CS262677B2

CS262677B2 - Fungicide

Info

Publication number: CS262677B2
Application number: CS866368A
Authority: CS
Inventors: Hideo Takaishi; Hiroshi Hamaguchi; Akira Nishimura; Kuniaki Taninaka
Original assignee: Nihon Nohyaku Co Ltd
Priority date: 1985-09-03
Filing date: 1986-09-03
Publication date: 1989-03-14
Also published as: KR920004934B1; HU198185B; ES2001924A6; HUT43932A; JPS6253970A; CS636886A2; JPH0572906B2; KR870003074A

Abstract

Pyrazole derivs. of formula (I) are new, where R1 = H, lower (halo)alkyl or phenyl; R2 = lower alkyl; R3 = H, lower alkyl or phenyl; X are each identical or different H, lower alkoxy(carbonyl), methylenedioxy, or phenoxy substd. by lower haloalkyl; n = 1 or 2. Prepn. of (I) comprises reacting pyrazole deriv. of formula (II) with phenol deriv. of formula (III), where Hal = halogen; M = H or alkali metal atom. - The reaction can be carried out in presence of base and solvent. Solvents are methanol, ethanol, diethylether, diisopropylether, THF, dichloroethane, benzene, water or their mixts. When conducting the two phase reaction, a phase transfer catalyst e.g. triethylbenzyl ammonium chloride, trioctylmethyl ammonium chloride, etc. can be used. Bases are inorganic bases (e.g. Na2CO3, K2CO3, CaCO3, NaOH, KOH, LiH), and organic bases (e.g. diethylamine, triethylamine, pyridine). Amt. of base is equimolar w.r.t. (III). Reaction temp. is room temp. to b. pt. of solvent.

Description

262677

The present invention relates to a process for the preparation of pyrazole derivatives of the general formula (Ia) as well as to agricultural and horticultural fungicides which use said pyrazole derivatives of the general formula (IR) as active ingredient.

Wherein R 1 represents a hydrogen atom, a C 1 -C 5 alkyl group, a C 1 -C 5 haloalkyl group, or a phenyl group; R 2 is C 1 -C 5 alkyl, R 3 is hydrogen, C 1 -C 5 alkyl or phenyl, X is independently hydrogen, halogen, nitro, alkyl C 1 -C 5 -alkoxy, C 1 -C 5 -alkoxy, C 2 -C 7 -alkoxycarbonyl, methylenedioxy or phenyloxy-substituted C 1 -C 5 haloalkyl and n is 1 to 2. of the present invention is to provide a process for the preparation of pyrazole derivatives of general formula (I), which are novel compounds which have not yet been prepared and disclosed in the publication, which are useful as intermediates in medicine and for agricultural chemicals or are useful in the art. as such, because they themselves have fungicidal activity.

It is a further object of the present invention to provide compositions which contain said pyrazole derivatives as active ingredient, which are useful as agricultural and industrial fungicides.

The process for making pyrazole derivatives of general formula I according to the invention is shown in the following reaction scheme:

wherein R 1, R 2, R 3, R e and n are as defined above, Hal represents a halogen atom and M represents a hydrogen atom or an alcalic metal atom.

Thus, the pyrazole of formula (II) is not reacted with the phenol derivative of general formula (III) in a solvent with or without a base to form a pyrazole derivative of formula (I).

Any solvent which does not hinder the reaction can be used as the solvent of the present invention. Examples include alcohols (e.g., methanol, ethanol, isopropanol, diethylene glycol), ethers (e.g., diethyl ether, diisopropyl ether, tetrahydrofuran, 0) dioxane, monoglyme, diglyme), halogenated hydrocarbons (e.g. dichloromethane, chloroform, tetrachloroethane), aromatic hydrocarbons (e.g. benzene, mono-chloro-benzene, nitrobenzene, toluene), nitriles (e.g. acetonitrile), dimethylsulfoxide , dimethylformamide, water and mixtures thereof.

Bases which may be used are inorganic or organic bases. As inorganic bases, for example, alkali metal or alkaline earth metal carbonates (e.g., sodium carbonate, potassium carbonate, calcium carbonate, sodium bicarbonate) and hydroxides or hydrides of alkali metals or alkaline earth metals (e.g., sodium hydroxide, potassium hydroxide, hydro- hydrate) may be used. Calcium hydroxide, sodium hydride, lithium hydride. Organic bases include, for example, diethylamine, triethylamine, pyridine, and 4-dimethylaminopyridine, and an organometallic compound such as methyllithium, butyllithium, methylmagne, and the like. If a mixture of solvents is used, a phase transfer catalyst such as triethylbenzylammonium chloride, trioctylmethylammonium chloride or the like can also be used, and the base can be used in equimolar amounts with respect to the phenol derivative of the general formula III, but can also be used over-flat basis.

The reaction temperature is appropriately selected from room temperature to the boiling point of the solvent. The reaction time varies according to the reaction temperature and the amount of the reactants, from about 1 minute to about 48 hours.

The amount of the reactants may be such that the amount is inter-equimolar since the reaction of this invention is equimolar. However, any reactant can be used in excess.

After completion of the reaction, the desired product can be separated by conventional means. If necessary, it is further purified by recrystallization, distillation or the like.

The pyrazole of formula (II) of the present invention can be prepared in a manner known per se [for example, as described in Chemical Abstracts 73, 3,844W (1970)].

Typical examples of compounds of Formula I are shown in Table 1.

Slouče- Rinina No. TABLE 1

Physical properties 1 H CH3 HH oil 2 CH3 CH3 HH nD20 1,5657 3 CH3 CH3 H 2-C1 nD20 1,5799 4 CH3 CH3 H 3-C1 melting point 59,8 CC 5 CH3 CH3 H 4-C1 oil 6 CH3 CH3 H 4-Br oil 7 CH3 CH3 H 2-F oil 8 CH3 CH3 H 3-F oil 9 CH3 CH3 H 4-F oil 10 CH3 CH3 H 2-CH3 oil 11 CH3 CH3 H3-CH3 oil 12 CH3 CH3 H4 -CH3 oil 13 CH3 CH3 H3-C2H5 nD20 1.5500 14 CH3 CH3 H4-C2H5 nD20 1.5498 15 CHs CH3 H4-tert. C4H9 oil 16 CH3 CH3 H 2-OCH3 oil 17 CH3 CH3 H 3-OCH3 oil 18 CH3 CH3 H 4-OCH3 oil 19 CHs CH3 H4-OC2H5 nD20 1,5485 20 CH3 CH3 H 3-CF3 oil 21 CH3 CH3 H4 -NO2 oil 22 CH3 CH3 H4-OCO (CH2) 2CH3 '' li '* nD20 1,5385 23 CH3 CH3 H 4-0- ^ 0 / - ^ 3 nD20 1,5303 24 CH3 CH3 H 2,4-dichloro melting point 132.0 ° C CH3 CH3 H 3.4-dichloro oil 26 CH3 CH3 H 3.5- (OCH3) 2 oil 262677

Ri R2 R3 nina no.

Xn 8

Physical Properties 27 CH3 CH3 H 3.4- (_O> CH2Ítt 81.7 to 81.9 ° C 28 CH3 CH3 CH3 H oil 29 CH3 CHs C2H5 H oil 30 CH3 CH3 SO-C3H7 H oil. 31 CH3 CH3 <O > H melting point 95.7 ° C 32 C2H5 CH3 HH melting point 84.7 ° C 33 1SO-C3H7 CH3 HH oil 34 CH3 HH oil 35 © CH3 HH melting point 99.4 ° C 36 <2> CH3 H 4- C1 Oil Table 2 shows NMR Spectrum - Compound No. NMR (CDCl3, TMS1 [ppm] data for those compounds of Table 1, which in the physical properties column are 11 2.3 (singlet, 3H), " oil " 2.4 (singlet, 3H), 3.6 (singlet, 3H), TABLE 2 6.7-7.5 (multiplet, 4H), 9.5 (singlet, 3H), 3.6 (singlet, 3H); 1H) Compound No. NMR (GDCl3, TMSa [ppm] 1 3.6 (singlet, 3H), 12 2.3 (singlet, 3H), 2.4 (singlet, 3H), 3.6 (singlet, 3H), 6.7 up to 7.5 (multiplet, 5H), 7.5 (singlet, 1H), 6.8-7.5 (multiplet, 4H), 9.4 (singlet, 1H) 9.6 (singlet, 1H, 2.4) ( singlet, 3H], 3.6 (singlet, 3H), 15 1.3 (singlet, 9H), 2.4 (singlet, 3H), 3.6 (singlet, 3H), 6.7-7.5 (multiplet, 5H), 9.5 (singlet, 1H) 6.8-7.4 (multiplet, 4H), 9.4 (singlet, 1H) [delta] 2.3 (singlet, 3H), 3.6 (singlet, 3H), 7, 2 to 7.5 (multiplet, 4H), 16 2.4 (singlet, 3H), 3.6 singlet, 3H], 3.7 (singlet, 3H), 9.5 (singlet, 1H); ), 6.6-7.2 (multiplet, 4H), 9.4 (singlet, 1H) 3.6 (singlet, 3H), 6.8-7.6 (multiplet, 4H), 9.6 (singlet, 1H) 17 2.4 (singlet, 3H, 3.6 (singlet, 3H), 3.7 (singlet, 3H, 7, 2.4 (singlet, 3H), 3.6 (singlet, 3H, 6.4 to 7.2 (multiplet, 4H), 9.4 (singlet, 1H, 6.5-7.4 (m, 4H), 9.5 (s, 1H) [delta] 2.4 (singlet, 3H), 18 2.4 (singlet, 3H), 3.6 (singlet, 3Hj, 3.75 (singlet, 3H), 3.6 (singlet, 3H), 6.5 to 7.5 (multiplet, 4H, 6.9 to 7.0 (multiplet, 4H), 9.4 (singlet, 1H) 9.5 (singlet, 1H) 9 2.4 (singlet, 3H), 20 2.4 (singlet, 3H), 3.6 (singlet, 3H, 3.6 (singlet, 3H), 6.9 to 7.1 (multiplet, 4H), 7.2-7.5 (multiplet, 4H), 9.5 (singlet, 1H) 9.5 (singlet, 1H) 10 2.3 (singlet, 3H), 21.2 , 5 (singlet, 3H), 3.7 (singlet, 3H), 2.4 (singlet, 3H), 3.6 (singlet, 3H), 6.7 to 7.4 (multiplet, 4H), 7.0-8.3 (multiplet, 4H), 9.7 (singlet, 1H) 9.5 (singlet, 1H) 262677 10

Compound No. NMR (CDCl3, TMS) [ppm]

Compound No. NMR (CDCl3, TMS) (ppm) 25 2.4 (singlet, 3H), 3.6 (singlet, 3H), 6.7-7.5 (multiplet, 3H), 9.6 (singlet, 1H) 26 2.4 (singlet, 3H), 3.6 (singlet, 3H), 3.7 (singlet, 6H), 6.0 to 6.2 (multiplet, 3H), 9.4 (singlet, 1H) 28 2.2 (singlet, 3H), 2.4 (singlet, 3H), 3.5 (singlet, 3H), 6.7-7.3 (multiplet, (H) 29 1.0 (triplet, 3H), 2.5 (singlet, 3H), 2.6 (quartet, 2H), 3.5 ( singlet, 3H), 6.8-7.5 (multiplet, 5H) 30 1.6 (doublet, 3H), 2.0 (multiplet, 1H), 2.1 (singlet, 3H), 3.6 (singlet, 3H), 6.8 to 7.4 (multiplet, 5H) 33 1.3 (doublet, 6H), 3.4 (multiplet, 1H), 3.6 (singlet, 3H), 6.8 to 7.3 (multiplet, 5H), 9.6 (singlet, 1H) 34 3.8 (singlet, 3H), 6.8 to 7.4 (multiplet, 5H), 9.7 (singlet, 1H) 36 3.7 (singlet, 3H), 6.9 to 8.0 (multiplet, 9H), 9.7 (singlet, 1H).

The invention is further illustrated by the following examples. Přikladl

Synthesis of 1,3-dimethyl-5-phenoxy-4-formylpyrazole (Compound No. 2)

0.94 g (0.01 mol) of phenol are dissolved in 10 ml of dimethyl sulfoxide. To this solution is added 0.264 g (0.011 mol) of hydride. The mixture was stirred. When the hydrogen evolution is complete, 0.79 g (0.005 mol) of 5-chloro-4-methyl-1,3-dimethylpyrazole is added. The whole mixture is reacted for 5 hours at 80 ° C to 100 ° C. After completion of the reaction, about 100 ml of water are added to the reaction mixture and the reaction mixture is extracted with ethyl acetate. The extract was washed with water, dried by distillation under reduced pressure, and the ethyl acetate was removed. One gram of the desired product was obtained, nD2O = 1.565 7. Yield 93%.

Synthesis of 1,3-dimethyl-5-p-bromophenoxy-4-formylpyrazole (Compound No. 6)

1.58 g (0.01 mol) of 5-chloro-4-formyl-1,3-dimethylpyrazole and 2.11 g (0.01 mol) of potassium salt of p-bromophenol were dissolved in 50 ml of dimethylformamide. The 262677 11 solution was reacted at 50 ° C to 60 ° C for 3 hours. After completion of the reaction, 200 ml of water were added to the reaction mixture, and the reaction mixture was extracted with ethyl acetate. The extract was washed with water, dried and the ethyl acetate was removed by distillation under reduced pressure to give the desired product in a yield of 2 g as an oily substance (yield: 68%).

Synthesis of 4-propionyl-5-phenoxy-1,3-dimethylpyrazole (Compound No. 29) c, z {is

0.94 g (0.01 mol) of phenol are dissolved in 10 ml of dimethyl sulfoxide. To this solution is added 0.264 g (0.011 mol) of hydride. By stirring the reaction mixture, the phenol is converted to the sodium salt. To this solution was added 1.22 g (0.005 mol) of 5-chloro-4-propionyl-1,3-dimethylpyrazole and the solution was heated to 70-80 ° C for five hours. After completion of the reaction, the reaction mixture is worked up in the same manner as described in Example 1 above. 1.5 g of the desired product are obtained as an oil, yield: 62%.

These pyrazole derivatives are capable of regulating various diseases caused by fungi attacking valuable crops grown on paddy fields, on highlands, in gardens and similar places, such as rice blight caused by Pyricularia oryzae, powdery mildew of barley and wheat, which causes Erysiphegraminis, oatiness caused by Puccinia coronata, brown blotch in rice-treated Cochliobolus miyabe-ianus, soybean ipurpurity, which causes Cercospora kikuchi, powdery mildew of Pseudopeconosphoracubensis and the like.

For the application of the compounds according to the invention as fungicides, these compounds are prepared in a suitable form for use according to the conventional methods for the preparation of agricultural chemicals. That is, the compounds of the invention are mixed with suitable inert carriers and, if necessary, adjuvants in a suitable ratio. By distillation, dispersing, suspending, mechanically mixing, impregnating, adsorbing, or sticking, a suitable formulation is prepared, for example, suspensions, emulsifiable concentrates, solutions, wettable powders, dusts, granules or tablets.

The inert carriers used in the compositions may be solids or liquids. As examples of acceptable solid carriers, plant powders such as soy meal, cereal flour, wood flour, bark meal, sawdust, powdered stems, powdered nut shells, bran, powdered cellulose and plant extract residues, fibrous may be mentioned. materials such as paper, cardboard and waste materials, synthetic polymers such as powdered synthetic resins, anorganic or mineral products such as clays (for example, kaolin, bentonite and acid clays), talc (e.g. talc and pyrophyllite) ), silicates [for example, diatomaceous earth, silica pin, mica, and " white coal " (highly dispersed synthetic silicic acid, sometimes referred to as finely divided hydrated silica or hydrated silicic acid; commercial products contain as the main component hydrated silicic acid)] , activated carbon, powdered clay, pumice, calcined diatomaceous earth, ground bricks, fly ash, sand, calcium carbonate, phosphorous carbonate, chemical fertilizers such as ammonium sulfate, ammonium nitrate, urea and chloride ammonium and farmer manure. These materials are used either alone or in combination. Materials that use as liquid carriers are selected from those which are the active ingredient solvents and non-solvent ones, but which can disperse the active compounds with adjuvants. For example, the following materials may be used alone or in combination: water, alcohols (e.g., methanol, ethanol, isopropanol, butanol, ethylene glycol), ketones (e.g., acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl) -ton and cyclohexanone), ethers (for example, ethyl ether, dioxane, full-length, dipropylether tetrahydrofuran), aliphatic hydrocarbons (e.g., gasoline and mineral oils), aromatic hydrocarbons (e.g., benzene, toluene, xylene, solvent benzol and alkylnaphthalenes), halogenated hydrocarbons (for example dichloroethane, chlorinated benzenes, chloroform and tetracalormethane), esters (for example ethyl acetate, dibutyl phthalate, diisipropyl phthalate and dioctyl phthalate), amides (for example dimethylformamide, dimethylformamide and dimethylacetamide), nitriles (for example acetonitrile) and dimethylsulfoxide.

Adjuvants, examples of which are given below, are used according to the purpose, in some examples, the B2S771314 is mutated. In some cases, no adjuvant is used.

Surfactants such as polyoxyethylene alkylaryl ethers, polyoxyethylene alkyl ethers, polyoxyethylene higher fatty acid esters, polyoxyethylene resins, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan monooleate, polyoxyethylene resorbitan monolaurate are used for emulsifying, dispersing, dissolving and / or wetting the active compounds. , alkylarylsulfonates, condensation products of naphthalenesulfonic acids, ligninsulfonates and sulfate esters of higher alcohols. For example, casei, gelatin, starch, alginic acid, methylcellulose, carboxymethylcellulose, gum arabic, polyvinyl alcohol, terpentine oil, rice oil, can be used to stabilize dispersion, improve tack and / or agglomeration active compounds. bran, benzene and lignin sulfonates.

It is recommended to use waxes, stearates or alkylphosphates to improve the liquid properties of the solid composition. It is recommended to use the naphthalenesulfonic acid condensation products and polyphosphonates as the dispersing agent. Antifoaming agents such as silicone oil may also be added.

The active ingredient content is adjusted according to the requirements. In the preparation of powdered or granulated products, the active ingredient content is usually 0.5 to 20% by weight. In the preparation of emulsifiable concentrates or wettable powdered products, a content of 0.1 to 50 weight percent is desirable. In the control of various fungi, inhibition of growth, or protection of useful fungal-damaging plants, a dose (which is capable of controlling and / or inhibiting fungi and thereby protecting useful plant fungicidal agents from agricultural and horticultural uses is applied) either as such or after dilution or suspension in water or other suitable medium on the soil or foliage of the crop to be protected prior to the action of the fungus.

The amount of fungicide according to the invention to be used depends on various factors, such as the purpose of application, crop growth stage, weather, ambient conditions, form of the fungicide, application, field type, which is For example, when applying the fungicidal composition alone, it is desirable that the selected dose of the active compound of this invention be in the range of 5 to 500 grams per 0.1 ha. It is also to be understood that, when combined with other fungicides, the optimum dose is often lower than the application of a single compound. Thus, the fungicide may be used at lower than the aforementioned doses when used in combination with another fungicide. In addition, the compounds of the present invention may be applied as a composition in general with other fungicides, insecticides, fertilizers and plant growth regulators, as long as they can be used together. Illustrative examples of fungicides used in conjunction with the present invention include isoprotiolane, pyroqui- lon, edifenphos, captan, chlorothalonil, caprolactol, thiophanate-methyl, benomyl, zineb, mab and the like. Illustrative examples of insecticides that are used together with the compound of the present invention include acephat, malathion, fenitrothione, BPMC, MTMC and the like insecticides. The following examples illustrate the fungicidal activity and formulation of the compounds of the invention. However, the present invention is not limited to these examples.

Test - Example 1

Test of regulation of false cucumber fallen

Two-leaf young cucumber seedlings (Suyo variant) are grown in plastic crucibles. These cucumbers are spray-sprayed with a chemical solution containing a compound of the invention at a predetermined concentration. After one day air drying, the cucumbers are sprayed with the suspension Pseu-doperonosphora cubensis conidia are placed in a humid room for 20 hours. The plants are then transferred to the greenhouse, and the 8th day of inoculation is examined for lesions that have developed on the leaves. Compound control values are calculated and the compound's regulatory effect is determined from the following criteria.

Criteria: A. .. control value ΐθ 95 to 100%, B. . ,. the control value is 80 to 94%; the control value is 60 to 79 ° / o. The results are shown in Table 3. 2B2B77 Test compound number

Concentration (ppm)

Regulatory Effect 15 16 TABLE 3 1 2 3 5 6 7 89 15 20 24 28 30

Test - Example 2

Test of rice control

Five-leaf young rice plants (variant: Nihonbare) are grown in 10 cm plastic pots (10 in each pot). The spray coating is sufficiently sprayed on the rice with a chemical solution containing the active compound of the present invention at a predetermined concentration. Denpo spraying of the rice is inoculated by spraying a conidium suspension of Pyricularia oryzae. He places the rice in a damp room for a period of 20 100010001 0001 0001 00010001000100010001 0001 0001 0001000

BABBBBBABBBBB hours. It is then transferred to the greenhouse. Six weeks after inoculation, the lesions developed are compared and compared to the control group of rice (without the compound of the invention). The control values are calculated by the compound. The regulatory effect of the compound is determined from the following criteria.

Criteria: A ... control value 95 to 100 ° / o, B ... control value 80 to 94%, C ... control value 60 to 79%. The results are shown in Table 4. Test Compound Number TABLE 4 Concentration (ppm) Regulatory Effect 1 2 4 6 7 89 17 21 28

Test - Example 3

Barley powdery mildew control test

Two-leaf young barley plants grown in pots inoculated with conidia of Erysiphe graminisf. sp. hordei. The day after inoculation, the barley plants are sprayed with a solution containing the compound of the invention in advance of 00010001000100010001 00010001 0001000

BBBBBBBABBB determined concentration. The barley is then left to stand at a constant temperature of 25 ° C. The area of damage is determined on the following week. These areas are compared to the barley control group areas (i.e., without the compound of the invention). The regulatory effect of the compound is determined by the same criteria used in the test of Example 1. The results are shown in Table 5.

Claims

Control effect 262577 17 18 Test compound number TABLE 5Concentration [ppm] 1 2 6 7 89 17 21 23 26 28 29 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 1000 BBBBBBBBBBAB Formulation - Example 1 Wettable Powder Compound No. 2 50 Parts Infusion soils and clays 45 parts polyoxyethyleninonylphenyl ether 5 parts The above materials are uniformly mixed. By milling, a wettable powder is obtained. Formulation Example 2 Emulsion Compound # 9 20 parts tetrahydrofuran 20 parts xylene 45 parts blend of polyoxyethylene nonylphenyl ether and alkylbenzene sulfonic acid salt 15 parts The above materials are uniformly mixed. Dissolution gives an emulsion. Formulation Example 3 Dust Compound No. 17 4 parts mixture of diatomaceous earth, clay and talc 95 parts calcium stearate 1 part The above materials are uniformly mixed. Powder is obtained by grinding - Example 4 Granules Compound No. 28 3 parts bentonite / clay mixture 92 parts calcium lignin sulfonate 5 parts The above materials are uniformly mixed. An appropriate amount of water is added. Bend the mixture. The pellet is obtained by granulation. pRedmEt c

A fungicidal composition for agricultural horticultural use, characterized in that it comprises as active ingredient a pyrazole derivative of the general formula I

EMBODIMENTS The substituents may independently be hydrogen, halogen, nitro, C 1 -C 5 alkyl, C 1 -C 5 alkoxy, C 2 -C 7 alkoxycarbonyl , methylenedioxy or phenoxy substituted with haloalkyl of 1 to 5 carbon atoms and means a number of from 1 to 2.

2. A process according to claim 1, for the preparation of compounds of formula I, wherein the pyrazole of formula II is reacted wherein R 1 is hydrogen, C 1 -C 5 alkyl, C 1 -C 5 haloalkyl. or phenyl, R 2 is C 1 -C 5 alkyl, R 3 is hydrogen, C 1 -C 5 alkyl or phenyl, X

Wherein R 1, R 2 and R 3 are as defined above and Hal is a halogen atom with a phenol derivative of formula III wherein X and n are as defined above M is a hydrogen atom or an alkali metal atom.

Clil)