DE3046329A1 - Phosphoric acid derivs. of 1,2,4-triazole and imidazole - fungicides for protecting plants, esp. effective against mildew - Google Patents

Abstract

and imidazole derivs. of formula (I) and their salts with (in)organic acids and their metal complex cpds., pref. with Cu or Zn are new. (R is halogen, pref. Cl, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio, halo(1-4C) alkyl, NO2, CN or Ph opt. substd. by any of the previous gps., R1 and R2 are each 1-8C alkyl, halo(1-4C) alkyl, or halo(1-4C) alkenyl, or R1 and R2 together form -CH2CH=CHCH2- or -CH=CH-CH2CH2-; X is CH or N; Y and Z are each O or S; n is an integer 0-5 (pref. 0,1 or 2). (I) are pesticides for use in plant protection. (I) are esp. effective against fungi e.g. Piricularia oryzae, Phytophthora infestans, Plasmopara viticola but esp. against mildew. (I) are highly effective against mildews which are resistant to benzimidazol derivs.

Description

Derivatives of 1,2,4-triazole and imidazole, method too

their manufacture and their use as pesticides The present invention relates to new 1,2,4-triazole and imidazole derivatives, Process for their manufacture and their use as pesticides in crop protection.

The compounds according to the invention have the general formula I, wherein R is halogen, preferably chlorine, C1 4 -alkyl, C1 4-alkoxy, C1-4-alkylthio, halogen (C1-4) -alkyl, nitro, cyano or phenyl optionally substituted by the aforementioned groups, R1 and R2, independently of one another , C1-8-alkyl, halo- (C1-4) 2-alkyl or - (C1-4) -alkenyl, where R¹, R2 and R together also represent the group -CH2-CH = CH-CH2- or the group -CH = CH-CH2-CH2-, X is a methine group or a nitrogen atom, Y and Z, independently of one another, are an oxygen or sulfur atom and n is an integer from 0 to 5, preferably 0, 1 or 2.

The compounds of formula I can also be in the form of their salts with organic or inorganic acids, especially in the form of their physiological compatible salts.

The azole derivatives of the formula I are obtained by either a) alcohols of the general formula II, in which R, X and n have the same meanings as in formula I, with acid chlorides of the formula III, in which R1, R2 and Z have the same meanings as in formula I and Hal is halogen, preferably chlorine, is reacted in a solvent and in the presence of a hydrogen halide binding agent, or b) compounds of the general formula IV, in which R, X and n have the same meanings as in formula I and Hal is halogen, preferably chlorine, in a solvent with compounds of formula V, in which R¹, R², Y and z have the same meanings as in formula I and M represents an alkali metal, preferably sodium, or the ammonium group.

Aprotic solvents are preferably suitable as solvents for both processes organic solvents, e.g.

Dioxane, tetrahydrofuran, dimethoxyethane, acetonitrile or acetone, DMF, N-methylpyrrolidone, dimethyl sulfoxide etc.

The hydrogen halide binding agents used are e.g.

according to method a) preferably tertiary organic bases, e.g. Triethylamine, pyridine or N, N-dimethylaniline.

But you can also use inorganic bases such as sodium hydride, K2CO3 or use Na2CO3.

The reactions are preferably carried out at temperatures between 20 ° C and 1200C, especially between 400C and 900C.

The alcohols of the formula II required as starting compounds are known (see. DE-OS 24 31 407, 26 28 420 and 29 17 244), as well as the connections of the formula IV (cf. DE-OS 25 47 954).

The compounds of the formulas III and V are also known (cf. i.a. Houben-Weyl, Methods of Organic Chemistry Vol. 12/1 (1963) pp. 241-247).

If appropriate, an organic can be added to the compounds of the formula I or inorganic acid or a complex-forming metal salt, such as CuCl2 or ZnCl2, add.

The compounds of the formula I according to the invention and also their salts and metal complex compounds, preferably copper or zinc complex compounds, are characterized by an excellent fungicidal effect, in particular e.g. when used in crop protection.

In doing so, they can already be incorporated into the plant tissue. compact successfully combating fungal pathogens with curative methods.

This is particularly important and beneficial in the case of fungal diseases such as which are no longer effective after infection with the usual fungicides can be combated. The spectrum of activity of the claimed compounds is recorded e.g. in addition to Piricularia oryzae various types of rust, Phytophthora infestans, Plasmopara viticola, but above all powdery mildew fungi in fruit, vegetable, cereal and ornamental plant cultivation.

Particularly noteworthy is the excellent effect of the compounds against powdery mildews that are resistant to benzimidazole derivatives (e.g. benomyl, carbendazim) are.

The compounds of the formula I are also suitable for use in technical area, for example in wood preservatives, in the paint sector and as a preservative.

Preferred compounds of the formula I are the 1,2,4-triazolyl derivatives.

The fungicidal compounds can be used in crop protection of the formula I in the usual way as dusts, wettable powders, dressings, dispersions, Solutions or emulsion concentrates can be formulated. The content of active ingredients of formula I is generally between 2 and 95% by weight, preferably 10 - 90% by weight. In addition, the active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetration, solvent, Fillers and carriers. Mixtures or mixed formulations with other active ingredients, such as insecticides, acaricides, herbicides or fungicides as well as fertilizers or growth regulators are optionally possible.

The invention is illustrated by the following examples.

A. Preparation Examples Example 1 1-71- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) -ethoxy7-2,5-dihydro- (1 H) -phosphol-1- oxide 19.4 g (0.075 M) 1-hydroxy-1- (2,4-dichlorophenyl) -2- (1,2,4-triazol-1-yl) ethane are dissolved in 100 ml of dioxane and mixed with 10.1 g (0.1 M) triethylamine are added. 13.7 g (0.1 M) of 1-chloro-1-oxo- # ³-phospholen in 30 ml of dioxane are added dropwise to this mixture. The temperature rises to 480C. When the exothermicity has ended, the mixture is stirred for 10 hours at 850 ° C., concentrated in vacuo and the residue is taken up in dichloromethane. It is carefully washed with water, dried and the residue from evaporation is recrystallized from gasoline. 20.1 g (78.4% of theory) of the desired product with a melting point of 113 ° -1140 ° C. are obtained.

Analysis: C14H14Cl2N3O2P; MW 358 calculated: C 46.93%; H 3.91%; N 11.73% Found: C 46.6%; H 4.0%; N. 11.9% Example 2 1-O- [1- (4-Chlorophenyl) -2- (imidazol-1-yl) -ethyl] -dimethylthiophosphinate-naphthalene-1,5-disulfonate 16.7 g (0.075 M) 1-hydroxy-1- (4-chlorophenyl) -2- (imidazol-1-yl) ethane are dissolved in 100 ml of dioxane and mixed with 7.9 g (0.1 M) of pyridine offset. 18.9 g (0.1 M) of dimethylthiophosphinic acid chloride in 20 ml of dioxane are added dropwise to this mixture, the mixture is stirred for 8 hours at 60 ° C. and the solvent is then removed under reduced pressure. The residue is taken up in dichloromethane, carefully washed with water and dried, and the solvent is removed by distillation. 14.2 g of a crude oil are obtained, which is dissolved in 50 ml of acetone and mixed with a solution of 7.2 g (0.025 M) of naphthalene-1,5-disulfonic acid in 50 ml of acetone. The precipitated salt is filtered off with suction, washed with a little acetone and dried. 9.5 g (27.6% of theory) of the desired product are obtained as a colorless solid with a melting point of> 2500 ° C.

Analysis: C18H20ClN204PS; MW 458.5 calc .: C 47.11%; H 4.36%; N 6.11% found: C 46.8%; H 4.4%; N 5.9% Example 3 1- [1- (4-Chlorophenyl) -2- (1,2,4-triazol-1-yl) -ethoxy] -2,5-dihydro- (1H) -phosphol-1 -oxide 16.7 g (0.075 M) of 1-hydroxy-1- (4-chlorophenyl) -2- (1 , 2,4-triazol-1-yl) ethane, heated to reflux for a further hour and then 10.3 g (0.075 M) of 1-chloro-1-oxo-! -phospholen in 20 ml of dioxane so that the temperature does not rise above 200C. After 48 hours at room temperature, the mixture is concentrated in vacuo, the residue is taken up in dichloromethane, washed with water, dried and a syrup is obtained as the evaporation residue, which crystallizes after trituration with ethyl acetate / gasoline. It is filtered off with suction and 18.0 g (74.2% of theory) of the desired product with a melting point of 134-135 ° C. are obtained.

Analysis: C11H15ClN3O2P; MW 323.5 calc .: C 51.93%; H 4.64%; N 12.98% found: C 51.9%; H 4.70%; N 12.9% Example 4 i 11 (2,8-dichlorophenyl) -2- (1,2,4-triazol-1 -yl) -ethyl / -dimethyldithiophosphinate-naphthalene-1,5-disulfonate It is allowed to add 20.8 g (0.075 M) of 1-chloro-1- (2,4-dichlorophenyl) -2- (1, Drop 2,4-triazol-1-yl) ethane in 30 ml of dimethoxyethane. The mixture is then stirred for 8 hours at 60 ° C. and 6 hours under reflux, concentrated in vacuo, the residue is taken up in dichloromethane, washed with water, dried and, after the solvent has been distilled off, 25 g of a syrup are obtained. This is dissolved in 30 ml of acetone and a solution of 10.4 g (0.036 M) naphthalene-1,5-disulfonic acid in 50 ml of acetone is added. The precipitated salt is filtered off with suction, washed with a little acetone and dried. 25.5 g (66.7% of theory) are obtained.

Theory) of the desired product, which decomposes at 2200C.

Examples 5-24 Examples 5-13 and Example 16 are used carried out as described in Example 1, but with pyridine instead of triethylamine as a base that binds hydrogen chloride.

Examples 14, 15 and 17 are carried out analogously to Example 3, the Examples 18 to 23 analogous to Example 1 and Example 24 analogous to Example 4.

In Table 1, the radicals Rn, R1, R2 are X, Y and Z in the formula I according to Examples 5-24 from the corresponding starting compounds of Formula II (Examples 5-23) or the formula IV (Example 24) compounds prepared of formula I and their melting points (mp. ° C) or refractive indices (nDC) combined reproduced.

Table 1 Formula I: At- R R1 R2 xyz play- n Fp C No. 0 nD 5 - n -CH3 NOS 108 ai 3 N 05 108 0C 6 ~ -CH2-CH = CH-CH2- NO 0 139 ° C 7 - CH2CH2C -CH3 NOS 4 = 1.5691 8 ~ CH2Cl CE3 NOO syrup 9 - -C2H5 - {2I3 NOO syrup 10 4-C1 -CZ13 to I3 NOS 94-95 "C 11 4-C1 -CH3 -CH3 NO 0 107-1090C 12 4-C1-CH2-CH = CH-CH2- NO 0) 2500C 13 401 0H17 -CH3 NOO 23 = 1.5193 14 4 t -CH2-CH = CH-CH2- NO 0 137-13900 15 2,4-C12-CH3 -CH3 NOS 103-1040C 16 2,4-C12 2 -CH3 NOO syrup 17 2,4-C12 -C8H17 -CH3 NO 0 18 2,4-C12 -C2H5 -CH3 NO 0940C 19 24012 -CH3 -CH3 CH O 0 20 2,4-C12 -C2I15 -CTI3 CH O 0 syrup 21 2,4-C12 -Cz12CH = CTIs I2 CH O 0970C 22 240l2 -C8H17 -CH3 CH o 0 i6 = 1.5325 23 2,4-C12 -CH2Cl -OH3 CH O 0 syrup 24 2,4-C12-CH3 CH SS * isolated as naphthalene-1,5-disulfonic acid salt B. Formulation examples Example A: A dusting agent is obtained by mixing 10 parts by weight of active ingredient of the formula I and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.

Example B: An easily dispersible, wettable powder cr is obtained by adding 25 parts by weight of active ingredient of the formula I 65 parts by weight kaolin-containing quartz as an inert substance 10 parts by weight of lignosulfonic acid calcium and 1 part by weight of sodium oleoylmethyltaurate as a wetting and dispersing agent mixes and grinds in a pin mill.

Example C: A dispersion concentrate that is easily dispersible in water is obtained by adding 20 parts by weight of active ingredient of the formula I to 6 parts by weight Alkylphenol polyglycol ether (Triton X 207) 3 parts by weight of isotridecanol polyglycol ether (8 AeO) +) and 71 parts by weight of paraffinic mineral oil (boiling range e.g. approx. 255 to over 3770C) and mixes in a friction ball mill to a fineness of below Ground 5 microns.

+) Number of AeO = number of ethylene oxide units in the polyglycol ether molecule.

Example D: An emulsifiable concentrate is obtained from 15th Parts by weight of active ingredient of the formula I 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxethylated nonylphenol (10 AeO)) as an emulsifier.

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

C. Biological Examples In the following examples the letters appear A and B for the commercially available comparison agents listed below with known ones fungicidal active ingredients: A: methyl 1- (butylcarbamoyl-2-benzimidazole carbamate (benomyl) B: N-tridecyl-2,6-dimethyl-morpholine (Tridemorph) Example I wheat plants in the 3-leaf stage heavily inoculated with conidia of wheat powdery mildew (Erysiphe graminis) and in a greenhouse at 200C and a relative humidity of 90 - 95% set up. 3 days after inoculation, the plants are treated with those listed in Table 1 Compounds in active ingredient concentrations of 500, 250, 125, 60 and 30 mg / liter Spray liquid sprayed dripping wet. As a comparison, the comparison means B is similar Wise used. After an incubation period of 10 days, the plants are up Wheat powdery mildew infestation examined. The degree of infection is expressed in% more infected Leaf area, based on untreated, infected control plants (= 100% infestation). The result is summarized in Table I.

Table I. Compound Leaf area infested with wheat powdery mildew according to by- in% with mg active ingredient / l spray liquid game no.500 250 125 60 30 10 0 0 0 0 - 3 3 - 5 15 0 0 0 0 - 3 3 2 0 0 - 3 3 3 - 5 5 - 10 12 0 0 0 - 3 3 - 5 5 - 10 1 0 0 0 0 0 16 0 0 0 0 0 4 0 0 0 0 0 Comparative 3 5 10 15 25 medium B Phyto- Phyto- toxis toxis Untreated, infiz. 100 plants EXAMPLE II Barley plants in the 3-leaf stage are heavily inoculated with conidium of barley powdery mildew (Erysiphe graminis sp. Hordei) and placed in a greenhouse at 2000 ° C. and a relative humidity of 90-95%.

3 days after inoculation, the plants are treated with those listed in Table II Compounds in active ingredient concentrations of 500, 250, 125, 60 and 30 mg / l spray mixture sprayed dripping wet. As a comparison, the comparison means B is used in an analogous manner used.

After an incubation period of 10 days, the plants are checked for infestation examined with barley powdery mildew. The degree of infection is expressed in% more infected Leaf area, based on untreated, infected control plants (= 100% infestation). The result is summarized in Table II.

Table II Compound leafy mildew infested with barley according to area in% at mg active ingredient / l spray game no broth 500 250 125 60 30 10 0 0 0 - 3 3 - 5 5 15 0 0 0 0 0 - 3rd 11 0 0 3 5 5 - 10 12 0 0 0 - 3 5 5 - 10 1 0 0 0 0 0 14 0 0 0 - 3 5 10 7 0 0 0 0 -3 5 - 10 13 0 0 0 0 - 3 3 - 5 16 0 0 0 0 0 4 0 0 0 0 0 Comparative 3 3 - 5 5 5 - 10 15 medium B Untreated, 100 infiz. plants Example III Cucumber plants (variety Delikateß) are heavily inoculated in the 2-leaf stage with a conidia suspension of cucumber powdery mildew (Erysiphe cichoracearum). After the spore suspension has dried on for 30 minutes, the plants are placed in a greenhouse at 220C and 90% rel. Humidity set up. 3 days after infection, the plants are sprayed to runoff with the compounds and active ingredient concentrations mentioned in Table III. As a comparison, the comparison agent A is used in an analogous manner. The assessment takes place after 10 days. The degree of infestation is expressed in% of infested leaf area, based on untreated, infected control plants (= 100% infestation). The result is summarized in Table III.

Table III Compound leafy mildew infested with cucumber according to area in% at mg active ingredient / l game no. spray mixture 500 250 125 60 30 5 0 0 0 - 5 10 25 10 0 0 0 0 - 3 3 15 0 0 - 3 3 - 5 5 10 2 0 0 0 0 0 11 0 0 0 3 - 5 5 12 0 0 0 3 - 5 5 1 0 0 0 0 0 Table III (continued) Compound leafy mildew infested with cucumber according to area in% at mg active ingredient / l game no. spray mixture 500 250 125 60 30 7 0 0 0 0 0 8 0 0 - 3 3 - 5 5 5 - 10 16 0 0 0 0 0 4 0 0 0 0 0 0 Comparative 3 5 10 15 25 medium A Untreated, 100 infiz. plants

Claims (6)

Claims: 1. Compounds of the general formula I, wherein R is halogen, preferably chlorine, C1-4 -alkyl, C1-4-alkoxy, C1-4-alkylthio, halogen (C1-4) -alkyl, nitro, cyano or phenyl optionally substituted by the aforementioned groups, R1 and R2, independently of one another, C1-8-alkyl, halo- (C1-4) -alkyl or- (C1-4) -alkenyl, where R¹ and R² together also represent the group -CH2-CH = CH-CH2- or the group -CH = CH-CH2-CH2-, X is a methine group or a nitrogen atom, Y and Z, independently of one another, an oxygen or sulfur atom and n is an integer from 0 to 5, preferably 0, 1 or 2, where 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. 2. Process for the preparation of compounds of the formula I according to claim 1, characterized in that a) alcohols of the general formula II, in which R, X and n have the same meanings as in formula I, with acid chlorides of the formula III, in which R1, R2 and Z have the same meanings as in formula I and Hal is halogen, preferably chlorine, is reacted in a solvent and in the presence of a hydrogen halide binding agent, or b) compounds of the general formula IV, in which R, X and n have the same meanings as in formula I and Hal is halogen, preferably chlorine, in a solvent with compounds of formula V, in which R1, R2, Y and Z have the meanings as in formula I and M represents an alkali metal, preferably sodium, or the ammonium group, and optionally converts the compounds of formula I with inorganic or organic acids into the salt or with metal salts in metal complex compounds. 3. Pesticides, characterized by a content on a compound of the formula I according to claim 1 as an active ingredient. 4. Pesticides, characterized by a content from 2 to 95% by weight of a compound of the formula I according to Claim 1 as active ingredient as well as usual formulation auxiliaries. 5. Use of compounds of the formula I according to Claims 1, 3 and 5 for pest control in crop protection. 6. A method of combating harmful fungi, characterized in that that one infested by them areas or plants or substrates with a fungicidally effective amount of active ingredients of the formula I according to claims 1, 3 and 4 treated.