WO1997005120A1 - Triazolone derivatives, use of the same and intermediates in the production of the same - Google Patents

Abstract

Triazolone derivatives represented by general formula (a), wherein R1 represents optionally substituted aromatic hydrocarbyl, etc.; R?2 and R6¿ represent each hydrogen, etc.; R3 represents C¿1-3? alkyl, etc.; R?4¿ represents C¿1-3? alkyl, etc.; W represents oxygen or sulfur; and -A- represents -O-, etc.; a plant disease control agent comprising the same as the active ingredient; and intermediates in the production of the same. The compounds exert excellent effects of controlling plant disease damages.

Description

 Description Triazolone derivatives, their uses and intermediates for their production Technical field of the invention

 The present invention relates to a triazolone derivative, its use, and an intermediate for its production.

Background art

 Conventionally, a certain triazolone derivative is described in Japanese Patent Publication No. 41-116, and it cannot be said that the triazolone derivative is always always sufficient in terms of plant disease control effect.

Disclosure of the invention

 The present inventors have conducted intensive studies to develop compounds having an excellent controlling effect on plant diseases. As a result, the triazolone derivative represented by the general formula (a) described below has an excellent controlling effect on various plant diseases. It has been found that the present invention has been made.

 That is, the present invention

 —General formula (a)

[In the formula, R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ² and R ⁶ are the same or different, and represent a hydrogen atom, methyl Group, halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), trifluoromethyl group or methoxy group, R ³ is d to C ₃ alkyl group (eg, methyl group, ethyl group, etc.), cyclopropyl group , C 2 _-C:, alkenyl group (e.g., vinyl-group), represents a triflate Ruo b methyl or Shiano group, R ⁴ (iC, -C ₃ § alkyl group (e.g., methyl group, Echiru group) W represents an oxygen atom or a sulfur atom, 1 A— is 10—, (hereinafter, R ′ is bonded to each leftmost atom) One OCH ₂ —, -S CH ₂ one, one CH ₂ O—, one CH ₂ OC (= 0) —, one C (R ⁵ ) = N-OCH _2- (where R ^s is a hydrogen atom ,) or a N double C (SCH ₃₎ SCH ₂ represents a methyl group or Echiru group - represents a group represented by.. ] (Hereinafter referred to as the compound of the present invention) and a plant disease controlling agent comprising the triazolone derivative as an active ingredient.

 The present invention further provides a compound of the general formula (b) useful as an intermediate for the preparation of some of the compounds of the present invention:

[In the formula, R ′, R ² , R ⁶ and one A— represent the same meaning as described above, and R ³ ′ represents a d-C ₃ alkyl group (eg, methyl group, ethyl group, etc.), cyclopropyl group, trifluoromethyl Or a cyano group. ]

A triazolone compound represented by the formula: and a general formula (c) useful as a production intermediate of the compound of the present invention.

( _c )

[In the formula, R ¹ , R ² , R ⁴ , R ⁶ , W and one A— represent the same meaning as described above. ]

A hydroxymethyltriazolone compound represented by

 General formula (d)

[Wherein, R ¹ , R ² , R ⁴ , R ⁶ , W and —A— have the same meaning as described above. ]

A formyl triazolone compound represented by the formula: and a general formula (e)

 HON = CH

[Wherein, R ¹ R ² , R ⁴ , R ^s , W and —A— have the same meaning as described above. ]

And a triazolone oxime compound represented by the formula:

In the present invention, examples of the substituent of the optionally substituted aromatic hydrocarbon group and the optionally substituted aromatic heterocyclic group represented by R ¹ include a halogen atom (a fluorine atom, a chlorine atom, Atom, bromine atom, etc.), C, -C ₄ alkyl group (for example, methyl group, ethyl group, isopropyl group, tert-butyl group, etc.), C, -C ₄ haloalkyl group (for example, trifluoromethyl group, etc.) ), A C, -C ₄ alkoxy group (for example, a methoxy group, an ethoxyquin group, etc.), a C, -C ₄ haloalkoxy group (for example, a trifluoromethoxy group, etc.), a phenoxy group (the phenoxy group is a methyl group , A halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, etc.), a methoxy group, a trifluoromethyl group or a cyano group).

In the present invention, examples of the aromatic hydrocarbon group in the optionally substituted aromatic hydrocarbon group represented by R ′ include a phenyl group, a mononaphthyl group, and a β-naphthyl group. Examples of the aromatic heterocyclic group in the optionally substituted aromatic heterocyclic group represented by R ′ include a 2-, 3-, 4-pyridyl group, a 21,41,5-pyrimidinyl group Group, pyrazine-1-yl group, 2-, 3-furyl group, 2-, 3-phenyl group, 2-, 4-1,5-thiazolyl group, 2-, 41-, 5-oxazolyl group, 3-, 4--1,5-isoxazolyl group, 3-, 4-, 5-isothiazolyl group, 1,3-, 4-pyrazolyl group, 1,2,3-triazolyl-1 1,2,3-triazolyl_4-yl group, 1,2,3-triazolyl-5-yl group, 1,2,4-triazolyl-1-yl group, 1,2, 4-triazolyl-3-yl, 1,2,4-triazolyl 4-yl, 1,2,5-thiadiazoyl-3-yl, 1,2,5-oxadiazoyl-3-yl And a benzothiazol-2-yl group.

In the compound of the present invention, a group represented by 1 OCH ₂ — (where an oxygen atom is bonded to R ′) is mentioned as a preferred embodiment 1A— from the viewpoint of plant disease control effect.

 The compound of the present invention may have two isomers (E) and (Z) based on a C = N double bond, each of which and a mixture thereof are included in the present invention.

 (The terms (E) and (Z) as used herein are defined by the Kahn-Ingold-Prog system, which is widely used to indicate geometric isomers.)

 Next, a method for producing the compound of the present invention will be described.

Among the compounds of the present invention, compounds in which W is an oxygen atom and R ³ is a C, -C ₃ alkyl group, cyclopropyl group, trifluoromethyl group or cyano group are described in, for example, the following scheme S-1

[Wherein, R ′, R ² , R ³¹ , R ⁴ , R ⁶ and A have the same meaning as described above, and X represents a chlorine atom, a bromine atom, an iodine atom, a tosyloxy group or a mesyloxy group. ]

Thus, it can be produced by reacting the triazolone compound of the general formula (b) with an alkylating agent (R ⁴ —X or R ′, SO,) in the presence of a base. In this case, the base used is, for example, potassium carbonate, sodium carbonate, Examples thereof include sodium hydride and sodium hydroxide.

Among the compounds of the present invention, compounds in which W is a sulfur atom and R ³ is Ci to (: ₃ alkyl group, cyclopropyl group or trifluoromethyl group are exemplified by the following scheme S—2

KOH aqueous solution

R ¹ — AN

During R 32 Industrial ^{formula, R ', R 2, R} 4, R 6 and A have the same meanings as defined above, R ³² is Wath -C ₃ alkyl group, a cyclopropyl group or a triflate Ruo Russia methyl table. ]

, For example, by cyclizing acylthiosemicarbazide [V] in, for example, an aqueous potassium hydroxide solution.

Further, among the compounds of the present invention, a compound in which R ³ is a cyano group is exemplified by the following scheme S_ 3 XS

 (1 1 3

[Wherein, R ¹ , R ² , R ⁴ , R ⁶ , W and A represent the same meaning as described above. By reacting a 3-chlorotriazolone derivative represented by the general formula (1 13) with a cyanating agent (for example, sodium cyanide, potassium cyanide, copper cyanide, etc.) You can also. The amount of the reagent used in the reaction is usually 1 to 3 mol per 1 mol of the 3-chlorotriazolone derivative represented by the general formula (113), and the reaction temperature And the reaction time is usually Each—20 ° C. to 150 ° C. or the boiling point of the solvent and about 30 minutes to 24 hours. In the above reaction, a solvent is not necessarily required, but usable solvents include amides such as N, N-dimethylformamide, sulfur compounds such as sulfolane and dimethyl sulfoxide, and ethers such as tetrahydrofuran. And aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as chlorobenzene, water, and mixtures thereof.

 After completion of the reaction, the reaction solution is subjected to usual post-treatments such as neutralization and extraction, and further purified as necessary by operations such as chromatography and recrystallization to isolate the desired compound of the present invention. be able to.

Further, among the compounds of the present invention, the following compound [VI] wherein R ³ is a cyano group is represented by the following scheme S—4

 (e) (VI)

Wherein R ′, R ² , R ⁴ , R ⁶ , W and A have the same meaning as described above. ], The hydroxymethyltriazolone compound (c) is oxidized with an oxidizing agent such as manganese dioxide to form a formyltriazolone compound (d), and then the compound is reacted with hydroxylamine hydrochloride or the like in the presence of a base such as pyridine. To give the triazolone oxime compound (e), followed by dehydration with acetic anhydride or the like.

In the compound of the present invention, R ³ is a cyano group or a trifluoromethyl group, and A is —OCH ₂ —, —S CH ₂ —, —C (R ⁵ ) = N-OCH ₂ (Where R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.) Or one N = C (SCHs) SCH _{2 The} compound [IX] represented by the following scheme S-5

[Wherein, R ′, R ² , R ⁶ and W have the same meaning as described above, Z is an oxygen atom, a sulfur atom, and C (R ⁵ ) = N—0— (where R ⁵ is a hydrogen atom , Or a methyl group or an ethyl group.) Or —NCC (SCH ₃ ) S—, and R ³³ represents a cyano group or a trifluoromethyl group. ]

In accordance with the above, a compound represented by the general formula [VII] and a promide [VIII] (for example, which can be produced according to Production Example 5 of the intermediate described below) are optionally added in a solvent in the presence of a base. It can also be obtained by reacting. In this case, usable bases include, for example, potassium carbonate, sodium carbonate, sodium hydroxide, sodium hydride, sodium methylate, and the like. Examples of the solvent include N, N— Examples thereof include dimethylformamide, tetrahydrofuran, methanol, ethanol, dimethylsulfoxide, toluene, and water.

Further, among the compounds of the present invention, a compound in which A is —0— or —CH ₂₀ — is represented by the following scheme S-6

 (X) (XI) (XII)

[Wherein, R ¹ , R ² , R ³ , R ⁶ and W represent the same meaning as described above, Y represents a halogen atom (a chlorine atom, a bromine atom, an iodine atom, etc.), and n represents 0 or 1. I will. ] In the presence of a base, a halide [X] and a phenolic compound [XI] (e.g., can be produced according to Production Example 6 of the intermediate described below) in a solvent if necessary Can also be obtained. In this case, usable bases include, for example, lithium carbonate, sodium carbonate, sodium hydroxide, sodium hydride, sodium methylate and the like, and examples of the solvent include N, N-dimethyl Examples thereof include formamide, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, toluene, and water. Further, among the compounds of the present invention, the compound in which R ³ is a C ₂ -C ₃ alkenyl group is, for example, a formyltriazolone compound (d) produced according to the above-mentioned scheme S-4 or the like,

 (d)

[Wherein, R ¹ , R ² , R ⁴ , R ⁶ , W and A have the same meaning as described above, R ⁷ represents a hydrogen atom or a methyl group, and Ph represents a phenyl group. ]

According to the reaction with a Wittig reagent or the like. Further, among the compounds of the present invention, a compound in which R ³ is a d to C ₃ alkyl group, a cyclopropyl group or a trifluoromethyl group is represented by the following scheme S-8

R ^{32 Wherein, RRR 3 2 R 4, R} 6, W and A Wath table as defined above. ]

Can be produced by reacting iso (thio) cyanate [XIII] with a hydrazide derivative to obtain acyl (thio) semicarbazide [XIV], followed by ring closure in, for example, an aqueous potassium hydroxide solution.

 Next, a method for producing an intermediate when producing the compound of the present invention will be described.

Among the triazolone compounds represented by the general formula (b), a compound in which R ³¹ is a C ₃ alkyl group, a cyclopropyl group or a trifluoromethyl group is produced, for example, according to the following reaction scheme S-9. be able to.

 (I) (II)

KOH aqueous solution

[Wherein, R ′, R ² , R ³² , R ⁴ , R ⁶ and A have the same meaning as described above. That is, the isocyanate of the formula [I] is reacted with a hydrazide compound to give an acylsemicarbazide of the formula [II], which can be obtained, for example, by ring closure in an aqueous solution of potassium hydroxide.

Among the triazolone compounds represented by the general formula (b), a compound in which R ³ ′ is a cyano group can be produced, for example, according to the following scheme S-10.

 CXVII

[Wherein, R ¹ , R ² , R ⁴ , R ⁶ and A have the same meaning as described above. The alcohol [XV] is oxidized to an aldehyde [XVI] with an oxidizing agent such as manganese dioxide, and then the aldehyde compound is treated with a hydroxyamine hydrochloride or the like in the presence of a base such as pyridine to obtain an oxime compound [XVII]. And then dehydrated with acetic anhydride or the like.

 The acylthiosemicarbazide represented by the formula [V] can be produced, for example, according to the following reaction scheme S-11.

[Wherein, R ¹ , R ² , R ³² , R ⁴ , R ⁶ and A have the same meaning as described above. That is, the isothiocynate of the formula [1Π] is reacted with an alkylhydrazine to give a thiosemicarbazide of the formula [IV], which is then converted to an acid chloride or an acid anhydride. And can be obtained by reacting

 —The 3-chlorotriazolone derivative of the general formula (113) can be prepared by the method described in JH Cooley et al., J. Org. Chem. 54, 1048-1051 (1989), or by using chloroformate formic acid instead of phosgene in the method. It can be produced by a method using trichloromethyl [diphosgene] or bis (trichloromethylenole) carbonate [triphosgene].

 The hydroxymethyltriazolone compound represented by the formula (c) can be produced, for example, according to the following reaction scheme S-12.

 HOCH

 (c)

[Wherein, R ¹ , R ² , R ⁴ , R ⁶ , W and A represent the same meaning as described above. That is, iso (thio) cyanate [XIII] is reacted with a 2-hydroxyacetohydrazide derivative to give 2-hydroxyacetyl (thio) semicarbazide [XVIII]. Can be obtained by closing the ring.

Among the hydroxymethyltriazolone compounds represented by the formula (c), compounds in which W is an oxygen atom, and alcohols represented by the formula [XV] can be produced according to the following reaction scheme S-13. R

[Wherein, R ¹ R ² R ⁴ R ⁶ X and A represent the same meaning as described above. That is, by reacting the isocyanate [I] with the 2-hydroxyacetohydrazide compound, 2-hydroxyacetyl semicarbazide [XIX] is obtained, for example, by ring closure in an aqueous solution of potassium hydroxide to give alcohol [XV]. , then in presence of a base alkylating agent (R ⁴ - X or R _⁴ 2 S0 ⁴⁾ and can be obtained by the reacting. In this case, examples of the base to be used include carbonated lime, sodium carbonate, sodium hydride, sodium hydroxide, and the like, and examples of the solvent include NN-dimethylformamide, toluene, and tetrahydrofuran. , Methanol, ethanol, dimethylsulfoxide, water and the like can be appropriately selected as needed.

 Examples of plant diseases against which the compound of the present invention has control effect include rice blast (Pyricularia oryzae) ヽ sesame leaf blight (Cochliobolus miyabeanus and crested blight)

(Rhizoctonia solani), wheat powdery mildew (Erysiphe graminis, f.s.hordei, f.sp.tritici), red mold (Gibberella zeae), rust (Puccinia stri iformis, P. graminis, P. recondita) , P. hordei), Snow rot (Typhula sp., Micronectriella nivalis). Naked smut (Ustilago tritici, U. nuda), Blue scab (Ti lletia caries) ^ Eye spot (Pseudocercosporella herpotrichoides), Scab Rhynchosporium secalis, Leaf blight (Septoria tritici), Blight blight (Leptosphaeria nodorum), Black spot of citrus (Diaporthe citri), Scab (Elsinoe fawcetti), Fruit rot (Penicillium digitatum, P. itali cum) , Mongolian disease of coral (Sclerotinia mali), rot (Valsa mali), powdery mildew (Podosphaera leucotricha), spot leaf rot (Alternaria mali).

(Venturia inaequalis), Pear scab (Venturia nashicola), Black spot

(Alternaria kikuchiana), red scab (Gy sleep sporangium haraeanum), peach scab (Sclerotinia cinerea), black scab (Cladosporium carpophilum), phomopsis rot (Phomopsis sp.), Grape black spot (Elsinoe ampelina) , Rot (Glomerella cingulate), powdery mildew (Unc inula necator), rust

(Phakopsora ampelopsidis), downy mildew (Plasmopara v icola), anthracnose of ikiki (Gloeosporium kaki), deciduous disease (Cercospora kaki, Mycosphaerella nawae), anthracnose (Col letori chum lagenarium) Powdery mildew (Sphaerotheca fuliginea, vine blight (Mycosphaerella melonis) ヽ Downy mildew (Pseudoperonospora cubensis) s Brown spot disease (Phomopsis vexans), powdery mildew (Erysiphe cichoracearum), black spot disease of Abufunaceae field (Alternaria japonica), white spot disease (Cercosporella brassicae li), dried spot of soybean (Puccinia allii), purple spot of soybean (Cercospora kikuchii), Black spot (Elsinoe glycines). Black spot (Diaporthe phaseolorum var. Sojae), Green anthracnose

 (Colletotrichum lindemuthia 麵), black rot of laccasey (Mycosphaerella perso octopus tum), brown spot (Cercospora arachidicola) ヽ Endo powdery mildew

 (Erysiphe pisi), Potato Summer Blight (Alternaria solani).

 (Phytophthora infestans), strawberry powdery mildew (Sphaerotheca humuli), chaff net (Exobasidium reticulatum). White scab (Elsinoe leucospila), evening scab (Alternaria longipes), powdery mildew (Ery) cichoracearum), Anthracnose (Colletotrichum tabacum), Sugar beet leaf spot (Cercospora beticola), Black spot of dill (Diplocarpon rosae), Powdery mildew (Sphaerotheca pannosa;), Brown spot of chrysanthemum (Septoria chrysanthemi-indici) ) ヽ White rust (Puccinia horiana) 灰色 Gray mold of various crops (Botrytis cinerea), Sclerotinia (Sclerotinia)

 sclerotiorum), plague (Phytophthora sp.), downy mildew (Plasmopara sp.,

Pseudoperonospora sp., Peronospora sp., Bremia sp., ¾cierospora sp.) No.

 When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, it may be used as it is without adding any other components.However, it is usually mixed with a solid carrier, a liquid carrier, a surfactant and other auxiliary agents for formulation. Into emulsions, wettable powders, suspensions, granules, powders, liquids, etc.

 These preparations generally contain the compound of the present invention as an active ingredient in a weight ratio of 0.1 to 99%, preferably 1 to 90%.

As the solid carrier, for example, fine powders or granular materials such as kaolin clay, attapulgitite clay, bentonite, acid clay, pyrophyllite, talc, diatomaceous earth, calcite, knollemi powder, urea, ammonium sulfate, synthetic hydrated silicon oxide, etc. Examples of the liquid carrier include aromatic hydrocarbons such as xylene and methylnaphthalene; alcohols such as isopropanol, ethylene glycol and cellosolve; acetone; ketones such as cyclohexanone and isophorone; soybean oil; Vegetable oils such as cottonseed oil, dimethylsulfoxide, acetonitrile, water and the like. Surfactants used for emulsification, dispersion, wet spreading, etc. include, for example, alkyl sulfate esterol, alkyl (aryl) sulfonate, Dialkyl sulfosuccinic acid , Anionic surfactants such as polyoxyethylene alkyl aryl ester phosphate, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ester, polyoxyethylene polyoxypropylene block copolymer And non-ionic surfactants such as sorbitan fatty acid ester and polyoxyethylene sorbitan fatty acid ester. Examples of the pharmaceutical adjuvant include lignin sulfonate, alginate, polyvinyl alcohol, gum arabic, CMC (carboxymethyl cellulose), PAP (acidic isopropyl phosphate) and the like. These formulations may be used as they are or diluted with water and sprayed on foliage, or may be used in various forms such as dusting, scattering and mixing with soil, or application to soil. Further, it can be applied as a seed treating agent by seed dressing treatment, seed immersion treatment, seed spraying treatment and the like. In addition, by using it in combination with other plant disease controlling agents, it can be expected to enhance the controlling effect. In addition, it can be used in combination with insecticides, acaricides, nematicides, herbicides, plant growth regulators, fertilizers, and soil conditioners. The compound of the present invention can be used as an active ingredient of a plant disease controlling agent for paddy fields, fields, orchards, tea fields, pastures, lawns, and the like.

 When the compound of the present invention is used as an active ingredient of a plant disease controlling agent, its application rate is

Per g are usually 0.1 g to 100 g, preferably 0.2 g to 20 g.When diluting an emulsion, a wettable powder, a suspension, a liquid, etc. with water, The application concentration is from 0.00000001% to 50%, preferably from 0.00001% to 10%. Granules, dusts, etc. are applied without dilution.

BEST MODE FOR CARRYING OUT THE INVENTION

 Hereinafter, the present invention will be described in more detail with reference to Production Examples, Formulation Examples, Test Examples, and the like, but the present invention is not limited to only these examples.

 First, Production Examples of the compound of the present invention will be described.

Production Example 1 (Example of production according to Scheme S-1)

4- {2 - [[<¾- methyl (3-triflate Ruo b-methyl) benzylidene] Amino Okishimechiru] Hue sulfonyl} -3-methyl-one delta ² - 1, 2, 4-Toriazorin one 5 one on [hereinafter intermediate 0.60 g (1.54 mol) and 0.26 g (1.85 mol) of methyl iodide were dissolved in 5 ml of N, N-dimethylformamide, and the mixture was cooled to 10 ° C or lower. 74 mg (1.85 mmol) of 60% oily sodium hydride was added. After stirring at the same temperature for a while, the temperature was gradually raised to room temperature and stirred for 1 晚. Ice water was added to the reaction solution, which was extracted with ethyl acetate. The extract was washed with water, concentrated, and the residue was subjected to silica gel column chromatography (eluent; ethyl acetate: n-hexane = 2: 1 (v / v)) to give 4- {2 — [[α - methyl one (3-triflate Ruo b-methyl) benzylidene] Amino Okishimechiru] Hue sulfonyl} - 1, 3-dimethyl-one delta ² - 1, 2, 4-Toriazori Hmm 5- one (present compound (22)) 0.49 g was obtained.

 NMR-NMR (CDC 13 / TMS) <5 (ppm)

 2.00 (3H, s), 2.20 (3H, s), 3.47 (3H, s), 5.18 (2H, s), 7.0-8.0 (8H, m) Production example 2 (Example of production by scheme 12)

4- [2- (2,5-dimethylphenoxymethyl) phenyl] -1-methyl-1-acetylthiosemicarbazide [Prepared in Intermediate Production Example 2] 0.23 g (0.64 mmol) of 2 The solution was added to a 2% aqueous solution of potassium hydroxide and stirred at 90 ° C. for 3 hours. After cooling the reaction solution, water was added, and the mixture was extracted with ethyl acetate. The extract was subjected to silica gel column chromatography (eluent: ethyl acetate: _n- hexane = 1: 1 (v / v)) to give 4- (2- (2,5-dimethylphenoxymethyl) phenyl). -1, 3 Jimechiru ^{- Δ 2 - 1, 2,} 4- WINCH Riazorin one 5- thione (present compound (1 5)) was obtained 0.21 g.

m p. 105.4 ° C

Production Example 3 (Example of production according to Scheme S-3)

4 one [2- (2, 5-dimethyl-phenoxyethanol methyl) phenyl] one 1-methyl-3-black port - delta ² - at 1, 2, 4-Toriazorin one 5- On Production Example 3 described later intermediates Production] 0.30 g (0.87 mmol) and 47 mg (0.96 mmol) of sodium cyanide were reacted in 3 ml of dimethylformamide at 70 to 80 ° C for 8 hours. Ice water was added to the resulting reaction solution, which was extracted with ethyl acetate. The extract was concentrated, and the residue was subjected to silica gel column chromatography (eluent; ethyl acetate: n-hexane = 1: 1 (v / V)) to give 4- [2- (2,5-dimethylphenyl). Enokishimechiru) phenyl] one 1-methyl 3- Shiano Δ ² - 1, ^2, 4- Toriazorin one 5- one (present compound (13)) was obtained 0.25 g.

 Ή-NMR (CDC 1 TMS) δ (ppm)

2.12 (3H, s), 2.28 (3H, s), 3.50 (3H, s), 4.98 (2H, s), 6.5-7.8 (7H, m)

Production Example 4 (Example of production by the final process of Scheme S_4)

4- (2-benzyloxy) phenyl 1-methyl-3-hydroxyimino 1 △ ² — l, 2,4-triazolin-1 5 _one [Prepared in Intermediate Production Example 4 described below] 1.73 (5.34 mmol) anhydrous It was dissolved in 10 ml of acetic acid and stirred at 130 to 140 ° C for 8 hours. The reaction mixture was concentrated under reduced pressure, and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate: _n- hexane = 3: 2 (v / v)) to give 4- (2-benzyloxy) phenyl-1. 1.37 g of —methyl-3-cyano-Δ ² —1,2,4-triazolin-5-one (compound of the present invention (44)) was obtained.

 Ή-NMR (CDC 1: ZTMS) δ (ppm)

3.59 (3H, s), 5.14 (2H, s), 7.05- 7.15 (2H, m), 7.30-7.50 (7H, m)

Production Example 5 (Example of production according to Scheme S-5) _i ^

60% oily sodium hydride (56 mg, 1.4 mL), dimethylformamide (2 ml) was added, and while stirring, 2,5-dimethylphenol (0.17 g, 1.4 mmol) was added, followed by stirring for 1 hour. did. To the resulting solution, under ice-cooling, with stirring, 4- [4 one-chloro 2- (Promo methyl)] Fuweniru 1 _ methyl one 3- Shiano one delta ² - 1, 2, 4-Application Benefits azolin - 5 _ ON [Manufactured in Production Example 5 of Intermediate described below] A solution prepared by dissolving 0.40 g (1.22 mol) in 2 ml of dimethylformamide was added dropwise. After completion, the temperature was raised to room temperature and stirring was continued. Ice water was added to the reaction solution, which was extracted with ethyl acetate. The extract was washed with water, concentrated, and the residue was subjected to silica gel gel chromatography (eluent: ethyl acetate: n-hexane = 1: 1 (v / v)) to give 4— [4_ one 2- (2, 5-methylphenoxy) methyl] phenylene Lu 1-methyl one 3- Shiano one delta ² - 1, 2, 4 one Toriazorin one 5- one (present compound (51)) the 3 2 5 mg Obtained.

 Ή-NMR (CDC 1 / TMS) δ (ppm)

2.14 (3H, s), 2.29 (3H, s), 3.55 (3H, s), 4.95 (1H, d, J = 12.6Hz), 5.08 (1H, d, J = 12.6Hz), 6.58 (lH, s), 6.71 (1H, d, J = 8Hz), 7.01 (1H, d, J = 8Hz), 7.26 (1H, d, J = 8Hz). 7.50 (1H, dd, J = 8Hz, 2Hz), 7.68 (1H, d, J = 2Hz)

Production Example 6 (Example of production according to Scheme S-6)

6 0% oily sodium hydride 6 4 mg (1.6 mmol) in dimethyl formamidine de 2 ml was added, here stirring 4 one at room temperature (2-heat Dorokishifuweniru) -1, 3-dimethyl-delta ² - 1, 2 , 4-1-triazolin-5-one [Prepared in Production Example 6 of Intermediate described below] 0.30 g (1.46 recited ol) was added, and the mixture was stirred for 1 hour. Then, 0.35 g (1.6 ol) of 2,3-dichloro-1- (trifluoromethyl) pyridine was added thereto and reacted at 60 ° C. for 6 hours with stirring. Ice water was added to the reaction solution, extracted with ethyl acetate, washed with water and concentrated. The residue was subjected to gel chromatography on silica gel (eluent: ethyl acetate: n-hexane = 2: 1 (v / v)) to give 4- [2- [3-chloro-5- (trifluoromethyl) ) Pirijiru 2 Okishi] phenyl 1 - 1, 3-dimethyl chill - delta ² - 1, 2, 4-Toriazorin one 5 _ one (present compound (67)) was obtained 0.56 g.

m.p. 150.5 ° C

Production Example 7 (Example of production according to Scheme S-7) 1.7 ml of an n-BuLi 1.6N hexane solution was added to 1 Oml of ether under a nitrogen atmosphere, and 0.96 g (2.7 mmol) of methyltriphenylphosphonium bromide was gradually added thereto at room temperature. After stirring for 4 hours, 4 i (2 - [(2, 5-Jimechirufueno) methyl] Fuweniru} - 1-methyl 3-formyl-one delta ² - 1, 2, 4-Doo Riazorin - 5-one [hereinafter intermediate 0.45 g (1.34 mmol) was added thereto, and the mixture was allowed to undergo a 氷 reaction. Ice water was added to the reaction solution, extracted with ethyl acetate, and the extract was washed with water and concentrated. The residue was subjected to silica gel column chromatography (eluent: ethyl acetate: _n- hexane = 2: 1 (vZv)) to give 4- {2-([2,5-dimethylphenoxy) methyl] phenyl. Le} one 1 one methyl one 3-vinyl Le ^{- Δ 2 - 1, 2,} 4- Toriazorin one 5- one (present compound (45)) to give the 1 1 2 mg.

 Ή-NMR (CDC 13 / TMS) δ (ppm)

2.14 (3H, s), 2.27 (3H, s), 3.54 (3H, s), 5.00 (2H, s), 5.36 (1H, d, J-12Hz), 5.69 (lH, d, J2 18Hz), 6.11 (1H, dd, J = 12Hz, 18Hz), 6.60 (1H, s), 6.67 (1H, d, J = 7Hz). 6.99 (1H, d, J = 7Hz), 7.23 (1H, t, J 7 Hz), 7.4-7.6 (2H, m), 7.71 (1H, d, J = 7 Hz) Next, examples of the compound of the present invention are shown in Table 1 (the definition of each substituent in the general formula (a) is shown below). ). In Table 1, Me represents a methyl group, Et represents an ethyl group, n—Pr represents a propyl group, i—Pr represents an isopropyl group, and c—Pr represents a cyclopropyl group. The leftmost atom of A is bonded to R '.

table 1

Table 1 (continued)

Table 1 (continued)

Compound R and R ⁴ AW

(19) CF, -oV H Me Me H CH O O

(20) Me- <0>-H Me Me H CHoO O

(21) H Me Me H CH, 0 O

(22) —0-CH ₂ -O

(23) _OCH ₂ - 0

 Me

(24)-OCH ₂ -O

(25) OCH ₂ — O

(26) H Me Me H - C = N- OCH 2 - 0

 Me

(27) H Me Me H ON- OCH ₂ -O

Me 1 (continued)

Table 1 (continued)

1 (continued)

Table 1 (continued)

Table 1 (continued)

Next, some physical properties of the examples of the present compound [ 'H- NMR (CDC 1 ZTMS, δ (ppm)) data, melting point (mp) or refractive index (n _D value)] are shown.

 (I) m.p. 99.7 ° C

 (4) m.p. 73.4 ° C

(II) 1.30 (3H, t, J = 7 Hz), 2.10 (3H, s), 2.26 (3H, s), 3.82 (2H, q, J = 7 Hz), 4.95 (2H, s), 6.5-7.8C7H, m)

(14) 2.15 (3H, s), 2.26 (3H, s), 3.87 (3H, s), 4.99 (2H, s), 6.5-7.8 (7H, m) (16) 2.13 (3H, s), 3.38 (3H, s), 6.8-7.6C9H, m)

(18) m.p. 108.1 ° C

(36) 2.00 (3H, s), 2.26 (3H, s), 2.30 (3H, s), 3.56 (3H, s), 5. ll (2H, s),

6.95 (2H, s), 7.0-7.3 (IH, m), 7.4- 7.7 (2H, m), 7.9-8.3 (lH, m) (41) 2.10 (3H, s), 3.41 (3H, s), 6.60 (1H, s), 7.2-7.5 (5H, m),

 7.5-7.7 (3H, m), 8.32 (1H, s)

 (46) 2.19 (3H, s), 2.23 (3H, s), 3.55 (3H, s), 5.03 (1H, d, J = 13Hz),

 5.16 (1H, d, J = 13Hz), 7.35-7.55 (3H, m), 7.63 (1H, d, J = 8Hz),

7.77 (1H, d, J = 8Hz), 7.83 (1H, s)

 (47) 2.22 (3H, s), 2.29 (3H, s), 3.57 (3H, s), 4.8K1H, d, J = 12Hz),

 4.97 (1H, d, J = 12Hz), 6.57 (1H, s), 6.72 (1H, d, J = 7Hz),

 7.02 (lH, d, J = 8Hz), 7.40 (1H, d, J = 2Hz), 7.48 (1H, d, J = 2Hz)

(48) 2.25 (3H, s), 3.57 (3H, s), 5.14 (1H, d, J = 13Hz), 5.26 (1H, d, J = 13Hz) 7.1-7.4 (3H, m), 7, 50 (1H, t, J = 9Hz), 7.62 (1H, d, J = 9Hz),

 7.78 (1H, d, J = 9Hz). 7.84 (1H, s)

 (49) 2.16 (3H, s), 2.29 (3H, s), 3.57 (3H, s). 4.97 (1H, d, J = 13Hz),

 5.07 (1H, d, J = 13Hz), 6.58 (1H, s), 6.72 (1H, d, J = 8Hz),

 7.03 (lH, d, J = 8Hz), 7.15-7.5 (3H, m)

 (50) 2.2K3H, s), 3.54 (3H, s), 5.13 (1H, d, J-13Hz), 5.28 (1H, d, J = 13Hz) 7.25 (1H, d, J = 10Hz), 7.4- 7.55 (2H, m), 7.6-7.7 (2H, m),

 7.76 (lH, d, J = 9Hz), 7.8K1H, s)

 (52) 2.23 (3H, s), 3.56 (3H, s), 5.13 (1H, d, J = 13Hz), 5.27 (1H, d, J = 13Hz) 7.4-7.7C5H, m), 7.74 (1H, d, J = 8Hz), 7.82 (1H, s)

 (53) m.p. 107.5 ° C

 (54) 2.16 (3H, s), 2.24 (3H, s), 2.29 (3H, s), 3.57 (3H, s),

 4.85 (1H, d, J = 12Hz), 5.03 (1H, d, J = 12Hz), 6.61 (lH, s),

6.70 (1H, d, J = 8Hz), 7.03 (1H, d, J = 8Hz), 7.35-7.55 (3H, m) (55) 0.87 (3H, t, J = 7Hz), 1.4-1.7 (2H, m), 2.16 (3H, s), 2.28 (3H, s),

2.2-2.4 (2H, m), 3.49 (3H, s), 4.43 (1H, d, J = 12Hz),

 5.02 (1H, d, J = 12Hz), 6.64 (lH, s), 6.68 (1H, d, J = 8Hz),

 7.00 (lH, d, J = 8Hz), 7.19 (1H, d, J-2 8Hz), 7.45 (1H, t, J-2 8Hz),

 7.53 1H, t, J = 8Hz), 7.7K1H, d, J = 8Hz)

 (56) Hi p. 105.5 ° C

 (57) 0.7-1.0C3H, m), 1.0-1.1 (1H, m), 1.3-1.45 (1H, m), 2.17 (3H, s), 2.28 (3H, s), 3.44 (3H, s). 5.04 (2H, s), 6.63 (lH, s),

 6.68 (lH, d, J = 8Hz), 7.00 (1H, d, J = 7Hz), 7.25-7.35 (1H, m),

 7.4- 7.55 (2H, m), 7.73 (1H, d, J = 8Hz)

 (58) 1.13 (3H, t, J = 8Hz), 2.15 (3H, s), 2.16 (3H, s), 2.30 (3H, s),

 2.15-2.40 (2H, m), 3.53 (3H, m), 4.77-4.9 (2H, m), 6.62 (1H, s),

6.68 (1H, d, J = 8Hz), 7.00 (1H, d, J = 7Hz), 7.33 (1H, d, J = 8Hz),

 7.42 (1H, t, J = 7Hz) ヽ 7.51 (1H, d, J = 8Hz)

(59) 1.07 (3H, t, J = 7Hz), 2.20 (3H, s), 2.22 (3H, s), 2.29 (3H, s),

 3.50 (3H, s), 4.98 (2H, s), 6.9-7.1 (5H, m), 7.31 (1H, t, J-8Hz)

(60) m.p. 95.1 ° C

(61) m.p. 94.8 ° C

(62) m p. 130.0 ° C

(63) m.p. 115.5 ° C

(64) nu .131.7 ° C

(65) m.p. 114.8 ° C

(66) 2.08 (3H, s), 3.34 (3H, s), 7.02 (1H, d, J: 8Hz), 7.32 (1H, d, J = 9Hz), 7.35-7.45 (2H, m), 7.5- 7.6 (1H, m), 7.88 (1H, d, J = 8Hz), 8.38 (lH, s) (68) 2.20 (3H, s), 3.54 (3H, s), 5.18 (1H, d, J = 13Hz) ), 5.34 (1H, d, J = 13Hz),

7.30 (lH, d, J = 8Hz), 7.4-7.65 (5H, m) _N 7.75 (1H, d, J = 8Hz),

 7.82 (lH, s)

(70) m.p. 146.9 ° C

Next, a production example of the triazolone compound represented by the general formula (b) will be described. _{2 g}

Production example 1 of intermediate

 1-Acetyl-4- (2-[[α-methyl- (3-trifluoromethyl) benzylidene] aminooxymethyl] phenyl} semicarbazide To 1.20 g (2.94 mmol) of 2% KOH aqueous solution 2 Oml was added. The reaction solution was heated to reflux for 4 hours, made acidic with hydrochloric acid, extracted with ethyl acetate, concentrated, and mixed with n-hexane and ethyl ether. Apart from that, 4— {2—

[[Mechiru one (3-triflate Ruo b-methyl) benzylidene] Aminookishimechi Le] Hue sulfonyl} - 3-methyl-one Δ ² - 1, ^2, to give 4-Bok Riazorin one 5-on 0.83 g.

a. 124.4 ° C

 Next, some other examples of the triazoloney conjugate represented by the general formula (b) are shown together with their physical property values.

 4- [2- (2,5-dimethylphenoxymethyl) phenyl] 1-3-methyl-1

△ ² — l, 2,4—triazoline-1 5—one

 m.p. 189.4 ° C

4- [2- (2,5-dimethylphenoxymethyl) phenyl] 1 3-ethyl

△ ² — l, 2,4—triazoline-1 5—one

 m.p. 198.2 ° C

4- (2-phenoxy) phenyl 3-methyl-1 2,4 triazolin-5-one

 m.p. 148.1 ° C

4 - [2 (2, 5-dimethylbenzyl O carboxylate) Fuweniru] one - 3-methyl-delta ² one 1, 2, 4-Toriazorin 5- ON

 m. p. 155.3. C 4— [2 (2,5-dimethylphenoxymethyl) phenyl] propyl

△ ² — 1,2,4-triazoline-5-one

 m.p. 119.2 ° C

4- [2 (2,5-Dimethylphenoxymethyl) phenyl] 13-Isopropyl-1,2,4-triazoline-5-one mp 143.6 ° C

4 one [2- (2, 5-dimethyl-phenoxyethanol methyl) phenyl] one 3- Shikuropuro pill one delta ² - 1, 2, 4 _ Toriazorin one 5- ON

 m. p. 141.9 ° C 4- [2- (2,5-dimethylphenoxymethyl) -1-6-methylphenyl] -1-3-ethyl-1—2,4-triazoline-5-one

 Ή-NMR (CDC 1 / TMS, <5 (ppm))

1.13 (3H, t, J = 7.5 Hz), 2.17 (3H, s), 2.18 (3H, s), 2.29 (3H, s), 4.80-4.93 (2H, m), 6.64 (lH, s), 6.69 (lH, d, J = 7.5Hz), 7.00 (1H, d, J = 7.5Hz), 7.35 (1H, d, J = 7.5Hz), 7.44 (1H, t, J two 7.5Hz), 7.57 (1H , d, J = 7.5Hz)

4- (2-benzyloxy-6-methyl) phenyl -3- 3-ethyl-Δ ² — 1, 2, 4-triazoline-5-one

 DL p. 163.6 ° C

4- [2 - [[α- methyl i (3-triflate Ruo b-methyl) benzylidene] Amino Okishimechiru]} phenylene Lou 3- Echiru one delta ² - 1, 2, 4-Toriazorin one 5 one on

 m.p. 174.0 ° C

4- (2-benzyloxy-6-methyl) phenyl-1-methyl-1-Δ ² — 1,2,4-triazoline-5-one

 m. p. 177.6. C Next, a production example of the acylthiosemicarbazide represented by the general formula [V] is shown. Production example 2 of intermediate

4- (2- (2,5-Dimethylphenoxymethyl) phenyl) Dissolve 0.32 g (0.1 mmol) of 1-2-methylthiosemicarbazide in 2 ml of tetrahydrofuran, and add 8 Omg of acetyl chloride at 5 ° C or lower. A solution of (0.10 ol) dissolved in 1 ml of tetrahydrofuran was added dropwise. After completion, the mixture was reacted at room temperature for 1 晚, added with ice water, and extracted with ethyl acetate. The extract was concentrated, and the residue was subjected to silica gel column chromatography (eluent: ethyl acetate: n-hexane = 2: 1 (v / v)) to give 4- [2- (2,5-dimethylphenol). Cimethyl) phenyl] 1-2-Methyl-1-acetyl 0.23 g of oi thiosemicarnoxide was obtained.

m.p. 141.6 ° C

 Next, an example of the production of the triclolone triazolone derivative represented by the general formula (113) will be described.

Production example 3 of intermediate

Dissolve 1.0 g of trichloromethyl methyl carbonate in 4 Oml of methylene chloride and add 1,1-dimethyl-4- [2- (2,5-dimethylphenoxymethyl) phenyl] semicarbazide at 10 ° C or lower. A solution prepared by dissolving 1.02 g (3.26 mmol) in 10 ml of methylene chloride was added dropwise. After completion, the mixture was stirred at the same temperature for 2 hours, and reacted under heating and reflux for 5 hours. The reaction mixture was washed with aqueous sodium hydrogen carbonate, concentrated, and the residue was subjected to silica gel column chromatography (eluent; ethyl acetate: n-hexane = 1: 1 (v / V)) to obtain a residue. - (2, 5-dimethyl-phenoxyethanol methyl) Fuweniru] one 1-methyl one 3- black port one delta ² - 1, 2, to give 4 Toriazorin _ 5-one 0.65 g.

 m.p. 86.8 ° C

 Next, production examples of a hydroxymethyltriazolone compound represented by the general formula (c), a formyltriazolone compound represented by the general formula (d), and a triazolone oxime compound represented by the general formula (e) will be described.

 Production example 4 of intermediate

 (1) Dissolve 7.25 g (0.032 cited ol) of 2- (benzyloxy) phenyl isocyanate in 30 ml of tetrahydrofuran, and dissolve 2.90 g of 2-hydroxyethanohydrazide in 60 ml of tetrahydrofuran at room temperature. The solution was added dropwise with stirring. After completion, stirring was continued overnight, and the resulting crystals were collected by filtration and dried to obtain 10.1 g of 11- (hydroxyacetyl) -14-[(2-benzyloxy) phenyl] semicarbazide.

 m.p. 145.9 ° C

1- (Hydroxyacetyl) -1-4-((2-benzyloxy) phenyl) semicarbazide To 8.91 g (0.030 mmol), add 180 ml of 2% aqueous potassium hydroxide solution and stir at 100 ° C for 6 hours Reacted. After cooling the reaction mixture, the oil was decanted off The aqueous layer was acidified with hydrochloric acid. The precipitated crystals are collected by filtration, washed with water, and dried,

4 one [(2-Benjiruokishi) phenyl] one 3-Hydroxymethyl-one Δ ² - 1, ^2, to give 4 Toriazorin one 5-one 5.50 g.

 m p. 207.9 ° C

4- [(2-Benjiruokishi) phenyl] one 3-Hydroxymethyl-one delta ² - 1, 2, 4-Bok Riazorin one 5-O emissions 5.508 (18.5 discussions 01), methyl iodide 3.16 g (22.2 mmol) and carbonate 3.06 g (22.2 mmol) of potassium was stirred at 60 ° C. in 3 Oml of dimethylformamide for 4 hours. Ice water was added to the reaction solution, and the mixture was extracted with ethyl acetate. The extract was washed with water and concentrated. An ether-n-hexane mixed solution was added to the residue to precipitate crystals. The crystals filtered and dried to 4- [(2-Benjiruokishi) Hue sulfonyl] one 1 one methyl one 3-hydroxymethyl-one delta ² _ 1, 2, 4-Toriazo phosphorus one 5-one 4.77 g Obtained.

m.p. 137.4 ° C

(2) 4- [(2-Benjiruokishi) phenyl] one 1-methyl 3-hydroxy Shimechiru delta ² - 1, 2, 4-Toriazorin one 5--on 4.77 g (15.3謹ol) and activated manganese dioxide 1 0 g The mixture was stirred for 6 hours under heating and reflux in a nitrogen atmosphere in 4 mL of form of black mouth. The reaction solution was filtered through celite, and the filtrate was concentrated. Then, a mixed solution of ether-n-hexane was added, and the mixture was cooled to precipitate crystals. The crystals filtered and dried to 4 one [(2-Benjiruokishi) phenyl] _ 1-methyl 3-formyl - [delta ² - to give a 1, 2, 4 one Toriazorin one 5-one 2.80 g.

mp.79.8 ° C

(3) 4-[(2-benzyloxy) phenyl] _1-methyl-3-formyl — △ 2 — 1,2,4-triazolin-5-one 1.80 g (5.83 mmol) is dissolved in pyridine 6 g and stirred. Then, 0.49 g (6.99 mmol) of hydroxylamine hydrochloride was added at room temperature, and stirring was continued for a while. The reaction solution was added to ice water, acidified with hydrochloric acid, and extracted with ethyl acetate. The extract was washed with water, concentrated, ether was added to the residue, and the precipitated crystals were collected by filtration to give 4-[(2-benzyloxy) phenyl] 1-1-methyl-13-hydroxyiminot —1,2, 1.73 g of 4-triazoline-5-one was obtained. „„

m.p. 177.7 ° C

 Next, some of other examples of the hydroxymethyltriazolone compound represented by the general formula (c) are shown together with their physical values.

4 one [(2, 5-dimethyl-phenoxyethanol methyl) phenyl] one 1-methyl 3-arsenide Dorokishimechiru one delta ² - 1, 2, 4 one WINCH Riazorin 5-one mp 129.7 ° C 4 -. [(2, 5- dimethyl phenoxyethanol methyl) phenyl] one 1-methyl-3-arsenide Dorokishimechiru Ichi厶² - 1, 2, 4-Toriazorin one 5- thione

4 one {2 - [[one-methyl (3-triflate Ruo b-methyl) benzylidene] Amino Okishimechiru] Hue sulfonyl} - 1 - methyl one 3-hydroxymethyl-one delta ² - 1, 2, 4-Toriazorin one 5- ON

 Next, some of the other examples of the formyltriazolone compound represented by the general formula (d) are shown together with their physical properties it.

4- [(2,5-dimethylphenoxymethyl) phenyl] 1-methyl-3-formyl-Δ ² — 1,2,4-triazoline-15-one mp. 141.9 ° C 4-(2-[[ one methyl one (3-Bok Rifuruoromechiru) benzylidene] Amino Okishimechiru] Hue sulfonyl} _ 1 - methyl one 3-formyl one Δ ² - 1, ^2, 4- preparative Riazorin 5- oN

 Next, some of other examples of the triazolone oxime compound represented by the general formula (e) are shown together with their physical properties.

4 - [(2, 5-dimethyl-phenoxyethanol methyl) Hue sulfonyl] one 1 one methyl one 3-arsenide Dorokishiimino one delta ² - 1, 2, 4 _ Toriazorin one 5- ON

4- [(2, 5-dimethyl-phenoxyethanol methyl) phenyl] one 1-methyl 3-arsenide Dorokishiimino one厶² - 1, 2, 4-Toriazorin one 5- thione

 m.p. 150.9 ° C

4-(2-C [-methyl-1- (3 trifluoromethyl) benzylidene] aminooxymethyl] phenyl} — 1-Methyl _ 3-hydroxyimino Δ ² — 1,2,4-triazoline-1 5-one

 Next, a production example of the promide represented by the general formula [VIII] will be described.

Production example 5 of intermediate 4 - (4 one black port one 2-methylphenyl) Single 1-methyl one 3- Shiano Ichi厶² - 1, 2, 4 one Toriazorin one 5--on 1.84 g (7.4 Yuzuru ol) and N- bromosuccinimide imide 1.45 g (8.14 mol) was added to 3 Oml of carbon tetrachloride, a catalytic amount of azobisisobutyronitrile was added, and the mixture was reacted with heating under reflux for 5 hours. The reaction solution is filtered, the filtrate is concentrated, and the residue is subjected to column chromatography (eluent; toluene: ethyl acetate = 2: 1 (v / v)) to give 4- [4-chloro-2- (bromomethyl) ) phenylene le] one 1-methyl one 3- Shiano Δ ² - 1, ^2, 4 to obtain an Toriazorin one 5-on 1. 30 g.

 Ή-NMR (CDC 1 a / TMS) δ (ppm)

3.65 (3H, s), 4.27 (1H, d, J = llHz), 4.57 (1H, d, J = llHz), 7.1-7.3 (2H, m), 7.4-7.6 (1H, m)

 Next, some other examples of the bromide represented by the general formula [VIII] are shown together with their physical property values.

 4- [4-Chloro-6-methyl-1- (bromomethyl) phenyl] -1-methyl-1-3-cyano — 1,2,4-triazoline-5-one

 Ή-NMR (CDC 1 ZTMS) δ (ppm)

2.19 (3H, s), 3.67 (3H, s), 4.22 (1H, d, J = llHz), 4.34 (1H, d, J = llHz), 7.1-7.4 (lH, m), 7.38 (1H, s )

4 - [4- Furuoro 2- (bromomethyl) phenyl] one 1-methyl 3-sheet § Roh one Δ ² - 1, ^2, 4 one Toriazorin one 5- ON

 Ή-NMR (CDC 1 a ZTMS) δ (ppm)

3.65 (3H, s). 4.27 (1H, d, J = llHz), 4.55 (1H, d, J-llHz), 7.1-7.4 (3H, m)

4 one [6- black opening one 2- (bromomethyl) phenyl] one 1-methyl 3-Xia no Δ ² - 1, ^2, 4- Toriazorin one 5- ON

m.p. 150.5 ° C

4 one [6- methyl-2- (bromomethyl) phenyl] one 1-methyl one 3-Xia Roh one Δ ² - 1, ^2, 4- Toriazorin one 5- ON

m.p. 143.2 ° C

4-1- [2- (Bromomethyl) phenyl] 1-1-methyl-3-1-cyano \ ^ΰ — 1, 2, 4—triazoline-1 5—one

m p. 107.1 ° C

 Ή-NMR (CDC 1, / TMS) δ (ppm)

3.68 (3H, s), 4.34 (1H, d, J = llHz), 4.64 (1H, d, J = llHz), 7.1-7.6 (4H, m)

 Next, a production example of the phenol compound represented by the general formula [XI] will be described.

Production example of intermediate 6

4- [2- (4-Methylbenzyloxy) phenyl] -1,3-dimethyl-1- △ ² -l, 2,4-triazolin-15-one 2.75 g (8.9 mmol) is dissolved in ethanol 20 ml. To the mixture was added a 10% PdZC catalyst amount, and the mixture was stirred under a hydrogen atmosphere for 3 hours. The reaction mixture was filtered through Celite, the filtrate was concentrated, added hexane .eta., by filtered off crystals, 4- (2-arsenate Dorokishifueniru) one 1, 3-dimethyl-one △ ² - 1, 2 1.81 g of, 4-triazoline-5-one was obtained.

m.p. 201.2 ° C

 Next, some of the other examples of the phenol compound represented by the general formula [XI] are shown together with their physical property values.

4- (2-Hydroxy-6-methylphenyl) 1-1,3-dimethyl-Δ ² —1,2,4-triazoline-1 5-one

m.p. 176.9 ° C

4 one (2-arsenide Dorokishi one 6-methylphenyl) _ 1 one methyl one 3- Echiru one Δ ² - 1, ^2, 4- Toriazorin one 5- ON

m p. 167.8 ° C

 Next, a production example of an acyl (thio) semicarbazide represented by the general formula [XIV] will be described.

 Production example of intermediate 7

2-([α-methyl-1- (3-trifluoromethyl) benzylidene] aminooxymethyl} phenylisocyanate 0.60 g (1.8 mmol) dissolved in tetrahydrofuran (5 ml) was treated with propanohydrazide 0.16 g (1.8 fraction ol). Was added dropwise to a solution of the compound dissolved in 30 ml of tetrahydrofuran with stirring at room temperature After stirring for 8 hours, the reaction solution was concentrated, and a mixed solution of ether and n-hexane was added to the residue to precipitate crystals. Conclusion The crystals were separated by filtration and dried to obtain 0.68 g of 4- {2-[[α-methyl-1- (3-trifluoromethyl) benzylidene] aminooxymethyl] phenyl} -11-propanoyl semicarbazide.

mp. 162.0 ° C

 Next, some other examples of the acyl (thio) semicarbazide represented by the general formula [XIV] are shown together with their physical property values.

 4- [6-Methyl-1- (benzyloxy) phenyl] -1-propanoylsemicarbazide

mp. 161.0 ° C

 4- [6-Methyl-1-2- (2,5-dimethylphenoxymethyl) phenyl] -11-propanoylsemicarbazide

DL p. 190.2 ° C

 4- [2- (2,5-dimethylphenoxymethyl) phenyl] 1-1-cyclopanyl panyl semicarbazide

m. p. 89.4. C

 4- [2- (2,5-dimethylphenoxymethyl) phenyl] 1-1-isobutyrylsemicarbazide

m.p. 182.3 ° C

 4- [2- (2,5-dimethylphenoxymethyl) phenyl] -1-butyryl semicarbazide

m.p. 160.5 ° C

 Next, formulation examples are shown. The compounds of the present invention are indicated by the compound numbers in Table 1, and parts represent parts by weight.

Formulation Example 1

 50 parts of each of the compounds (1) to (70) of the present invention, 3 parts of calcium ligninsulfonate, 2 parts of sodium lauryl sulfate and 45 parts of synthetic hydrous silicon oxide are thoroughly pulverized and mixed to obtain each wettable powder.

Formulation Example 2

10 parts of each of the compounds (1) to (70) of the present invention, Nyl ether (14 parts), calcium dodecylbenzenesulfonate (6 parts) and xylene (70 parts) are mixed well to obtain each emulsion.

Formulation Example 3

 Two parts of each of the compounds of the present invention (1) to (70), 1 part of synthetic hydrous silicon oxide, 2 parts of calcium ligninsulfonate, 30 parts of bentonite and 65 parts of olcin clay are mixed and ground well, and water is added. After well kneading, granulate and dry to obtain each granule. Formulation Example 4

 25 parts of each of the compounds (1) to (70) of the present invention, 3 parts of polyoxyethylene sorbitan monooleate, 3 parts of CMC and 69 parts of water are mixed, and the particle size of the active ingredient becomes 5 microns or less. Wet mill to obtain each suspension.

Formulation Example 5

 10 parts of each of the compounds of the present invention (1) to (70), 1 part of polyoxyethylene styrylphenyl ether and 89 parts of water are mixed to obtain each liquid preparation.

 Next, Test Examples show that the compound of the present invention is useful as an active ingredient of a plant disease controlling agent. The compounds of the present invention are indicated by the compound numbers in Table 1, and the compounds used as comparative controls are indicated by the following compound symbols.

Compound A: 4- (2-methoxy) phenyl-1-methyl-3-ethyl- ² -one-1,2,4-triazoline-5-one [Example 30 of JP-B-41-16] Described compounds)

 The control efficacy was determined by visually observing the disease state of the test plant at the time of the survey, ie, the degree of the flora and lesions on the leaves and stems, and if no flora or lesions were observed, “5”, 10 4% if it is recognized about 30%, 3 or 50% if it is recognized

"2" and "1" when about 70% were recognized, and "0" when there was no difference from the onset of disease when no compound was tested. Indicated by 4, 3, 2, and 0.

Test example 1 Rice blast control test (preventive effect)

Plastic pots were filled with sandy loam, rice (Nipponbare) was sown, and grown in a greenhouse for 20 days. Then, dilute the water-dispersed test preparation with water according to Formulation Example 1 to a predetermined concentration (50 O ppm), and spray it with foliage so that it adheres well to the rice leaf surface. did. After spraying, the plants were air-dried, sprayed with a spore suspension of the blast fungus, and inoculated. After inoculation, the plants were left at 28 ° C and high humidity for 6 days, and the control efficacy was examined. As a result, the compound having the following compound number showed a control value of “5”.

匕 合 番号: (1), (4), (7), (11), (13), (16), (22), (45), (47), (48), (50) , (54), (55), (56), (57), (58), (61), (68)

In contrast, Compound A showed a control value of “0”.

Test example 2 Rice sheath blight control test (preventive effect)

 Plastic pots were filled with sandy loam, and rice (Nipponbare) was sown and grown in a greenhouse for 20 days. The test agent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a predetermined concentration (50 O ppm), and was sprayed with foliage so as to sufficiently adhere to the leaf surface of the rice. After spraying, the plants were air-dried and inoculated with the bran culture mycelium of the sheath blight fungus at the root. After inoculation, the plants were placed at 28 ° C and high humidity for 4 days, and the control efficacy was examined. As a result, the compounds having the following compound numbers exhibited a control value of “5”.

Compound number: (7), (16), (45), (46), (47), (48), (54), (5)

7), (58), (60), (61), (65)

Test example 3 Wheat powdery mildew control test (Therapeutic effect)

 Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. The wheat seedlings that had developed the second leaf were sprinkled with wheat powdery mildew and inoculated. After inoculation, the seeds are grown in a greenhouse at 23 ° C for 3 days, and the suspension prepared in accordance with Formulation Example 4 is diluted with water to a predetermined concentration (50 O ppm). The foliage was sprayed so as to sufficiently adhere to the leaves. After spraying, the plants were grown for 7 days under lighting, and the control efficacy was investigated. As a result, the compound having the following compound number exhibited a control value of “5”.

 Compound number: (1), (4), (7), (13), (14), (16), (22), (45), (47), (54), (57), (58) ), (59), (61), (68)

 In contrast, Compound A showed a control value of “0”.

 Test example 4 Wheat rust control test (preventive effect)

Fill plastic pots with sandy loam, sow wheat (Norin 73), greenhouse For 10 days. The reagent prepared as an emulsion according to Formulation Example 2 is diluted with water to a prescribed concentration (50 O ppm), and adheres well to the leaves of the wheat seedlings in which the second to third true leaves have developed. Foliage was sprayed as follows. After air-drying, spores of wheat rust were inoculated, left at 23 ° C in a dark and humid environment for 1 day, and then grown for 6 days under illumination to investigate their control efficacy. As a result, the compound having the following compound number exhibited a control value of “5”.

Compound number: (4), (7), (13), (16), (22), (45), (50), (61), (62), (68)

Test Example 5 Wheat leaf blight control test (preventive effect)

 Plastic pots were filled with sandy loam, inoculated with wheat (Norin 73), and grown in a greenhouse for 10 days. The test agent prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration (50 O ppm), and was sprayed onto the wheat seedlings so as to sufficiently adhere to the leaves of the seedlings. After spraying, a spore suspension of wheat leaf blight was sprayed and inoculated. After inoculation, they were left at 15 ° C in a dark and humid environment for 3 days, and then grown under illumination for 18 days, and the control effect was examined. As a result, the compound having the following compound number exhibited a control value of “5”. Compound number: (1), (7), (13), (22), (45), (54), (68)

Test Example 6 Wheat eye spot control test (preventive effect)

 Plastic pots were filled with sandy loam, and wheat (Norin 73) was sown and grown in a greenhouse for 10 days. The test agent prepared as an emulsion according to Formulation Example 2 was diluted with water to a predetermined concentration (50 O ppm), and was sprayed onto the wheat seedlings so as to sufficiently adhere to the leaves of the seedlings. After spraying, a spore suspension of wheat eye spot bacterium was inoculated to the root of the wheat and kept at 15 ° C and high humidity for 14 days, and the control effect was examined. As a result, the compound having the following compound number exhibited a control value of “5”.

Compound number: (1), (4), (7), (11), (13), (15), (22), (45), (54), (57), (61), (68) )

 In contrast, Compound A showed a control value of “0”.

Test Example 7 Test for Control of Cucumber Gray Mold (Preventive Effect)

Plastic pots were filled with sandy loam, sown with cucumber (Sagami Hanjiro), and grown for 12 days in a greenhouse. The reagent prepared as a wettable powder according to Formulation Example 1 was diluted with water to a specified concentration (50 Ο ρρπ), which was then adhered to the leaf surface of the Cucumber seedling. Foliage. After spraying, a spore suspension of the fungus of gray mold was inoculated. After inoculation, the plants were grown for 10 days in a humid, dark place for 10 days, and their control efficacy was examined. As a result, the compound having the following compound number exhibited a control value of “5”.

Compound number: (7), (22), (45), (54), (61), (68)

Test example 8 Apple scab control test (preventive effect)

 Plastic pots were filled with sandy loam, apples were sown, and grown in a greenhouse for 20 days. The test reagent, which was made into a suspension according to Formulation Example 4, was diluted with water to a predetermined concentration (500 ppm), and sufficiently applied to the leaf surface of apple seedlings with the fourth to fifth true leaves developed. Foliage was sprayed to wear. After spraying, a spore suspension of apple scab was sprayed and inoculated. After inoculation, the plants were kept at 15 ° C, in a humid environment and in the dark for 4 days, and then grown under illumination for 15 days, and the control effect was examined. As a result, the compounds with the following compound numbers

"5 J showed.

Compound number: (1), (4), (7), (13), (22)

Industrial applicability

 The compound (a) of the present invention exhibits an excellent plant disease controlling effect and can be used as a plant disease controlling agent. The compounds (b), (c), (d) and (e) of the present invention are the compound (a) of the present invention. Can be used as an intermediate for the production of

Claims

1. General formula (a)

 α blue

Wherein R ¹ represents an aromatic hydrocarbon group which may be substituted or an aromatic heterocyclic group which may be substituted, and R ^{2 and} R ⁶ are the same or different, and each represents a hydrogen atom , Represents a methyl group, a halogen atom, a trifluoromethyl group or a methoxy group, represents an R ³ group, a C ₃ alkyl group, a cyclopropyl group, a C ₂ -C ₃ alkenyl group, a trifluoromethyl group or a cyano group, R ⁴ represents a C, to C ₃ alkyl group, W represents an oxygen atom or a sulfur atom, — A— is 10—, (hereinafter, R ′ is bonded to the leftmost atom) — OCH ₂ —, — SCH ₂ —, —CH ₂ 0—, —CH ₂ OC (= 0) —, one C (R ⁵ ) = N-OCH ₂ — (where R ⁵ is a hydrogen atom, a methyl group or Echiru represents a group) or -. represents an N = C (SCH ₃₎ group shown by SCH ₂ scratch. ]

A triazolone derivative represented by the formula:

2. The aromatic hydrocarbon group is phenyl, α-naphthyl or —naphthyl, and the aromatic heterocyclic group is 2-, 3-, 4-pyridyl, 2-, 4-, 5- Pyrimidinyl group, pyrazine-1-yl group, 2-, 3-furinole group, 2-, 3-phenyl group, 2-, 4-, 5-thiazolyl group, 2_, 4-, 5-oxazolyl group, 3 1,4-, 5-Isoxazolyl group, 3-, 4-, 5-Isothiazolyl group, 1,3-, 4-Bilazolyl group, 1,2,3-Triazolyl_1-yl group, 1,2,3 —Triazolyl— 4-yl group, 1,2,3-Triazolyl—5-yl group, 1, 2, 4-triazolyl-1-yl group, 1, 2, 4, 4-triazolyl-3-yl group , 1,2,4-triazolyl-4-yl group, 1,2,5-thiadiazole-3-yl group, 1,2,5-oxadiazol_3-yl group or benzothiazole 2-pill 3. The triazolone derivative according to claim 1, which is a group.

3. The triazolone derivative according to claim 1, wherein R ¹ is a phenyl group which may be substituted.

4. The substituent of the optionally substituted aromatic hydrocarbon group, the optionally substituted aromatic heterocyclic group and / or the optionally substituted phenyl group is a halogen atom or a C ₄ alkyl group. , C, -C ₄ haloalkyl group, -C ₄ an alkoxy group, -C ₄ haloalkoxy group and Fuwenokishi group [said phenoxy group methylcarbamoyl group, a halogen atom, main butoxy group, with triflate Ruo Russia methyl or Shiano group 4. The triazolone derivative according to claim 1, wherein the triazolone derivative is 1 to 3 members selected from the group consisting of:

 5. A plant disease control agent comprising the triazolone derivative according to claim 1, 2, 3, or 4 as an active ingredient.

 6. General formula (b)

( ^b)

[In the formula, R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ² and R ⁶ are the same or different, and represent a hydrogen atom, methyl Represents a group, a halogen atom, a trifluoromethyl group or a methoxy group, represents an R ³ ′ bond, a —C ₃ alkyl group, a cyclopropyl group, a trifluoromethyl group or a cyano group; , (Hereinafter, it is assumed that R 'is bonded to each leftmost atom.) One OCH ₂ —, -SCH ₂ —, one CH ₂₀ —, -CH ₂ OC (= 0) one, -C (R ⁵ ) = N—OCH ₂ — (where R ⁵ represents a hydrogen atom, a methyl group or an ethyl group.) Or a group represented by N = C (SCH ₃ ) SCH ₂ —. ] The triazolone compound shown by these.

7. The aromatic hydrocarbon group is a phenyl group, an α_naphthyl group or a 3-naphthyl group, and the aromatic heterocyclic group is a 2_, 3—, 4-pyridyl group, 2—, 4—, 5 - Pyrimidinyl group, pyrazine-1-yl group, 2-, 3-furyl group, 2-, 3-phenyl group, 2-, 4-, 5-thiazolyl group, 2-, 4-, 5-oxazolyl group , 31-, 4--, 5-isoxazolyl group, 3-, 4-, 5-isothiazolyl group, 1-1,

3-, 4-pyrazolyl group, 1,2,3-triazolyl-1-yl group, 1,2,3-triazolyl-4-yl group, 1,2,3-triazolyl-5-yl group, 1, 2,

4-triazolyl-1-yl group, 1,2,4-triazolyl 3-yl group, 1,2,4-triazolyl_4-yl group, 1,2,5-thiadiazoyl-3-yl 7. The triazolone compound according to claim 6, which is a 1,2,5-oxoxadiazole-3-yl group or a benzothiazole-2-yl group.

8. The triazolone compound according to claim 6, wherein R ¹ is a phenyl group which may be substituted.

9. When the substituent of the optionally substituted aromatic hydrocarbon group, the optionally substituted aromatic heterocyclic group and / or the optionally substituted phenyl group is a halogen atom, C , -C <alkyl groups, d to c ₄ haloalkyl group, c, -C ₄ alkoxy, -C 4 haloalkoxy group and Fuwenokishi group [said Fuwenokishi groups are methyl group, a halogen atom, main butoxy group, triflate Ruo b methyl Or a triazolone compound selected from the group consisting of a triazolone and a cyano group.

 1 0. General formula (c)

(c)

[In the formula, R ¹ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ² and R ⁶ are the same or different, and represent a hydrogen atom, methyl R ⁴ represents a d-C ₃ alkyl group; W represents an oxygen atom or a sulfur atom; —A— is 10—, (hereinafter, referred to as R 'is bonded to each leftmost atom.) — OCH ₂ One, -S CH ₂ One, One CH ₂ O, One CH ₂ 〇C (= 0) One, One C (R ⁵ ) = N -0CH _2- (where R ⁵ is a hydrogen atom, a methyl group or an ethyl group represent.) or represents a group shown by a _{N = C (S CH 3)} S CH 2 scratch. ]

A hydroxymethyltriazolone compound represented by the formula:

 11. General formula (d)

[In the formula, R ′ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ² and R ⁶ are the same or different, and represent a hydrogen atom, methyl R ⁴ represents a d-C ₃ alkyl group; W represents an oxygen atom or a sulfur atom; —A— is 10—, (hereinafter, referred to as R 'is strongly bonded to each leftmost atom) — OCH ₂ —, one SCH ₂ —, one CH ₂₀ —, one CH ₂ OC (= 0) one, — C (R ⁵ ) = N -OCH ₂ i (where R ⁵ is a hydrogen atom, a methyl group or Echiru group.) or _{- N = C (S CH 3} ) represents a group represented by S CH ₂ scratch. ]

A formyl triazolone compound represented by the formula:

 12. —General formula (e)

 HON = CH

[In the formula, R ′ represents an optionally substituted aromatic hydrocarbon group or an optionally substituted aromatic heterocyclic group, and R ² and R ⁶ are the same or different, and represent a hydrogen atom, methyl Represents a group, a halogen atom, a trifluoromethyl group or a methoxy group, represents R ⁴ , represents a C ₃ alkyl group, W represents an oxygen atom or a sulfur atom, and — A— Is — 0—, (hereafter, R 'is bonded to each leftmost atom) — OCH ₂ , 1 SCH _2- , -CH ₂ 0-, -CH ₂ OC (= 0) 1, 1 C (R ⁵ ) = N—OCH ₂ — (where R ⁵ represents a hydrogen atom, a methyl group or an ethyl group) or —N = C (S CH ₃ ) SCH ₂ —. ]

A triazolone oxime compound represented by the formula:

 13. The aromatic hydrocarbon group is a phenyl group, an α-naphthyl group or a —naphthyl group, and the aromatic heterocyclic group is a 2-, 3-, 4-pyridyl group, 2-, 4-1, 5- Pyrimidinyl group, pyrazine-1-yl group, 2-, 3-furyl group, 2-, 3-thienyl group, 2-, 4-, 5-thiazolinole group, 2-, 4-, 5-oxazolyl group , 3-, 4-I, 5-isoxazolinole group, 3-, 4-, 5-isothiazolyl group, 1,3-, 4-pyrazolyl group, 1,2,3-triazolyl-1-inole group , 1,2,3-triazolyl 4-inole group, 1,2,3-triazolyl-5-yl group, 1,2,4-triazolyl-1-yl group, 1,2,4-triazolyl-13 —Inole group, 1,2,4-triazolyl— 4-yl group, 2,5-thiadiazole—3-inole group, 1,2,5-oxadiazol-3-yl group or benzothia Ichiru - 2 - claims a I le group 1 0, 1 1 or 1 2 compounds according.

14. The compound according to claim 10, 11, or 12, wherein R ¹ is a phenyl group which may be substituted.

15. Substituents of an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group and an Ζ or an optionally substituted phenyl group, a halogen atom, C, to C ₄ alkyl group, -C ₄ haloalkyl group, -C ₄ alkoxy group, C, ~ C ₄ haloalkoxy group and Fuwenokishi group [said Fuwenokishi group methylation group, a halogen atom, main butoxy group, triflate Ruo Russia methyl or 15. The compound according to claim 10, wherein the compound may be replaced by a cyano group.