 g (60.2 % of theory) of 2- (4-chlorophenyl) -3-chloro-acrylic acid isopropyl ester,

^K P0, mbar ⁹² ° ^C »3 · _i 2- (4-chlorophenyl) -3-chloro-acrylic acid isobutyl ester Gr

115 g (0.5 mol) of 2- (4-chlorophenyl) -3-chloro-acrylic acid methyl ester are refluxed with 153 g of isobutanol and 4 g of p-toluene sulfonic acid for 14 hours. During this time, 5 times 100 ml of alcohol are distilled off and at the same time replaced by fresh. Thereafter, the reaction mixture is allowed to cool, the excess alcohol is taken off, the residue is taken up in methylene chloride, the solution is washed with water, dried, concentrated and distilled.

This gives 82 g (60 % of theory) of 2- (4-chlorophenyl) -3-chloro-acrylic acid, butyl ester

^K P0.3mbar ^{115 to} f 4. 2-phenyl-3-chloro- acyl rylsäu ethyl ester

With stirring at 40 to 45 ⁰ C to a mixture

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from 140.8 g (0.733 mol) of 3-hydroxy-2-phenyl-acrylic acid ethyl ester and 53.5 g (0.733 mol) of dimethylformamide added dropwise 112.3 g (0.733 mol) of phosphorus oxychloride. Thereafter, 90 minutes at 105 ⁰ C is stirred. After cooling, the mixture is stirred into ice-water and the separated oil taken up with methylene chloride. After the neutral washing of the methylene chloride solution, this is dried and distilled.

There are obtained 133.5 g of 2-phenyl-3-chloro-acrylic acid ethyl ester. Yield: 86 % d. Theory.

.3 to 0.4, »bar ^{76 to 78} ° ^C · 5 · _[ 3 ~ hydroxy-2-phenyl-acrylic acid ethyl ester

24 g of sodium (1.04 g-atom) are suspended in 500 ml of toluene in finely divided form. At 20 to 22 ⁰ C, a mixture of 164.1 g (1.0 mol) Phenylessigsäureethyl ester and 74.1 g (1.0 mol) of ethyl formate with stirring and ice water cooling within 1 hour added dropwise and the mixture stirred for 5 hours , After standing for 15 hours, the mixture is heated again to 45 ^° C. for 1 hour.

The reaction mixture is carefully mixed with 1 1 of ice water. After phase separation, the aqueous phase is worked up with acidification with acetic acid, shaking with methylene chloride, drying of the methylene chloride extract and distillation. There are obtained 140.8 g of 3-hydroxy-2-phenyl-acrylic acid ethyl ester.

, ^K P0.4 to 0.5 mbar ^{78 to 79} ° ^C; Yield 73.3 %

d. Th.

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B) Production examples

example 1

2- (4-chlorophenyl) -3- (1,2,4-triazol-l-yl) acrylic acid isobutyl ester

C-COOCH ₀ CH (CH,)

50 g (0.183 mol) of 2- (4-chlorophenyl) -3-chloro-acrylic acid isobutyl are dissolved in 20 ml of anhydrous dimethylformamide and at 25 ⁰ C to a suspension of 11.36 g (0.164 mol) of 1,2,4-triazole and dropwise added 27.6 g (0.2 mol) of potassium carbonate in 180 ml of dimethylformamide. The mixture is stirred for 3 hours at 80 ° C _# 1.26 g (0.018 mol) of 1,2,4-triazole and stirred for a further 2 hours at 80 ° C. After cooling, the mixture is filtered and the solvent removed under vacuum. There remain 59.7 g of a viscous oil, which was taken up in methylene chloride, extracted with water, dried, concentrated and digested with 60 ml of toluene / hexane = 1: 1. The precipitated 2- (4-chlorophenyl) -3,3-bis (l, 2,4-triazol-l-yl) -propionäureisobutylester is filtered off with suction (2.6 g) and the mother liquor freed from the solvent under vacuum. There remain 46.4 g of waxy 2- (4-chlorophenyl) -3- (1,2,4-trlazol-l-yl) isobutyl acrylate

Yield: 82.9 % of theory

Analysis:

^C 15 ^H 16 ^ClN 3 ° 2 ⁱ < ^{M = 305} ' ⁷ >

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Calc .: C 58.92% Get = .: C 58.4% H 5.24% H 5.2%

N 13.75 % N 13.4 %

Example 2

2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -acrylic acid isopropyl ester . ,

C-COOCH (CH,) H-C-N -

51 g (0.2 mol) of 2- (4-chlorophenyl) -3-chloracrylsäureisopropylester be in 30 ml of anhydrous dimethylformamide at 25 ⁰ C to a suspension of 12.42 g (0.18 mol) of 1,2,4-triazole and 28.9 g (0.21 mol) of potassium carbonate in 180 ml of DMF.

The mixture is stirred for 6 hours at 70 ⁰ C, 1.38 g (0.02 mol) of 1,2,4-triazole and stirred again for 2 hours at 70 ⁰ C After cooling, filtered and the solvent removed under vacuum. There remain 72 g of oily residue, which was taken up in methylene chloride, extracted with water, dried and freed from the solvent under vacuum.

The oily residue solidifies to form the semi-crystalline isomer mixture (44.4 g) of 2- (4-chlorophenyl) -3- (1,2,4-triazol-1-yl) -acrylic acid isopropyl ester. Yield: 76.1 % of theory

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R_ values: 0.53 and 0.42 for the cis / trans (about 1: 1) isomeric mixture (measured on ready-made silica gel 60 plates (Merck), eluent: ethyl acetate).

Analysis:

C ₁₄ H ₁₄ ClN ₃ O ₂ ; (M = 291.7)

Ber. C 57,64% Gef.:57%

H 4.84 % H 4.7%

N 14.41 % N 14.2 %

Example 3

2-phenyl-3- (1,2,4-triazol-l-yl) -acrylsäureethyloster

31 "6 g (0.15 mol) of 3-chloro-2-phenyl-acrylic acid ethyl ester, 10.35 g (0.15 mol) of 1,2,4-triazole and 27.6 g (0.20 mol) Potassium carbonate are stirred for 11 hours at 80 ^° C. in 100 ml of dimethylformamide. Then, the potassium salt is filtered off with suction and the dimethylformamide is largely removed from the filtrate by vacuum distillation. The residual oil is taken up in methylene chloride and washed with water. After drying the solution, the solvent is removed under vacuum.

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There are obtained 32.9 g of oily 2-phenyl-3- (1,2,4-triazol-1-yl) · acrylic acid ethyl ester, n ^ 1.5662 Yield: 90.1 % of theory

Analysis: 2 64 (M = : 243 , 3) Found .: C 63 , 9 ^C i3 ^H 13 ^N 3 ° 5 , 18 % H 5 , 5 Ber .: C 17 , 39 % N 16 .9 H 4 , 27 % N to 94 Examples

In an analogous manner as described in Example 1, Examples 4 to 94 are carried out. In Table 1, the 12th

Radicals R, R, A and η in the formula Ia of the compounds prepared according to Examples 4 to 94 from the corresponding compounds of the formula II and their melting points or the refractive index.

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Table 1

Formula I a;

Example no. R ¹ η A R ² Schmp. ⁰ C Refractive index η 4 4-Cl 1 -N = -C-OC ₂ H ₃ O syrup 3 4-Cl 1 -N = -C-OCH ₀ CH ₀ CH, ι έ. C. 0 semi-krist. 6 4-Cl 1 -N = -C-OCH, II O 0 93-105 7 4-Cl 1 -N = -CO (CH ₂ ) ₃ CH ₃ 57-68 0 8th 4-Cl 1 -N = -CO (Oy ₄ CH ₃ O syrup η ²² 1.5618 9 4-Cl 1 -N = -CO (CH ₀ J ₁ -CH, 0 syrup η ²² 1,5502 10 11 4-Cl 4-Cl 1 1 -N = -N = -CO (CH ₂ J ₂ CH (CH ₃ ) δ -CO-CH-CH ₀ CH (CH, ι · C ό 0 CH ₃ 2 syrups> 2 semi-krist. η ²³ 1.5608 12 4-Cl 1 -N = -C- _O -CH (CH _O ) _o CH, CH, semi-krist. 13 4-Cl 1 -N = -co- / TS \ H \ f 0 semi- <rist.

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Example no. R ¹ η A R ² . Schmp. ⁰ C Refractive index η 14 4-Cl 1 -N = -CO-CH ₂ -Zq) syrup ti ™ · \ ä 0 15 0 -N = -C-OCH ₃ syrup δ 16 0 -N / A -CO (CH ₂ ) ₂ CH ₃ syrup δ 17 0 -N = -C-OCH ₀ CH (CH,) _o 0 semi-krist. 18 0 -N = -C-OCH (CH ₃ ) ₂ oil ny * ° 1,5572 0 19 0 -N = -CO (CH ₃ ) ₃ CH ₃ δ oil np ° 1,5542 20 0 -N = -CO (CHg) ₄ CH ₃ oil np ° 1.5470 δ 21 0 -N = -CO (CH ₂ ) ₂ CH (CH ₃ δ 2 oil Πρ ° 1,5500 22 0 -N = -CO-CH ₀ CHCH ₀ CH, II C. ι έ. 4 »0 CH ₃ oil n ^ ° 1.5452 23 0 -N = -CO- (CHg) ₅ -CH ₃ oil η "* ⁰ 1.5402 0 24 0 -N = -s ^ocH 2 ^ 5) oil Πρ ° 1,5960 0 25 0 -N = -COCH ₀ CH = CH ₀ oil Πρ ° 1,5760 0

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Example no.

Mp.

Refractive index η

26

27 28

29

31

32

33

4-Cl

-N =

-N =

-N =

-N =

-COCH (CH _{0) O} CH, nt cc ο

0 CH ₃

-CN -CN

CH

-N =

-C-N

oil

148.5

172 173

syrup

^C 2 ^H 5

-N =

-C-N

• I I

oil

C ₂ H ₅

-C-N-

HI

104 108

-N =

-C-N ·

η (

-N =

0CH (CH ₃ ) ₂ x

-C-N-

0 CH (CH ₃ ) ₂

127 134

oil

1.5500

1.5739

1.5800

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At game no. R ¹ η A 34 0 -N = 35 0 -N = 36 0 -N = 37 0 -N = 38 0 -N = 39 4-Cl 1 -N = 40 4-Cl 1 -N =

Schmp. ⁰ C

Refractive index η

-C-N

η ι

-Cl

-C-N

Il ·

116 118

0 CH (CH ₃ ) ₂ OCH ₃

-C-N

Il

OCH.

0 CH (CH ₃ )

120 122

-C-N-

0 CH (CH ₃ ) ₂

110 113

CH.

-C-N-

Il

O CH (CH ₃ ) ₂

CH.

-C-N-

• I ·

0 CH (CH ₃ J ₂

semi-crystalline.

-C-N-

0 CH (CH ₃ ) ₂

CH.

1.5735

ny * ° 1.5691

ny * ° 1.5548

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At game No, R ¹ η A R ^{2 C} 2 ^H 5 ν Mp. ⁰ C Refractive index η 41 4-Cl 1 -C = f -C-O (CH ₂ ) ₅ CH ₃ δ CH (CH) _p I syrup H 0 CN 42 4-Cl 1 -C = -CO-CH ₂ -ZO) -C-OCH (CH 2), it is Od. 0 syrup $ H δ -C-CCH ₂ -CH = CH ₂ 43 4-Cl * 1 -C = H -COCH ₅ CH, II Cm O 0 δ 131.5 44 4-Cl 1 i H -COCH, ei * * 0 -CN (C ₂ H ₅ J ₂ 152 to 153 45 0 H -COCH, • 1 <- * 0 0 102 to 103 46 0 • H syrup 47 0 -C = I H 131 to 132 48 0 H 89 to 90 49 4-Cl 1 -N = syrup 50 4 "C1 1 -N = 113

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Example no.

R ¹ η A 4-Cl 1 -N = 4-Cl 1 -N = 4-Cl. 1 N * 4-Cl 1 -N = 4-Cl 1 -N = 4-Cl 1 -N = 4-Cl 1 -N = 4-Cl 1 -N = 4-Cl • 1 -N =

Mp.

Refractive index η

-CN (nC ₃ H ₇ ) ₂ 0

-C-f /

H ₃ C

0 CH.

-C-N-

Il ·

0 CH.

CH ₃ O

CH.

-C-N-

 I t

OC ₂ H ₅

H ₃ C

= -C-N-

CH ₃ -CH-C ₂ H ₅

136

196 to 198

91 to 92

135 to 137

vitreous

162

140 to 142

80 to 90

24

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At game no. R ¹ η 1 1 A CH ₃ O Schmp. ⁰ C 2 ' syrup ₂ syrup Refractive index η -C- M / ^ ~ S \ 3 60 4-Cl 1 0 -N = 0 CH H ₃ C ^/ C ₂ H ₅ 114 61 1 -N = -C-OCH, Il «^ 0 94 to 102 62 * ® 1 0 CH = -C-OCH, Il - '0 159-161 63 3-0CF ₂ CF ₂ H 1 -N = -C-OC ₀ H ₁ , 0 syrup 64 3-0CF ₂ CF ₂ H 1 CH = -C-OC ₂ H ₅ O semi-krist. 65 3-CF ₁ -N = -C -OCH, 0 61 to 65 66 3-CF -N = -C-OCH ₂ -CH ₂ -CH ₂ -CH. 0 -CH ₂ -CH. n °: 1.5089 67 -N = η ι fc b 0 CH ₃ 68 -N = -CO-CH-CH ₀ -CH (CH, Il t ^ W 0 CH ₃

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At game no. R ¹ η A R ² Schmp. ⁰ C Refractive index η 69 0 -N = -CN (C ₂ H ₅ J ₂ O. 100 to 101 70 71 0 0 -N = -N = -CN (CH ₂ C ₂ H ₅ J ₂ O 68 to. 72 106 to 110 72 0 CH = -C-NHC (CH,), H OO 0 80 to 84 73 2-Cl .1 -N = -C-OCH, t «-> syrup 0 74 2-Cl 1 -N = -C-OC ₅ H ₁ - syrup n ^ ° 1.5724 0 H ₃ C 75 2-Cl 1 -N = ~ ^C ~ ¹ ^ \ / syrup 0 HC (CH ₃ J ₂ 76 2-Cl 1 -N = -CN (CH ₂ C ₂ H ₅ J ₂ • ₁₀ syrup n ^ ⁰ 1.5493 77 2-Cl 1 -N = -CN (C ₂ H ₅ J ₂ δ syrup

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At game no. 3, R ¹ η A CN 5> 2 Schmp » ⁰ C Refractive index η 78 3, 2-Cl 1 CH = -C -OCH, 0 syrup 79 3, 2-Cl 1 CH = -C-OC ₀ H, - • I C Xi 0 5> 2 80 to 81 80 2-Cl 1 CH = -CN (C ₂ H ₅ ) ₂ 97 to 99 81 2, 2-Cl 1 CH = 0 syrup -CN (CH ₃ ) ₂ 6 82 2-Cl 1 CH = H c D 0 87 to 89 83 0 CH = -C - N) 0 42 to 47 84 0 CH = -CN (CH ₃ ) ₂ O 142 to 150 85 4-Cl ₂ 2 -N = -CN (C ₂ H) H COC 0 158 to 160 86 4-Cl ₂ 2 -N = -CN (CH ₂ C ₂ H 136 to 138 87 4-Cl ₂ 2 -N = 0 syrup -CN (CH ₀ C ₀ H 88 4-Cl ₂ 2 -N = 0 syrup

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At game no. R ¹ n A R ² Schmp, ⁰ C Refractive index η 89 2,4-Cl ₂ 2 -N =  so syrup 0 90 2,4-Cl ₂ 2 CH = -CN (C ₂ H ₅ J ₂ Syrup · 0 91 2,4-Cl ₂ 2 CH = 0 131 to 132 92 4-CH ₃ O- 1 -N = -C -OCH, 0 86 to 88 93 4-CH ₃ O- 1 CH = -C -OCH, 0 92 to 96 94 4-CH ₃ O- 1 CH = -C-OC ₂ H ₅ O 84 to 88

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Examples 95-105

The organic ligands of the complex compounds of the formula Ib of Examples 95 to 105 are first prepared analogously to Example 1 and then with the corresponding metal chlorides Met. Cl ₂ (ZnCl ₂ or CuCl ₂ ) in the usual way in the complex compounds of the formula Ib, as they shown in Table 2, transferred. In Table 2

1 2 are the radicals R, R, A ₁ η and the metal (Met) in the formula Ib of the metal complex compounds prepared according to Examples 95 to 105 and their melting points listed.

Table 2

Formula Ib:

C - R '

Met. Cl,

At game no. R ¹ η A R ² Met. Schmp. (Under decomposition) 95 O CH = rCN Cu 233 96 O CH = -C0C _o H _K ·· 2 5 O Cu 139 to 140 97 2-Cl 1 -N = -c-oc ^ v Zn 151 0

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At game no. R ¹ η A R ² Met. Schmp. (Under decomposition) 98 2-Cl 1 CH = CN Zn 200 to 201 99 0 -N = H έ- «5 c. 0 Cu 207 to 208 100 0 -N = -CN (CH ₂ C ₂ H ₅ J ₂ Cu 187 0 101 0 -N = -CN (C ₂ H ₅ J ₂ Zn 230 0 H ₃ C io2 2-Cl 1 -N = -C - NH (ζ)) Cu 195 0 HC (CH ₃ ) ₂ 103 0 -N = -C-NH-C (CH,), Cu 247 0 104 4-Cl 1 -N = -COOCH ₃ Cu 242 105 4-Cl 1 -N = -COOC ₀ H ₁ -d . t> Cu 187

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219324 _ ₂₇ _

C) Formulation Examples Example A

A dust is obtained by

10 parts by weight of active ingredient and 90 parts by weight of talc as inert substance

mixed and crushed in a hammer mill.

Example B

A readily dispersible in water, wettable powder is obtained by

25 parts by weight of active ingredient

64 parts by weight of kaolin-containing quartz as inert substance 10 parts by weight of potassium lignosulfonate and 1 part by weight of oleoylmethyltaurine sodium

as wetting and dispersing agent

mixed and ground in a pin mill.

Example C

A water-dispersible dispersion concentrate is obtained by reacting

20 parts by weight of active ingredient with 6 parts by weight of alkylphenol polyglycol ether

(Triton X 207) 3 parts by weight isotridecanol polyglycol ether (8 AeO) "

⁺ 'Number AeO = number of ethylene oxide units in the polyglycol ether molecule »

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2ff324

- 28 -

and 71 parts by weight of paraffinic mineral oil (boiling range

z. B. about 255 to about 377 ⁰ C)

mixed and ground in a ball mill to a fineness of less than 5 microns.

Example D

An emulsifiable concentrate is obtained

15 parts by weight of active ingredient

75 parts by weight of cyclohexanone as solvent and 10 parts by weight of ethoxylated nonylphenol (10 AeO) '

as emulsifier,

'Number AeO = number of ethylene oxide units in the nonylphenol polyglycol ether molecule.

D ) Biological examples

In the following examples, the letters A, B, C represent the commercial comparison means mentioned below:

A j methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate (benomyl)

B: N-tridecyl- ^ jG-dimethyl-morpholine (tridemorph) C j 2- (sec-butyl) -4,6-dinitrophenyl- (3-methyl-2-butenoate) (binapacryl)

219324

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Example I

Wheat plants are strongly inoculated in the 3-leaf stage with conidia of wheat powdery mildew (Erysiphe graminis) and placed in a Gevvächstaus at 20 ⁰ C and a relative humidity of 90 to 95 % , 3 days after inoculation, the plants with the compounds listed in Table I in The active ingredient concentrations of 500, 250, 125, 60, 30 and 15 mg / liter of spray sprayed dripping wet. As a comparison, the comparison agent B is used in an analogous manner. After an incubation period of 10 days, the plants are examined for infestation with wheat powdery mildew. The degree of infestation is expressed in % of infected leaf area, based on untreated, infected control plants (= * 100 % infestation). The result is summarized in Table I.

Table I

Connection according to example no. 500 with VVeize in % at 250 Mildew t mg IVirkstc 125 5 > failed> ff / liter 60 Leaves, sprayed 30 ache 15 3 15 O O 3 - 5-10 15 6 O O O 3 O O O - 17 O O O - 3 5 15 16 O O O - 5 15 3 29 O O O 5 15 3 9 "O O O O O O - 3 1 O O O O O O - 8th O O O 5 O O O - 19 O O 3 - 5 10 23 O O O O 0-3 5

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- 30 -

20 0 O 0 3-5 5 10 - 15 21 0 O 0 3-5 5 10 24 0 O 0 3 .5 - 10 15 comparison 3 5 10 15 25 medium B 'hyto- phyto- toxis toxis untreated , te infiz. 100 plants

Example II

Barley plants are in the 3-leaf stage with conidia of the

Barley powdery mildew (Erysipho graminis sp. Hordei) strongly inoculated and placed in a greenhouse at 20 C and a relative humidity of 90 to 95 % . 3 days after inoculation, the plants are sprayed to drip point with the compounds listed in Table II in the active compound concentrations of 500, 25O ₁ 125, 60, 30, 15 and 7.5 mg / liter of spray. As a comparison, the comparison agent B is used in an analogous manner. After an incubation period of 10 days, the plants are examined for infestation with barley powdery mildew. The degree of infestation is expressed in % of infected leaf area, relative to untreated, infected control plants (= 100 % infestation). The result is summarized in Table II.

2193 24

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- 31 -

Table II

Connection according to example no. 500 with Gers % at mg 250 thurs flour »125 dew infected leaf surface Dff / liter spray mixture 60 30 15 15 O before 7.5 15 O O 3-5 5 O 10 - 15 6 O O O O 5 15 0-3 17 O O O 3-5 10 16 O O O 5 15 5 30 O O 3 - 5 5 0-3 0-3 29 O O O O O 0-3 9 O O O O O 0-3 1 O O O O O 5 8th O O O O 3 3 19 O O O O 0-3 15 23 O O O O 5-10 15 20 O O O 3-5 5-10 3 21 O O O 3-5 0-3 25 24 O O O O 15 Vergloichs- medium B 3 3 - 5 5 5 -10 untreated infiz. plants 100

ß , Q , play I II

Cucumber plants (variety Delikateß) are strongly inoculated in the 2-leaf stage with a conidia suspension of cucumber powdery mildew (Erysiphe cochoracearum). After a drying time of the spore suspension of 30 minutes, v / ground the plants in a greenhouse at 22 ⁰ C and placed 90% relative humidity. 3 days after infection, the plants with the in

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Table III and drug concentrations sprayed dripping wet. As a comparison, the comparison agent A is used in an analogous manner. After 10 days, the rating is done. The level of infestation is expressed in % of infected leaf area, based on untreated, infected control plants (= 100 % infestation). The result is summarized in Table III:

Table III

Connection according to example no. with at 500 Cucumber mg 250 mg iltau fabric / Lit 125 5 ifallene E: he fuel; 60 3-lattice broth 30 hey in % 15 15 0 0 3 - 5 15 6 0 0 0 0 0 0 - 3 17 0 0 0 0 3 5 16 0 0 0 3 - 5 5 30 O 0-3 5 10 15 29 0 0 0 0 0 0 - 3 9 O 0 0 0 0 0 - 3 1 0 0 0 0 0 O - 3 8th O 0 0 0 0 0 - 3 19 0 0 0 3 0 0-3 3 23 0 0 0 - 5 5 10 15 21 0 0 3 - 10 15 24 0 0 5 5-10 10 - 15 Comparison means A 3 5 10 15 25 60

untreated infiz

 plants

100

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- 33 -.

Example IV

Cucumber plants (variety Delikateß) are strongly inoculated at the 2-leaf stage with a conidia suspension of a benomyl-resistant cucumber powdery strain (Erysiphe cochoracearum). After a drying time of the spore suspension of 30 minutes, the plants are placed in a greenhouse at 22 C and 90 % relative humidity. 3 days after infection, the plants are sprayed to drip point with the compounds listed in Table IV and drug concentrations. As a comparison, the comparison agent A is used in an analogous manner. After 10 days, the scoring is carried out, the level of infestation is expressed in % of infected leaf area, based on untreated, infected control plants (= 100 % infestation). The result is summarized in Table IV.

Table IV

Connection according to example no. with Gu infested liter 500 rkenmeh. a Bla Spritzb 250 Flat (floor area: rest 125 :> myl-resiste Ln % at mg 60 O parent strain) active ingredient / 30 15 O O 3-5 5-10 100 15 6 O O O O 0-3 17 O O O O 5 16 O O 3 5 10 30 O 3 5 10 15 29 O O O O Comparison means A 35 60 100 100

untreated, infiz. plants

100

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Example V

Apple rootstocks of the variety EM IX are strongly infected in the 4-leaf stage with a conidia suspension of apple powdery mildew (Podosphaera leucotricha). The plants then come for 16 hours in a climatic chamber with 20 ⁰ C and a relative humidity of about 100 %. Thereafter, the plants are placed in a greenhouse at 22 ⁰ C and a relative humidity of 85 % . 3 days after infection, the plants are sprayed to drip point with the compounds listed in Table V and drug concentrations. As a comparison, the comparison agent C is used in an analogous manner. After 2 to 3 weeks, the powdery mildew infestation is scored and the degree of infestation expressed in % of infected leaf area, based on untreated, infected control plants (= 100 % infestation). The result is summarized in Table V:

Table V

Connection according to example no. with at 500 Ap mg felmehlta Wirkstof 250 u infested f / liter S 125 Leaflet: broth 60 before in % 30 15 O 0-3 3-5 5 10 6 O O O 3 3 - 5 17 O O O 3 5 16 O 0-3 5 5-10 10 30 O 3 5 10 15 29 O O O 0-3 3 Comparison means C 3 5 10 10 - 15 25 untreated infection. Plants 100

Claims (3)

29 · 8, 80 AP C 07 D / 219 324 GZ 56 972 11 219324. - 35 - He fin η μsa η epruc h 1 «pesticides, characterized by a content of 2 to 95 wt .-% of a compound of general formula I. CR ² (I), H ^X azole wherein R is halogen, phenyl, C ^ ₄ alkyl, C _1-4 -alkoxy, C _1-3 genalkoxy, C _1, alkylthio or CF, group, η Ο, 1, 2 or 3,
O 3 ' R is an R XC group in which X is oxygen or sulfur, R is Cg-alkyl which is optionally substituted by halogen, C _1-3 -alkoxy radicals or by alkoxycarbonyl radicals having up to 5 C atoms, or by dialkylamino radicals having up to 8 C- Is substituted atoms, C ^ -Alkenyl, C ^ g-alkynyl, C ^ g-cycloalkyl, which is optionally substituted by C _1. -Alkyl radicals. Phenyl which is optionally substituted by halogen atoms, C _1, alkyl, ^ l-3 ~ ^A '""'^<0X y ^{reste oc} * ^er ^ ^ie CF ₃ group, benzyl which is optionally substituted by halogen, or the epoxide-containing alkyl radical having up to 4 carbon atoms, or 4 ° R ^{2 is} -CN or a ¹ V NC group in which R ⁴ Is hydrogen or C _1-4 -alkyl and for R ^{5 is} C "-alkyl or phenyl which is optionally substituted by halogen atoms, CF ₃ radicals _f 219324 C 1-4 alkyl or C 1-4 alkoxy radicals or substituted by the phenoxy or halophenoxy radical, or R and R optionally together with the amide N atom form a heterocyclic ring, and
Azole 1,2,4-triazol-1-yl -NN or l, 2,4-triazol-4-yl N-N or - imidazole, 1-yl mean. The compounds of the formula I can also be present in the form of their salts with inorganic or organic acids or as metal complex compounds, as active ingredient in addition to customary formulation auxiliaries. 2. Use of compounds of the formula I, characterized in that they are used for pest control in crop protection. Method for controlling harmful fungi, characterized in that the surfaces and / or plants and / or substrates affected by them are brought into contact with a fungicidally effective amount of active compounds of the formula I.