DE2908377A1 - Fungicidal alpha-triazolyl-benzylidene-malonic acid ester(s) - prepd. by reacting a di:alkyl alpha-halo-benzylidene-malonate with 1,2,4-triazole - Google Patents

Abstract

New 1,2,4-triazole derivs. are of formula (I): (where R' is halogen, 1-4C alkyl, 1-4C alkoxy, 1-4C alkylthio or CF3; R2 is 1-4C alkyl; n is 0, 1 2, 3 or 4; and Az is 1,2,4-triazol-1-yl or 1,2,4-triazol-4-yl). (I) are fungicides with a curative effect, particularly against true mildews (including benzimidazole-resistant mildews) on fruit, vegetables, cereals and ornamentals. (I) are also suitable for use as technical fungicides e.g. in wood preservation, in paints, and as preservatives in metal-working lubricants.

Description

Derivatives of 1,2,4-triazole

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

The compounds according to the invention have the general formula I, where R1 is halogen, C1 4 alkyl, C1 4 alkoxy, C1 4 alkylthio or the CF3 group, R C1 ~ 4 alkyl, linear or branched, n 0, 1, 2, 3 or 4 and azole denotes 1, 2,4-triazol-1-yl residue or the 1,2,4-triazol-4-yl radical mean.

In formula I, R1 is preferably halogen, in particular chlorine, n = 0, 1 or 2 and azole is the 1,2,4-triazol-1-yl radical.

The compounds of the formula I are obtained by adding compounds of the general formula II in which R1, R2 and n have the meanings as in formula I and Hal is halogen, preferably chlorine or bromine, in particular chlorine, in the presence of a hydrogen halide binding agent, preferably at least a stoichiometric or excess amount of this agent, for example inorganic or organic basic compounds, at higher temperatures, preferably 60 to 120 ° C., in particular at 80 to 100 cm, with at least one mole of 1,2,4-triazole per mole of compound of the formula II.

The reaction can advantageously be carried out in inert organic solvents be performed.

Inert organic solvents are, for example, aprotic solvents, for example acetonitrile, dimethylformamide, methyl tert-butyl ketone or dioxane in question.

As hydrogen halide binding agents are e.g.

inorganic bases such as sodium carbonate, sodium bicarbonate, potassium carbonate, Potassium bicarbonate or organic bases, e.g. tert-amines, such as triethylamine, Pyridine or ethyldicyclohexylamine.

The compounds of the formula II, which are new per se, can be prepared by known methods, for example by using the known benzoylmalonic esters of the formula III, in which R11, R2 and n have the same meanings as in formula I, are reacted with a halogenating agent, preferably in a solvent or diluent.

Known compounds are preferred as halogenating agents Chlorinating agents in question, such as PC15, POCl3, PCl3, thionyl chloride or phosgene, the use of excess halogenating agent as a solvent or diluent can be beneficial.

The chlorination is preferably carried out with PCl5, preferably in POCl3 or PC13 as a solvent or diluent.

If, in the halogenation of the compounds of the formula III, for example, phosphorus pentachloride is used as the chlorinating agent and phosphorus oxychloride or phosphorus trichloride as the diluent, then in addition to the compounds of the formula II, some compounds of the formula IV are also obtained, in which R1, R2 and n have the same meanings as in formula I.

By subsequent esterification with an alcohol of the formula R2 -OH the compounds of the formula IV can be converted into the compounds of the formula II.

The compounds of the formula III are known or can be traced known methods, e.g. by reacting acid chlorides with malonic esters (see, inter alia, Houben-Weyl, Methods of Organic Chemistry, Vol. 8 (1952) p. 611, as well as Bull. Soc. Chim. Fr., 1969, p. 2456).

The yields of the compounds of the formula I, based on the amount used Compounds of formula II are very good and are generally above 80 % of theory.

The compounds of the formula I according to the invention are distinguished by an excellent fungicidal effect. Fungal pathogens that are present in the Plant tissues penetrate or have already penetrated, can be dealt with with their Help successfully fight curatively. This is particularly advantageous with such Fungal diseases after infection with the usual, prophylactic effective fungicides can no longer be controlled. The spectrum of action of the claimed compounds include, for example, in addition to Puccinia triticina and Piricularia oryzae mainly powdery mildew fungi in fruit, vegetable, cereal and ornamental plant cultivation. Particularly noteworthy is the good effect of the claimed compounds against Powdery mildew resistant to benzimidazole derivatives (e.g. benomyl, carbendazim) are.

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

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 - 95 wt .- *, preferably at 10 - 90 wt. In addition, the active ingredient formulations mentioned may contain the usual adhesive, wetting, dispersing, emulsifying, penetration, solvent, Fillers and carriers. Also mixtures or mixed formulations with other pesticides Active ingredients such as insecticides, acaricides, herbicides or fungicides as well fertilizers or growth regulators are possible.

The invention is illustrated by the following examples: A. Precursors for the preparation examples 1) Preparation of the precursor 2- (carboethoxy) -3- (2,6-dichlorophenyl) -3-chloro-acrylate 66.6 g (0.2 mol) of 2,6-dichlorobenzoylmalonic ester are dissolved in 100 ml of phosphorus oxychloride, and 125.2 g (0.6 mol) of phosphorus pentachloride are added. The mixture is stirred under reflux for 8 hours, excess phosphorus oxychloride is drawn off on a rotary evaporator, the residue is taken up in 200 ml of methylene chloride and 50 ml of abs is added dropwise with good cooling at 00C. Ethanol too. The mixture is stirred for 1 hour at room temperature, then concentrated on a rotary evaporator, the residue is taken up in methylene chloride, the solution is washed with water and, after drying, first of all from the solvent and then the evaporation residue is distilled.

45.3 g (64% of theory) of the desired precursor are obtained as yellowish oil with a boiling point of 1400C at 0.53 mbar.

2) Preparation of the precursor 2-Carbcthoxy-3- (4-methylphenyl) -3-chloro-acrylic acid ethyl ester 69.5 g (0.25 mol) of 4-methylbenzoylmalonic ester are dissolved in 100 ml of PC13, and 156.5 g (0.75 mol) of phosphorus pentachloride are added. The mixture is stirred under reflux for 8 hours, the volatile components are removed on a rotary evaporator and the residue is taken up in 200 ml of abs. On ether and, while cooling at OOC, a mixture of 46 ml of pyridine and 40 ml of ethanol is added. The mixture is stirred for 1 hour at room temperature, concentrated, the residue is taken up in methylene chloride and the solution is washed successively with dilute sulfuric acid and water. After drying, the evaporation residue is distilled under high vacuum. 48 g (64.8% of theory) are obtained.

) Theory) of the desired precursor as an oil with a boiling point of 1360C at 0.29 mbar and the refractive index 25 nD: 1.5251.

B. Preparation Examples Example 1 2-Carboethoxy-3- (2,6-dichlorophenyl) -3- (1,2,4-triazol-1-yl) -acrylic acid ethyl ester 17.6 g (0.05 mol) of 2-carboethoxy-3- (2,6-dichlorophenyl) -3-chloro-acrylic acid ethyl ester are dissolved in 20 ml of acetonitrile and made into a suspension of 3.5 g (0.05 mol) 1,2,4-triazole and 13.8 g (0.1 mol) of potassium carbonate in 80 ml of acetonitrile were added dropwise. After refluxing for 8 hours, a further 0.5 g of 1,2,4-triazole are added and the mixture is stirred under reflux for a further 3 hours. The mixture is then allowed to cool, filtered, the solvent is drawn off, the residue is taken up in methylene chloride, washed with H 2 O, dried and, after the solvent has been drawn off, 16 g (83% of theory) of the desired TLC-pure product with a melting point of 940 ° C. is obtained.

Analysis: C16H15C12N3 ° 4 M = 384 calcd. C 50.00% found - C 49.8% H 3.91% H 3.8% N 10.94% N 10.8% Example 2 2-Carboethoxy-3 - (4-methylphenyl) -3- (1,2,4-triazol-1-yl) -acrylic acid ethyl ster 20.7 g (0.07 mol) of 2-carboethoxy-3- (4-methylphenyl) -3-chloroacrylic acid ethyl ester are dissolved in 20 ml of acetonitrile and added to a suspension of 5.3 g (0.077 mol) 1,2,4- Triazole and 20 g (0.14 mol) of potassium carbonate in 80 ml of acetonitrile were added dropwise.

The mixture is stirred under reflux for 6 hours, filtered and evaporated on a rotary evaporator a, the residue is taken up in methylene chloride and the solution is washed with water. After drying, the solvent is first used on a rotary evaporator, then under High vacuum removed. There remain 18.9 g (82% of theory) of the desired product as a syrupy substance.

Analysis: C17H19N3O4 = 329 calcd. C 62.00% found. C 62.0% H 5.78% H 6.2% N 12.77% N 12.9% Examples 3-11 In a manner analogous to that described in Example 2 Examples 3-11 are carried out. In Table 1, the radicals R1 are R2 and n in formula Ia according to Examples 3-11 from the corresponding compounds of the formula II prepared compounds and their melting points are listed.

Table 1 Formula Ia: Ex. R1 n R2 Fp. No. 3 2-C1 1 -C2H5 syrupy o1 4 4-Cl 1 2 5 58-61 5 2,4-di-Cl2 -C2H5 99-102 6 0 -C2H5 81-83 7 4,5-di-Cl2 -C2H5 119-121 8 4-Br 1 -C2H5 54 9 3-Cl 1 -C2H5 67 10 4-OCH3 1 -C2H5 i syrupy oil 11 2-Cl 1 -nC4Hg syrupy oil C. FORMULATION EXAMPLES Example A A dusting agent is obtained by mixing 10 parts by weight of active ingredient and 90 parts by weight of talc as an inert substance and comminuting in a hammer mill.

Example B A wettable powder readily dispersible in water is obtained by adding 25 parts by weight of active ingredient, 64 parts by weight of kaolin-containing Quartz as an inert substance, 10 parts by weight of potassium lignosulfonate and 1 part by weight oleoylmethyltaurinsaures Sodium as a wetting and dispersing agent mixes and in one Stiftinühle grinds.

Example C A dispersion concentrate which is easily dispersible in water is obtained by mixing 20 parts by weight of active ingredient with 6 parts by weight of alkylphenol polyglycol ether (Triton X 207), 3 parts by weight of isotridecanol polyglycol ether (8 AeO) and 71 parts by weight paraffinic mineral oil (boiling range e.g.

B. approx. 255 to over 3770C) and mixes up in a friction ball mill ground to a fineness of less than 5 microns.

Example D An emulsifiable concentrate is obtained from 15 parts by weight Active ingredient, 75 parts by weight of cyclohexanone as solvent and 10 parts by weight oxethylated nonylphenol (10 AeOj as an emulsifier.

D. Biological Examples The letters A, B and C stand for the the following commercially available comparison agents: A: N-tridecyl-2,6-dimethyl-morpholine (Tridemorph) B: methyl 1- (butylcarbamoyl) -2-benzimidazole carbamate (benomyl) C: manganese (11) - (N, N'-ethylene-bidithiocarbamate) (Maneb) Example I Wheat plants are in the 3-leaf stage with conidia of wheat powdery mildew (Erysiphe graminis) heavily inoculated and in a greenhouse at 200C and one relative humidity of 90 - 95%. 3 days after inoculation the plants with the compounds listed in Table I in the active compound concentrations of 1000, 500, 250, 125 and 60 mg / liter spray liquid sprayed to runoff.

As a comparison, the comparison agent A is used in an analogous manner. After an incubation period of 10 days, the plants are checked for wheat powdery mildew examined. The degree of infestation is expressed as a percentage of the infested leaf area on untreated, infected control plants (= 100% infestation). The result is summarized in Table I.

Table I. Combination of leaf area infested with wheat powdery mildew according to the example in% at mg active ingredient / liter spray liquor No. 1000 500 1 250 125 60 3 OO 0 o 5 15 1 OOO 3-5 10-15 5 0 0 5 15-15 25 11 0 0-3 3 5-10 15 ~ Comparison 0 3 5 medium A set egg phyto- phyto- phyto- toxic toxic toxic untreated, infect. 100 plants Example II 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 22 ° C. and 90% relative humidity. 3 days after infection, the plants are sprayed to runoff with the compounds and active compound concentrations mentioned in Table II used in an analogous manner.

The assessment takes place after 10 days. The degree of infestation is expressed in% infected leaf area, based on untreated, infected control plants (= 100% infestation). The result is summarized in Table II.

Table II Connection with cucumber powdery mildew infested leaf area according to the example in% at mg active ingredient / liter spray liquor No. 1000 500 250 125 60 3 OOO 0-3 5-10 1 0 0 0 3-5 5-10 5 0 0 0 5 10-15 ... ~. ~ 2 0 0 0-3 5 15 11 0 0 0 0-3 3 Comparative 0 3 5 10 15-25 medium B untreated , infiz. 100 plants Example III Barley plants in the 3-leaf stage are heavily inoculated with conidia of barley powdery mildew (Erysiphe graminis sp. Hordei) and placed in a greenhouse at 220 ° C. and a relative humidity of 90-95%. 3 days after inoculation, the plants are sprayed to runoff with the compounds listed in Table III in active compound concentrations of 1000, 500, 250, 125 and 60 liters of spray liquor. The comparison agent C is used as a comparison 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 infested leaf area, based on untreated, infected control plants (= 100% infestation). The result is summarized in Table III.

Table III Connection with barley powdery mildew infested leaf area according to example no. in% at mg active ingredient / liter spray mixture 1000 500 250 125 60 3 0 0 0 0-3 5 1 0 0 5 10 15 5 0 0 0 0-3 5 2 0 0 0-3 5-10 10-15 11 0 0 0 0-3 5 Comparison agent C 10 25 35 60 untreated, infected Plants 100

Claims (6)

Claims 1. Compounds of the general formula I wherein R1 is halogen, C14-alkyl, C14-alkoxy, C14-alkylthio or the CF3 group, R2 is C1-4-alkyl, linear or branched, n is 0, 1, 2, 3 or 4 and azole is 1,2,4 -Triazol-1-yl radical or the 1,2,4-triazol-4-yl radical mean. 2. Process for the preparation of compounds of the formula I according to claim 1, characterized in that compounds of the general formula II, in which R1, R2 and n have the meanings as in formula I and Hal is halogen, at higher temperatures in the presence of a hydrogen halide binding agent with at least one mole of 1,2,4-triazole per mole of compound of formula II, optionally in inert organic Reacts solvents. 3. Pesticides, characterized by a content purifier 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 4 for pest control in crop protection. 6. A method of combating harmful fungi, characterized in that that they infested areas and / or plants and / or substrates with an effective amount of active ingredients of the formula I according to claims 1, 3 and 4 in Brings contact.