JPH0237352B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a triazole compound useful as an agricultural and horticultural fungicide, a method for producing the same, and an agricultural and horticultural fungicide composition containing the same. According to the invention, the general formula (): A triazole compound (its cis- or trans isomer, or a mixture thereof) represented by [wherein R ¹ represents a (C _1-4 ) alkyl group or a halophenyl group, and R ² represents a halophenyl group]
and acid addition salts and metal complex salts thereof. The triazole compound of the present invention is usually obtained in the form of a mixture of isomers, but this mixture can be separated into individual isomers by known methods. A (C _1-4 )alkyl group may be a straight-chain or branched alkyl group having 1 to 4 carbon atoms; examples are, for example, methyl, ethyl, propyl (n- or iso-
-propyl) and butyl groups (n-, iso- or t-butyl). Examples of halo substituents on halophenyl groups are fluorine, chlorine or bromine. Either R ¹ or R ² , preferably both R ¹ and R ² are halophenyl groups having 1, 2 or 3 ring substituents as described above. Preferably, the phenyl group has one or two ring substituents at the 2- or 4-position. Examples of these groups are 2-, 3- or 4-chlorophenyl groups, 2,
4- or 2,6-dichlorophenyl group, 2-,
3- or 4-fluorophenyl group, 2,6-difluorophenyl group, 2-, 3- or 4-bromophenyl group, 2-chloro-4-fluorophenyl group, 2-chloro-6-fluorophenyl group The basis is. Therefore, according to one aspect of the present invention, there is provided a triazole compound in which, in the general formula (), R ¹ is a butyl group or a halophenyl group, and R ² is a halophenyl group. According to another aspect of the present invention, in the general formula (), R ¹ is a butyl group, a 2-chlorophenyl group,
2-fluorophenyl group, 2-bromophenyl group, 4-chlorophenyl group or 2,4-dichlorophenyl group, and R ² is 4-fluorophenyl group, 4-chlorophenyl group or 2,4-dichlorophenyl group. A triazole-based compound is provided. According to a preferred embodiment of the present invention, there is provided a triazole compound in which R ¹ is an n-butyl group and R ² is a 2,4-dichlorophenyl group in the general formula (). Salts are inorganic or organic acids, such as hydrochloric acid, nitric acid,
It can be a salt with sulfuric acid, acetic acid, 4-toluenesulfonic acid or oxalic acid. Suitably, the metal complex salt contains copper, zinc, manganese or iron as a metal. This complex has the general formula: (In the formula, R ¹ and R ² have the same meanings as above,
M represents a metal, A represents an anion such as chlorine, bromine, iodide, nitrate, sulfate or phosphate, n is 2 or 4, and y is 0 or 1.
~12, where n is an integer corresponding to the valence). Examples of the triazole compounds of the present invention are shown in Table 1.

【table】

[Table] Triazole compounds of general formula () are (wherein R ¹ and R ² have the same meanings as above) may be prepared by dehydrating the compound by refluxing in a suitable solvent under acidic conditions. Preferably, the compound of general formula () is reacted with phosphoric acid or trifluoroacetic acid by refluxing in toluene or other solvent. The resulting product can be isolated by pouring the reaction mixture into water and purifying it by column chromatography. The products are usually obtained as oils which easily form salts, such as nitrates. A compound of general formula () is a compound of general formula () or ():

【formula】

[Formula] (wherein R ¹ and R ² have the same meanings as above,
Y represents a halogen atom, preferably a chlorine or bromine atom),
- 1, in the form of an alkali metal salt, reacted with a triazole in the presence of an acid binder or in a customary solvent;
It can be produced by reacting with 2,4-triazole. A compound of general formula () or () is dissolved in a conventional solvent such as acetonitrile, methanol, ethanol or dimethylformamide for 20 to 100 hours.
It is suitable to react with the sodium salt of 1,2,4-triazole (this salt can be prepared by adding sodium hydride or sodium methoxide to 1,2,4-triazole) at a temperature of be. The product may be isolated by injecting the reaction mixture into water and recrystallizing the resulting solid from a convenient solvent. Compounds of general formula () and () have general formula (a) or (b):

【formula】

[Formula] (wherein R ¹ , R ² and Y have the same meanings as above), respectively, a ketone compound represented by the general formula (a) or (b): Z-Mg-R ² (a ), Z〓−Mg−R ¹ (b) (wherein R ¹ and R ² have the same meanings as above,
Z represents halogen, preferably chlorine, bromine or iodine) with a Grignard reagent in a convenient solvent such as diethyl ether or tetrahydrofuran. Usually, mixtures of compounds of general formulas () and () are obtained. For example, when a compound of general formula (a) in which R ¹ is a (C _1-4 ) alkyl group is reacted, the compound of general formula () is usually mainly contained in the ^mixture ; When is a halophenyl group, the compound of general formula () is usually mainly contained in the mixture. Compounds of general formula () and () are useful intermediates and form part of the present invention. Compounds of general formulas () and () can be prepared by methods described in the literature. A compound of the general formula () in which each of R ¹ and R ² (which may be the same or different) is a halophenyl group is a compound of the general formula (): R ¹ −CO−R ² () (wherein R ¹ and R ² have the same meaning as above) is reacted with dimethyloxosulfonium methylide (Corey and Chaykousky, JACS, 1965, 87,
1353-1364) or with dimethylsulfonium methylide (Corey and
Chaykousky, JACS, 1962, 84, 3782). Ketone compounds of general formula () can be prepared using Friedel-Crafts reactions according to literature methods. These ketone compounds are useful intermediates and as such form part of the present invention. A compound of the general formula () in which R ¹ is a (C _1-4 ) alkyl group or a halophenyl group and R ² is a halophenyl group is a compound of the general formula (): It can be produced by reacting β-hydroxyselenide (wherein R ¹ and R ² have the same meanings as above) and methyl iodide in potassium t-butoxide. (Van Ende, Dumond and
Krief's method, Angew, Chem.Int.Ed.1975, 14,
700). β-hydroxyselenide compounds can be prepared by treating diselenide with a suitable ketone in the presence of butyllithium. Salts and metal complex salts of compounds of general formula () can be produced from the former by known methods. For example, complex salts may be prepared by reacting the uncomplexed compound with a metal salt in a suitable solvent. The compounds of the present invention are effective as agricultural and horticultural fungicides, particularly against the following diseases: - Piricularia oryzae of rice; Puccinia recondita, Puccinia rust of wheat;
striiformis and other rusts), barley rust (Puccinia hordei, Puccinia striiformis and other rusts) and rusts of other host plants, such as coffee, apples, vegetables and ornamental plants; downy mildew of grapes (Plasmopara viticola); powdery mildew of barley and wheat (Erysiphe
gramihis) and powdery mildew of cereals (Helminthosporium spp), powdery mildew of cucurbits (e.g. cucumber) (Sphaerotheca fuliginea),
Apple powdery mildew (Podosphaera)
leucotricha) and other powdery mildews on various host plants such as Uncinula necator of grapes; Cercospora arachidicola of groundnuts and others such as Cercospora spp of sugar beets, bananas and soybeans; tomatoes , gray mold on strawberries, grapes and other host plants
(Botrytis cinerea); phytophthora infestans on tomatoes; Venturia inaequalis on apples. Also, some of the compounds according to the invention exhibit a wide range of activity against fungi in vitro. These compounds are also responsible for various post-harvest diseases of fruit, such as orange green mold (Penicillium
digitatum and italicum) and banana blight (Gloeosporium musarum). Furthermore, some of the compounds have been shown to be effective against cereal diseases such as Eusarium spp. and Septorium spp.
Tilletia spp. (smut, a disease that grows on wheat seeds), Ustilago spp. and powdery mildew (Helminthosporium spp.), Rhizoctonia solani of cotton and rice Shows activity in the form of a seed dressing against Corticium sasakii. Compounds of the invention may move acropetally within plant tissue. Furthermore, the compounds of the invention have sufficient volatility in the vapor phase to exhibit activity against fungi on plants. The compounds of the invention are also useful in the treatment of candidiasis and human dermatophyte diseases. While the compounds of the invention may be used as such as agricultural and horticultural fungicides, they may be conveniently formulated into compositions for use for such purposes. Accordingly, the present invention further provides an agricultural and horticultural fungicidal composition containing a compound of general formula (), or a salt or metal complex thereof as an active ingredient. The compounds of the invention, their salts and metal complexes can be applied in a variety of ways; for example, they can be applied directly to the foliage of plants, with or without formulation, or when the seeds or plants are grown. It can be applied to other media where it is growing or to be planted, or by spraying or dusting or as a cream or paste preparation or in the form of steam. Application can be made to any part of the plant, shrub or tree, such as the leaves, stems, branches, roots or the soil around the roots or to the seeds before sowing. As used herein, the term "plant" includes seedlings, shrubs and trees. Furthermore, sterilization methods include preventive, protective and eradication treatments. The compounds of the invention are preferably used for agricultural and horticultural purposes in the form of compositions. The type of composition used will vary depending on the particular purpose intended. The composition comprises the active ingredient and a solid diluent or carrier, such as kaolin, bentonite, diatomaceous earth, dolomite, calcium carbonate, talc, powdered magnesia,
It may be in the form of powders or granules for dispersion with fillers such as Fuller's earth, gypsum, Hewitt's earth, diatomaceous earth and china clay. Such granules may be preformed granules suitable for application to soil without further treatment. These granules may be prepared by impregnating pellets of filler with the active ingredient or by pelletizing a mixture of active ingredient and powdered filler. Compositions for seed dressings may contain, for example, agents that promote adhesion of the composition to the seeds, such as mineral oil; and organic solvents such as N
- The active ingredient may be formulated for seed dressing using methylpyrrolidone or dimethylformamide. The composition may also be in the form of a dispersible powder or granules containing a wetting agent to facilitate dispersion of the powder or granules in a liquid, such powders or granules further comprising fillers and suspending agents. may contain. Aqueous dispersions or emulsions are prepared by dissolving the active ingredient in an organic solvent which may optionally contain wetting agents, dispersing agents or emulsifying agents and then dissolving the resulting mixture in water which may also contain wetting agents, dispersing agents or emulsifying agents. It can be prepared by adding it to. Suitable organic solvents include ethylene dichloride, isopropyl alcohol, propylene glycol, diacetone alcohol, toluene, kerosene, methylnaphthalene, xylene, trichlorethylene, furfuryl alcohol, tetrahydrofurfuryl alcohol and glycol ethers such as 2-ethoxyethanol and -butoxyethanol). A spray composition can also be in the form of an aerosol, in which the formulation is held in a dispenser under pressure in the presence of a propellant, such as fluorotrichloromethane or dichlorodifluoromethane. The compounds of the invention can also be mixed in dry form with a pyrotechnic mixtnre to give compositions suitable for producing smoke containing them in closed spaces. Alternatively,
The compounds can also be used in the form of microcapsules. suitable additives, e.g. spreading on the surface to be treated;
By incorporating additives to improve adhesion and rain resistance, various compositions can be better adapted to the various intended uses. The compounds according to the invention can also be used in mixtures with fertilizers (for example nitrogen-, potassium- or phosphorus-containing fertilizers). Preference is given to compositions consisting solely of fertilizer granules into which the compound has been incorporated, for example by coating. Suitably such granules contain the active compound in an amount of up to 25% by weight. Furthermore, the compositions can be prepared as dipping liquids or spray liquids, which are usually aqueous dispersions or emulsions containing the active ingredient in the presence of one or more surface-active agents, such as wetting agents, dispersing agents, emulsifying agents or suspending agents. It can also be in the form of liquid preparations used. Such agents may be cationic or nonionic active agents. Suitable cationic activators are quaternary ammonium compounds such as cetyltrimethylammonium bromide. Suitable anionic active agents are soaps, salts of aliphatic monoesters of sulfuric acid (e.g. sodium lauryl sulfate), salts of sulfonated aromatic compounds (e.g. sodium dodecylbenzenesulfonate, sodium, calcium or ammonium lignosulfonate, butylnaphthalene). sulfonate and a mixture of the sodium salts of diisopropyl and triisopropylnaphthalene sulfonic acids). Suitable nonionic surfactants are condensation products of ethylene oxide and aliphatic alcohols such as oleyl, alcohol or cetyl alcohol or alkylphenols such as octylphenol, nonylphenol or octylcresol. Other nonionic surfactants are partial esters derived from long chain fatty acids and hexitol anhydride, condensation products of the partial esters with ethylene oxide, and lecithin. Suitable suspending agents are, for example, hydrophilic colloids (for example polyvinylpyrrolidone and sodium carboxymethyl cellulose) and vegetable gums (for example gum arabic and gum tragacanth). Compositions used in the form of aqueous dispersions or emulsions usually contain the active ingredient. It is supplied in the form of a concentrated liquid containing a high proportion and diluted with water before use. Such concentrates often withstand long-term storage and are applied with conventional spray devices when diluted with water after such long-term storage. The concentrate should be capable of forming an aqueous formulation that remains homogeneous for a sufficient period of time.Such concentrates are advantageously up to 95% by weight, preferably 10%
It may contain up to 85% by weight of active ingredient, such as 25-60%. These concentrates suitably contain organic acids (e.g. alkaryl or aryl sulfonic acids such as xylene sulfonic acid or dodecylbenzenesulfonic acid; because of the presence of such organic acids, The solubility of the active ingredient in the polar solvent used is increased.The concentrate suitably also contains a high proportion of surfactant, so that the emulsion is sufficiently stable in water. When diluted for the preparation of aqueous formulations, such formulations may contain varying amounts of active ingredient depending on their intended use, but generally between 0.0005 (usually 0.01) and 10% by weight.
Aqueous formulations containing the active ingredients can be used. The compositions of the invention may further contain other compounds with biological activity, such as compounds with similar or supplementary fungicidal activity, or compounds with herbicidal, plant growth regulating or insecticidal activity. . Other fungicidal compounds are used for cereal (e.g. wheat) ear diseases such as Septoria, Gibberella and
It can be a compound capable of eradicating diseases of the genus Helmin thoporium, seeds and soil, downy mildew and powdery mildew of grapes, and powdery mildew and rot of apples, etc. These fungicidal mixtures exhibit a broader range of activity than the compound of general formula () alone; furthermore, other fungicides exhibit additive effects on the fungicidal activity of the compound of general formula (). Examples of other fungicides include: imazalil, benomyl, carbendazim,
thiophanate-methyl,
captofol, captan, sulfur, triforine, dodemorph, tridemorph, pyrazophos, furalaxyl, ethirimol, dimethirimol,
bupirimate, chlorothalonil, vinclozolin, procymidone,
iprodione, metalaxyl, forsetyl-aluminium, carboxin, oxycarboxin, fenarimol,
nuarimol, fenfuram, methfuroxan,
Nitrotal-isopropyl (nitrotal-
isopropyl), triadimefon,
thiabendazol, etridiazole, triadimenol, biloxazol,
dithianon, binapacryl, quinomethionate, guazitine,
dodine, fentin acetate, fentin hydroxide, dinocap, folpet, dichlofluanid, ditalimphos, kitazin, cycloheximide ( cycloheximide), dichlobutrazol, dithiocarbamates, copper compounds, mercury compounds, DPX 3217, RH 2161, Chevron RE 20615, CGA 64250,
CGA 54251, RO 14−3169 and fenpropemorph. The compounds of general formula () may be mixed with soil, compost or other media for protecting plants from fungal diseases occurring on seeds, soil or leaves. Suitable insecticides include Pirimor;
Mention may be made of Croneton, dimethoate, Metasystox and formothion. Examples of suitable plant growth regulators are gibberellins (eg GA3, GA4 or GA7), auxins (eg indoleacetic acid, indolebutyric acid, naphthoxyacetic acid or naphthylacetic acid), cytokinins (eg kinetin, diphenylurea, benzimidazoles). , benzyladenine or BAP), phenoxyacetic acid (e.g. 2,4-D or MCPA), substituted benzoic acids (e.g. TIBA), morphactins (e.g. chlorfluorecol), maleic hydrazide, glyphosate ( glyphosate), glyphosine, long chain fatty alcohols or fatty acids (e.g. Off Shoot O or Off Shoot T), dikegulac, Sustar, Embark, substituted quaternary ammonium or Phosphonium compounds (e.g. CCC or Phosphon-D), Ethrel, carbetamide, Racuza, Alar, asulam, abseissic acid, isopyrimol , RH 531, hydroxybenzonitrile [e.g. bromoxynil],
Avenge, Suffix or Lontorcl. Examples of the present invention are shown below. Example 1 1-(1,2,4-triazol-1-yl)-
2-(2-chlorophenyl)-2-(4-fluorophenyl)ethylene (Compound No. 1 in Table 1)
and its nitrate (Compound No. 2 in Table 1) Sodium hydride (0.03 mol), powdered trimethyloxosulfonium iodide (0.03 mol) and anhydrous dimethyl sulfoxide (DMSO; 30 ml)
A dimethyloxosulfonium methylide solution was prepared from the above under a nitrogen atmosphere. 2-chlorophenyl-4-fluorophenyl ketone (0.025 mol)
A solution consisting of and DMSO (10 ml) was added dropwise at room temperature. The solution was heated at 50° C. for 1.5 hours, then cooled to room temperature and poured into water. This solution was extracted with diethyl ether (100 ml), washed with water (3 x 100
ml) and then dried over anhydrous sodium sulfate. Removal of solvent gives 1-(2-chlorophenyl)-1-
(4-fluorophenyl)ethylene oxide was obtained as a colorless liquid (yield 90%). 1,2,4-triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in dimethylformamide (DMF) (40 ml) and the resulting solution was stirred at room temperature until boiling ceased. 1-
(2-chlorophenyl)-1-(4-fluorophenyl)ethylene oxide (0.02 mol) and DMF (10
ml) was added dropwise and the solution was heated at 80°C to
Stir for hours. The solution was poured into water and triturated with petroleum ether to give a white crystalline solid which was filtered and dried. 1-(1,2,4-
triazol-1-yl)-2-(2-chlorophenyl)-2-(4-fluorophenyl)-ethane-
2-ol was obtained as a white crystalline solid (melting point 115-6°C). (yield 70%). 1-(1,2,4-triazol-1-yl)-
A mixture of 2-(2-chlorophenyl)-2-(4-fluorophenyl)ethane-2-ol (0.01 mol) and orthophosphoric acid (30 ml) was stirred at room temperature for 30 minutes, then heated at 50°C for 1 hour. It was warm. After standing overnight at room temperature, the mixture was poured into water (200ml) and extracted with diethyl ether (150ml). The ether solution was washed with water (3x100ml) and dried over anhydrous sodium sulfate. Removal of the solvent gave a yellow oil which was purified by medium pressure column chromatography (silica gel; eluting with ethyl acetate/petrol 1:1) to give the title compound as a pale brown oil (yield 80 %). This oil was dissolved in diethyl ether (30ml) and concentrated nitric acid (6 drops) was added to give the nitrate salt of the title compound (mp 124°C). Example 2 1-(1,2,4-triazol-1-yl)-
2-(4-chlorophenyl)-2-(4-fluorophenyl)ethylene (Compound No. 9 in Table 1)
Preparation of sodium hydride (0.03 mol), powdered trimethyloxosulfonium iodide (0.03 mol) and anhydrous dimethyl sulfoxide (DMSO; 30 ml)
A dimethyloxosulfonium methylide solution was prepared from the above under a nitrogen atmosphere. 4-chlorophenyl-4-fluorophenyl ketone (0.025 mol)
A solution consisting of and DMSO (10 ml) was added dropwise at room temperature. The solution was heated at 50° C. for 1.5 hours, then cooled to room temperature and poured into water. This solution was extracted with diethyl ether (100 ml), washed with water (3 x 100
ml) and then dried over anhydrous sodium sulfate. After removing the solvent, 1-(4-chlorophenyl)-1-
(4-fluorophenyl)ethylene oxide was obtained as a colorless oil (yield 90%). 1,2,4-triazole (0.04 mol) was added portionwise to sodium hydride (0.04 mol) in dimethylformamide (DMF) (40 ml) and the resulting solution was stirred at room temperature until boiling ceased. 1-
(4-chlorophenyl)-1-(4-fluorophenyl)ethylene oxide (0.02 mol) and DMF (10
ml) was added dropwise and the solution was heated at 80°C to
Stir for hours. The solution was poured into water and triturated with petroleum ether to give a white crystalline solid which was filtered and dried. 1-(1,2,4-
Triazol-1-yl)-2-(4-chlorophenyl)-2-(4-fluorophenyl)-ethane-
2-ol was obtained as a white crystalline solid (melting point 154-5°C) (75% yield). 1-(1,2,4-triazol-1-yl)-
A mixture of 2-(4-chlorophenyl)-2-(4-fluorophenyl)ethane-2-ol (0.07 mol) and orthophosphoric acid (30 ml) was stirred at room temperature for 30 minutes and then heated at 50°C for 1 hour. It was warm. After standing overnight at room temperature, the mixture was poured into water (200ml), extracted with ether (150ml) and washed with sodium bicarbonate solution. The ether solution was washed with water (2 x 100ml) and dried over anhydrous sodium sulfate. Removal of the solvent gave a solid which was recrystallized from petroleum ether (60-80°C)/chloroform to give the title compound (melting point 101-2°C) (yield 50
%). Example 3 An emulsifiable concentrate was prepared by mixing the following ingredients and stirring the mixture until all ingredients were dissolved: Compound of Table No. 1 10% Ethylene dichloride 40% Calcium Dodecylbenzenesulfonate 5% “Lubrol” L 10% “Aromasol” H 35% Example 4 The first three of the ingredients below were triturated in the presence of water and sodium acetate was added. After drying the mixture thus obtained, pass it through a British standard sieve, size 44.
A granular composition easily dispersible in a liquid, e.g. water, was prepared by passing it through -100 to obtain the desired particle size: “Dispersol”) T 25% “Lubrol” APN5 1.5% Sodium Acetate 23.5% Example 5 A powder formulation easily dispersible in liquids was prepared by grinding all of the following ingredients together: Table No. 7 Compound 45% “Dispasol” T 5% “Lissapol” NX 0.5% “Cellofas” B600 2% Sodium acetate 47.5% Example 6 After dissolving the active ingredient in a solvent, the The solution was sprayed onto the china clay granules. The solvent was then evaporated to obtain a granular composition: Table No. 8 compound 5% china clay 95% Example 7 A seed dressing was prepared by mixing the following three components: Table No. 8 Compound of .9 50% Mineral oil 2% china clay 48% Example 8 A dusting powder was prepared by mixing the active ingredient and talc: Compound of Table No. 1 5% Talc 95% Example 9 Below A Col formulation was prepared by ball milling the ingredients and suspending the milled mixture in water: Compound of Table No. 2 40% "Dispazol" T 10% "Lubrol" APN5 1% Water 49% Example 10 A dispersible powder formulation was prepared by mixing the following ingredients and grinding the mixture until all ingredients were thoroughly mixed: Compound of Table No. 7 25% “Aerosol” ( “Aerosol”) OT/B 2% “Dispasol” AC 5% Pottery clay 25% Silica 40% Example 11 Dispersion by mixing the following ingredients and grinding the mixture with a comminution mill. A powder formulation was prepared: Compound No. 8 of Table 1 25% “Perminal” BX 1% “Dispazol” T 5% Polyvinylpyrrolidone 10% Silica 25% Ceramic clay 34% Example 12 Below A dispersible powder formulation was prepared by mixing the ingredients and grinding the mixture: Compound of Table No. 9 25% "Aerosol" OT/B 2% "Dispasol" A 5% Ceramic clay 68% The proportions of ingredients in Examples 3-12 are by weight. Descriptions of the various compositions and materials indicated by trade names and trade names in the examples above are provided below. “Lubrol” L: Nonylphenol (1 mol)
and ethylene oxide (13 mol) "Aromazole" H: Solvent mixture consisting of alkylbenzene "Dispazole" T and AC: Mixture of sodium sulfate and formaldehyde-sodium naphthalene sulfonate condensate "Lubrol" APN5: Nonyl Condensation product of phenol (1 mol) and naphthalene oxide (5.5 mol) "Cellophas" B600: Sodium carboxymethylcellulose thickener "Lisapol" NX: Condensation product of nonylphenol (1 mol) and ethylene oxide (8 mol) Aerosol" OT/B: Dioctyl Sodium Sulfosuccinate "Perminal" BX: Sodium Alkyl Naphthalene Sulfonate Example 13 The compounds of the present invention were tested against diseases caused by various fungi that parasitic the leaves of plants. The test method used was as follows. The test plants were grown in John Innes potting compost (No. 1 or No. 2) in small pots with a diameter of 4 cm. A layer of fine sand was placed at the bottom of the pot containing the dicots to facilitate uptake of the test compound by the roots. Test compounds were formulated either by bead milling with aqueous Dispersol T or as solutions in acetone or acetone/ethanol, which were diluted to the desired concentration immediately before use. For leaf diseases, a suspension of 100 ppm of active ingredient was sprayed on the leaves and applied through the soil to the roots of the same plants. In the case of tests for Botrytis cineaa, Plasmopara viticola and Venturia inaequalis, the test compound was applied only to the leaves. The spray solution was applied to maximize retention and the root drench solution was applied to a final concentration equal to approximately 40 ppm active ingredient per dry soil. Tween 20 was added to a final concentration of 0.05% when the spray solution was applied to the grain. For most studies, test compounds were applied to the soil (roots) and foliage (by spraying) 1 to 2 days before inoculating the plants with the pathogen, with the exception of the case of barley powdery mildew (Erysphe graminis). Plants were inoculated 24 hours before treatment. After inoculation, the plants were transferred to a suitable environment for infection and then cultured until the severity of disease was evaluated. The period from inoculation to evaluation was 4 to 14 days depending on the type of disease and environment. Disease control was recorded according to the following grades: 4 = no disease 3 = 0-5% 2 = 6-25% 1 = 26-60% 0 = 60% or more The results are shown in the table.

【table】

[Table] “-” means not tested.

Claims (1)

[Claims] 1 General formula (): (In the formula, R ¹ represents a (C _1-4 ) alkyl group or a halophenyl group, and R ² represents a halophenyl group) (its cis- or trans isomer, or a mixture thereof)
and its acid addition salts and metal complex salts. 2 R ¹ is a butyl group or a halophenyl group,
2. The compound according to claim 1, wherein R ² is a halophenyl group. 3 R ¹ is a butyl group, 2-chlorophenyl group, 2
-fluorophenyl group, 2-bromophenyl group,
4-chlorophenyl group or 2,4-dichlorophenyl group, R ² is 4-fluorophenyl group,
The compound according to claim 1 or 2, which is a 4-chlorophenyl group or a 2,4-dichlorophenyl group. 4. The compound according to claim 1 or 2, wherein R ¹ is an n-butyl group and R ² is a 2,4-dichlorophenyl group. 5 General formula (): General formula (), characterized in that the compound represented by (wherein R ¹ and R ² have the meanings given below) is dehydrated by refluxing it in a solvent under acidic conditions: (In the formula, R ¹ represents a (C _1-4 ) alkyl group or a halophenyl group, and R ² represents a halophenyl group) (its cis- or trans isomer, or a mixture thereof)
manufacturing method. 6 General formula () or (): [Formula] [Formula] (wherein R ¹ and R ² have the same meanings as above,
Y represents a halogen atom, preferably a chlorine or bromine atom),
- preparing compounds of the general formula () by reacting the triazole with a 1,2,4-triazole in the presence of an acid binder or in the form of an alkali metal salt in a customary solvent; The method described in scope item 5. 7 Compounds of general formula () or () are dissolved in a conventional solvent such as acetonitrile, methanol, ethanol or dimethylformamide for 20 to
Reacting with the sodium salt of 1,2,4-triazole (this salt can be prepared by adding sodium hydride or sodium methoxide to 1,2,4-triazole) at a temperature of 100°C. The method described in item 6. 8 General formula (a) or (b): [Formula] [Formula] (wherein R ¹ , R ² and Y have the same meanings as above), respectively, a ketone compound represented by the general formula (a) ) or (b): Z-Mg-R ² (a), Z-Mg-R ¹ (b) (wherein R ¹ and R ² have the same meanings as above,
Patent for the preparation of compounds of general formulas () and () by reaction with a Grignard reagent of Z represents halogen, preferably chlorine, bromine or iodine, in a convenient solvent such as diethyl ether or tetrahydrofuran. The method according to claim 6. 9 A suitable benzophenone compound represented by the general formula (): R ¹ -CO-R ² () (in the formula, R ¹ and R ² have the same meanings as above) is dimethyloxosulfonium methylide or dimethylsulfonium methylide. By reacting with Ride, each of R ¹ and R ² (even if they are the same,
Claim 6, which produces a compound of general formula (), in which (which may be different) is a substituted phenyl group
The method described in section. 10 General formula (): (In the formula, R ¹ represents a (C _1-4 ) alkyl group or a halophenyl group, and R ² represents a halophenyl group) (cis- or trans isomer thereof, or a mixture thereof),
An agricultural and horticultural fungicide composition comprising a salt or a metal complex salt thereof, and a carrier or diluent thereof.