WO1999033810A1 - Pyridyloxy(thio)alkanoic acid amide derivatives and agricultural/horticultural bactericides - Google Patents

Pyridyloxy(thio)alkanoic acid amide derivatives and agricultural/horticultural bactericides Download PDF

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Publication number
WO1999033810A1
WO1999033810A1 PCT/JP1998/005816 JP9805816W WO9933810A1 WO 1999033810 A1 WO1999033810 A1 WO 1999033810A1 JP 9805816 W JP9805816 W JP 9805816W WO 9933810 A1 WO9933810 A1 WO 9933810A1
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group
alkyl group
come
alkyl
substituted
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PCT/JP1998/005816
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French (fr)
Japanese (ja)
Inventor
Katsumi Masuda
Atsushi Shibayama
Katsunori Matsumoto
Norihisa Yonekura
Katsumi Furuse
Kazuo Kumakura
Norimichi Muramatsu
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Kumiai Chemical Industry Co., Ltd.
Ihara Chemical Industry Co., Ltd.
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Application filed by Kumiai Chemical Industry Co., Ltd., Ihara Chemical Industry Co., Ltd. filed Critical Kumiai Chemical Industry Co., Ltd.
Priority to AU16859/99A priority Critical patent/AU1685999A/en
Publication of WO1999033810A1 publication Critical patent/WO1999033810A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings

Definitions

  • the present invention relates to a pyridyloquin (thio) alkanoic acid amide derivative which is a novel compound not described in any literature, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.
  • Japanese Patent Application Laid-Open Nos. 5-286937 and 6-36050 disclose that pyridyloxycarboxylic acid amide derivatives have bactericidal activity. .
  • the compound of the present invention is not described at all.
  • the present invention provides a pyridyloxy (thio) alkanoic acid amide derivative having a novel and excellent bactericidal activity.
  • the present inventors have synthesized various pyridyloxy (thio) alkanoic acid amide derivatives and examined the physiological activities thereof. It has been found that it has a bactericidal activity and does not cause any harm to useful crops, and thus completed the present invention.
  • the present invention provides:
  • n represents an integer of 1-4
  • R 1 represents hydrogen
  • Atom, di-alkyl group, C. Represents ⁇ CP a cycloalkyl group or a C ⁇ -C 4 Ha port alkyl group
  • R 2 and R 3 are each independently, C j C g alkyl group, C 0 -C Arukeniru group, c 3 to c Hashikuroaruki Le group (This group may be substituted by a halogen atom or a C ⁇ -C 6 alkyl group.)
  • Q is a C 2 -C p alkyl group, ethynyl group, group — COR 4 (R 4 is a
  • the C. 1 to C 6 alkyl group a linear or indicates branched alkyl group, for example, methylation group, Echiru group, n- propyl group, an isopropyl group, n- butyl group, Isobuchi Le group, sec- butyl Group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group and the like.
  • the 99/33810 c 3 ⁇ c 6 cycloalkyl group includes for example cyclopropyl group, a cyclopentyl group, cyclohexylene a cyclohexyl group.
  • ⁇ c Ha cycloalkyl Ci ⁇ c 6 alkyl group for example, cyclopropylmethyl group, cyclopentylmethyl group, forces include cyclohexylmethyl group or the like cyclohexane, can be '.
  • the Ci ⁇ c 4 Ha port alkyl group substituted by a halogen atom, a linear or represents a branched alkyl group, for example Furuoromechiru group, chloromethyl group, blanking Romomechiru group, Jifuruoromechiru group, dichloromethyl group, Examples thereof include a dibromomethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, and a pentafluoroethyl group.
  • Halogen atom means fluorine atom, chlorine atom, bromine atom and iodine atom.
  • the C. 1 to c 6 alkoxy group a linear or branched alkoxy group, for example if main butoxy group, an ethoxy group, n - propoxy group, isopropoxy group, n- butoxy sheet group, Isobutokishi group, sec —Butoxy group, tert-butyne group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group and the like.
  • c 2 -c 6 alkenyloxy group refers to a linear or branched alkenyloxy group, and examples thereof include an aryloxy group, an isopropyloxy group, a 2-butenyloxy group and the like.
  • c 2 -c 6 alkynyloxy group refers to a linear or branched alkynyloxy group, and examples thereof include a 2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group. .
  • Chokukusarimata represents a branched chain alkoxy group, for example Furuorome butoxy group, Jifuruorome Bok alkoxy group, Torifuruorome butoxy group, penta full O b ethoxy And the like.
  • the ci- 6 alkylthio group is a linear or branched alkylthio group, for example, a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, tert- Examples thereof include a butylthio group and an n-hexylthio group.
  • the C ⁇ -C 4 haloalkylthio group, substituted by a halogen atom, a linear or branched shows an alkylthio group, for example, full-O b methyl thio group, Jifuruo Romechiruchio group, triflate Ruo b methylthio group, Pentafuruo And a loethylthio group.
  • Some of the compounds of the present invention represented by the general formula [I] have one or more asymmetric carbon atoms in the molecule, and such compounds have optical isomers. Exists. Pure individual diastereomers, enantiomers and mixtures thereof are also included in the compounds of the present invention.
  • Preferred compounds of the compound of the present invention represented by the general formula [I] include X is a methyl group, trifluoromethyl group, chlorine atom, bromine atom or iodine atom and R 1 is a hydrogen atom, methyl group or ethyl group.
  • R 2 is a hydrogen atom, a methyl group, an ethyl group or an n-propyl group
  • R 3 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group Or a compound in which Q is an ethynyl group, an acetyl group, a propionyl group, a cyclopropylcarbonyl group or a 1-hydroxyxethyl group in a dichloromethyl group.
  • Me represents a methyl group
  • Et represents an ethyl group
  • Pr represents an n-propyl group
  • Pri represents an isopropyl group
  • Bu represents an n-butyl group.
  • Bu-i represents an isobutyl group
  • Bu-t represents a tert-butyl group
  • Pr-cyc represents a cyclopropyl group
  • Pen-cyc represents a cyclopentyl group
  • P-cyc represents a cyclopentyl group.
  • h represents a phenyl group.
  • P h (4-C 1) represents a 4_chlorophenyl group. (table 1 )
  • the compound of the present invention represented by the general formula [I] can be produced, for example, according to the following production method.
  • the compound [I] of the present invention is a pyridyloxy (thio) alkane represented by the general formula [II]
  • the acid derivative can be produced by reacting an acid derivative with an amine represented by the general formula [III] using a condensing agent in the presence of a catalyst and / or a base, if necessary. This reaction is usually performed in a solvent.
  • Solvents that can be used may be solvents that do not inhibit the reaction, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, rigoin, hydrocarbons such as benzene, toluene or xylene, dichloromethane, dichloroethane. Halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene, or dichlorobenzene; ethers such as ethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, or dioxane; acetone, methylethyl ketone , / Ten
  • Ketones such as methyl isopropyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; ditriles such as acetonitril or propionitrile; or dimethyl sulfoxide, N,
  • a nonprotonic polar solvent such as N-dimethylformamide or sulfolane, or a mixed solvent in which a solvent selected from these is combined can be used.
  • condensing agent examples include 1-ethyl-3- (3-dimethylaminopropyl) force rubodiimide 'hydrochloride, N, ⁇ '-dicyclohexylcarbodiimide, carbonyldimidazole, and 2 — Black mouth—1,3-dimethylimidazolium chloride, etc.
  • hornworm medium examples include 4-dimethylaminopyridine, 1-hydroxybenzotriazole, dimethylformamide and the like.
  • alkali metal hydroxides such as sodium hydroxide or hydroxylated lime
  • alkaline earth metal hydroxides such as calcium hydroxide
  • alkalis such as sodium carbonate or carbonated lime
  • Metal carbonates or triethylamine, trimethylamine, ⁇ , ⁇ -methylylaniline, pyridine, ⁇ -methylpiperidine, 1,5-diazabicyclo [4.3.0] non-15-ene (DBN) or Organic bases such as 1,8-diazabicyclo [5.4.0] -17-pandacene (DBU) and the like, preferably tertiary amines such as triethylamine, pyridine and ⁇ -methylbiperidine Is mentioned.
  • the reaction temperature was 150. C. is carried out in the range of 150 ° C., preferably in the range of 0 ° C. to 100 ° C.
  • the reaction time is preferably 1 to 30 hours.
  • the compound represented by the general formula [II] can be produced, for example, according to the following production method. 99/33810
  • R 1 X, n and A represent the same meaning as described above, 6 represents a 1 to 6 alkyl group, and Z represents a leaving group such as a halogen atom.
  • the pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II] can be obtained, for example, by converting a pyridine derivative represented by the general formula [IV] or [VII] in the presence of a base into the general formula [V] or [VIII] By reacting with an alkanoic acid ester derivative represented by the general formula [VI], and then hydrolyzing the pyridyloxy (thio) alkanoic acid ester derivative. be able to.
  • the reaction between the pyridine derivative represented by the general formula [IV] or [VII] and the ester derivative represented by the general formula [V] or [VIII] is usually performed in a solvent.
  • Solvents that can be used may be solvents that do not inhibit the reaction, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, rig-mouth, benzene, toluene or hydrocarbons such as xylene, dichloromethane, Halogenated hydrocarbons such as chloroethane, chloroform, carbon tetrachloride, carbon benzene or dichlorobenzene, dimethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane W 99/33810
  • Ethers acetone, methyl ethyl ketone, ketones such as methyl isopropyl ketone or methyl isobutyl ketone, ester acetates such as methyl acetate or ethyl acetate, nitriles such as acetonitrile or propionitrile,
  • a non-protonic polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide or sulfolane, or a mixed solvent obtained by combining solvents selected from these solvents can be used.
  • an inorganic base such as sodium hydroxide, sodium hydroxide, sodium carbonate, carbonated carbonate, sodium bicarbonate, sodium hydride or hydrogenated potassium, or triethylamine, trimethylamine, N , N-dimethylaniline or pyridine.
  • the reaction is carried out at a temperature in the range of 50 ° C to 150 ° C, preferably in the range of 0 ° C to 100 ° C.
  • the reaction time is preferably 1 to 30 hours.
  • a reaction for hydrolyzing a pyridyloxy (thio) alkanoic acid ester derivative represented by the general formula [VI] in the presence of an acid or an alkali to obtain a pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II] Is usually performed in a solvent.
  • Any solvent that does not inhibit the reaction may be used, for example, water, alcohols such as methanol, ethanol or 2-propanol, getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane.
  • Ethers ketones such as acetone, methylethylketone, methylisopropylketone or methylisobutylketone, or a mixed solvent obtained by combining solvents selected from these.
  • the compound represented by the general formula [III] can be prepared by a known method [for example, Journal of the Chemical Society. Parkin Transaction Society. 1, Journal of Chemical Society]. y. Perkin Transaction s. 1), Vol. 8, pp. 1645 (1998); The 'Journal' Ob '' Organic 'Chemistry (The Journal of O.) rganic Chemistry), vol. 49, p. 1208 (1 984)] or a method analogous thereto. be able to
  • the compound [I] of the present invention is a pyridine derivative represented by the general formula [VII] It can be produced by reacting with an alkanoic acid amide derivative represented by the general formula [IX] in the presence of a base. This reaction is usually performed in a solvent.
  • any solvent that does not inhibit the reaction may be used.
  • examples include pentane, hexane, heptane, cyclohexane, petroleum ether, rigoin, hydrocarbons such as benzene, toluene, and xylene, dichloromethane, and the like.
  • Halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride, cyclobenzene or dichlorobenzene, ethers such as getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, acetone, methyl Ketones such as rutile ketone, methyl isopropyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; nitriles such as acetonitrile or pentionitrile; or dimethyl sulfoxide, N
  • Non pro ton polar solvents such as N- dimethyl formamide or sulfolane, or may be a mixed solvent combining solvents selected from these.
  • inorganic bases such as 7K sodium oxide, hydroxylated lime, sodium carbonate, carbonated lime, sodium bicarbonate, sodium hydride or hydrogenated lime, or triethylamine, trimethylamine, N, N-dimethyl Organic salts such as aniline or pyridine And the like.
  • the reaction temperature is in the range of —50 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C.
  • the reaction time is preferably 1 to 30 hours.
  • the compound represented by the general formula [IX] can be produced, for example, by reacting a halogenated alkanoic acid halide with an amide derivative represented by the general formula [III]. .
  • the compound [I] of the present invention is obtained by converting a pyridine derivative represented by the general formula [IV] into a base In the presence, the compound can be produced by reacting with an alkanoic acid amide derivative represented by the general formula [X]. This reaction is usually performed in a solvent.
  • a solvent that can be used any solvent that does not inhibit the same reaction as in Production Method 2 may be used.
  • the reaction is carried out at a temperature ranging from ⁇ 50 ° C. to 150, preferably from 0 ° C. to 100 ° C.
  • the reaction time is preferably 1 to 30 hours.
  • the compound represented by the general formula [X] is obtained, for example, by reacting the halogenated alkanoic acid amide derivative represented by the general formula [IX] with sodium acetate. It can be produced by deacylation of a derivative.
  • the compound of the present invention ⁇ —II] is a pyridyloxy (thio) represented by the general formula [II]
  • the alkanoic acid amide derivative can be produced by performing a hydration reaction in the presence of an acid. This reaction is performed without a solvent or in a solvent.
  • Solvents that can be used may be any solvents that do not inhibit the reaction, such as ethers such as getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, acetone, methyl ethyl ketone, and methyl iso- Ketones such as propyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; nitriles such as acetonitrile or propionitrile; or dimethyl sulfoxide, N, N-dimethylformamide or sulfolane Or a mixed solvent obtained by combining solvents selected from these aprotic polar solvents.
  • ethers such as getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, acetone, methyl ethyl
  • Examples of the acid include sulfuric acid, hydrochloric acid, formic acid and the like.
  • the reaction is carried out at a temperature in the range of 0 to 150 ° C, preferably in the range of 20 to 100 ° C.
  • the reaction time is preferably 1 to 10 hours.
  • the compound [I-IV] of the present invention reduces the pyridyloxy (thio) alkanoic acid amide derivative represented by the general formula [I-III]. It can be produced by reacting with an agent. This reaction is usually performed in a solvent. As a solvent that can be used, any solvent that does not inhibit the reaction may be used. For example, pentane, hexane, heptane, cyclohexane, petroleum ether, lignin, benzene, toluene, xylene, etc.
  • Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethers such as dimethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. , methanol, ethanol, 2-alcohols such as propanol or water and it is in monkey c a mixed solvent of alcohol
  • reducing agent those generally used in this type of reaction can be used.
  • examples include lithium borohydride, sodium borohydride, potassium borohydride, lithium trialkylborohydride, sodium trialkylborohydride or sodium cyanoborohydride, and preferably sodium borohydride. Is mentioned.
  • the reaction is carried out at a temperature in the range of 170 ° C. to 150 ° C., preferably in the range of ⁇ 20 ° C. to 50 ° C.
  • the reaction time is preferably 1 to 30 hours.
  • the isomer A represents diastereomer A
  • the isomer B represents diastereomer B
  • the isomer M represents diastereomer mixture.
  • Diastereomer A indicates a low-polarity diastereomer separated by silica gel column chromatography or high performance liquid chromatography
  • diastereomer B indicates a similarly separated high-polarity diastereomer.
  • the agricultural and horticultural fungicide of the present invention contains a pyridyloquin (thio) carboxylic acid amide derivative represented by the general formula [I] as an active ingredient.
  • the active ingredient can be used in an appropriate dosage form depending on the purpose. Normally, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, a surfactant and other substances can be added to the active ingredient for use in the form of powders, wettable powders, emulsions, granules, etc. .
  • Suitable carriers include, for example, talc, bentonite, clay, kaolin, diatoms
  • solid carriers such as soil, white water, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea
  • liquid carriers such as 2-propyl alcohol, xylene, cyclohexanone, and methylnaphthalene.
  • surfactants and dispersants include dinaphthyl methanesulfonate, alcohol sulfate, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, and polyoxyethylene. Sorbi monoalkylate and the like.
  • Auxiliary agents include carboxymethylcellulose and the like. These preparations are diluted to an appropriate concentration and sprayed or applied directly.
  • the fungicide for agricultural and horticultural use of the present invention can be used by foliage application, nursery box application, soil application or water surface application.
  • the compounding ratio of the active ingredient is appropriately selected as required, but is preferably 0.1 to 20% (by weight) in the case of powders and granules, and 5 to 80% (by weight) in the case of emulsions and wettable powders. It is.
  • the application rate of the agricultural and horticultural fungicide of the present invention varies depending on the type of the compound used, the target disease, the tendency to occur, the degree of damage, the environmental conditions, the dosage form used, and the like.
  • a suitable amount from the range of O.lg to 5 kg, preferably lg to lkg, per 10 ares of the active ingredient.
  • a suitable amount from the range of O.lg to 5 kg, preferably lg to lkg, per 10 ares of the active ingredient.
  • a liquid such as an emulsion and a wettable powder
  • the compound according to the present invention can control plant diseases caused by fungi belonging to algal fungi (Oomycetes), ascomycetes (Ascomycetes), incomplete fungi (Deuteromycetes), and basidiomycetes (Basidiomycetes) by the above-mentioned application forms.
  • fungi belonging to algal fungi Olemycetes
  • ascomycetes Ascomycetes
  • Deuteromycetes incomplete fungi
  • Basidiomycetes Basidiomycetes
  • Genus Pyricularia for example, Pyricularia oryzae
  • Gibberella for example, Gibberella fujikuroi
  • Botrytis j Botrytis j
  • the compound of the present invention may be mixed with an insecticide, other fungicides, herbicides, plant growth regulators, fertilizers and the like, if necessary.
  • the formulation method will be specifically described with reference to typical examples of the agricultural and horticultural fungicides of the present invention. In the following description, “%” indicates weight percentage.
  • Emulsion was prepared by uniformly dissolving 30% of compound (A-1), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene.
  • the compound of the present invention has a high control effect against rice blast and the like, and also has characteristics that it does not cause phytotoxicity to crops and has excellent residual effect and rain resistance. Useful as a fungicide.
  • Test example 1 Rice blast prevention effect test
  • Rice seedlings in the 1.5 leaf stage were transplanted into four white spots at a height of 9 cm in white porcelain pots and raised in a greenhouse.
  • the wettable powder prepared according to Formulation Example 2 at the 2.5 leaf stage was subjected to water application to the pot such that the active ingredient concentration was 300 g per 10 ares.
  • a conidia suspension of the rice blast fungus (Pyricu 1 ariaoryzae) was inoculated by spraying and immediately placed in 25 wet chambers for 24 hours. Then, they were transferred to a greenhouse, and 5 days after the inoculation, the number of lesions on the highest leaf at the time of the inoculation was examined.
  • the control value was determined by Equation 1, and the results of evaluation based on the criteria in Table 19 are shown in Tables 24 to 25.

Abstract

Pyridyloxy(thio)alkanoic acid amide derivatives represented by general formula (I): wherein X represents hydrogen, C1-6 alkyl, C1-4 haloalkyl, etc.; n is an integer of 1 to 4; R1 represents hydrogen, C¿1-6? alkyl, etc.; R?2 and R3¿ independently represent each C¿1-6? alkyl, C2-6 alkenyl, etc.; Q represents C2-6 alkyl, ethynyl, -COR?4¿ (wherein R4 represents C¿1-6? alkyl, etc.) or -CH(OH)R?5¿ (wherein R5 represents C¿1-6? alkyl, etc.); and A represents oxygen or sulfur. The bactericides have high preventive effects on rice blast, etc., and moreover, are featured by causing no chemicla injury to crops and being excellent in residual effectiveness and resistance to rainfall.

Description

明細書  Specification
ピリジルォキシ （チォ） アルカン酸アミ ド誘導体及び農園芸用殺菌剤  Pyridyloxy (thio) alkanoic acid amide derivatives and fungicides for agricultural and horticultural use
[技術分野]  [Technical field]
本発明は、 文献未記載の新規化合物であるピリジルォキン （チォ） アルカン酸 ァミ ド誘導体及びこれを有効成分として含有する農園芸用殺菌剤に関するもので ある。  The present invention relates to a pyridyloquin (thio) alkanoic acid amide derivative which is a novel compound not described in any literature, and a fungicide for agricultural and horticultural use containing the same as an active ingredient.
[背景技術]  [Background technology]
特開平 5— 2 8 6 9 3 7号公報、 特開平 6 - 3 0 6 0 5 0号公報明細書には、 ピリジルォキシカルボン酸ァミ ド誘導体が殺菌活性を有する事が開示されてい る。 しかしながら、 本発明化合物については全く記載されていない。  Japanese Patent Application Laid-Open Nos. 5-286937 and 6-36050 disclose that pyridyloxycarboxylic acid amide derivatives have bactericidal activity. . However, the compound of the present invention is not described at all.
近年、 農園芸用殺菌剤の多用により薬剤に対する耐性菌が出現し、 既存の薬剤 では充分な殺菌活性を示さないことがある。 また、 環境問題から低濃度で効率良 く有害菌を防除できる新しい殺菌剤が求められている。 そこで本発明は、 新規か つ優れた殺菌活性を有するピリジルォキシ （チォ） アルカン酸アミ ド誘導体を提 供するものである。  In recent years, the use of agricultural and horticultural fungicides has led to the emergence of drug-resistant bacteria, and existing drugs may not show sufficient fungicidal activity. In addition, new fungicides that can efficiently control harmful bacteria at low concentrations are demanded due to environmental problems. Therefore, the present invention provides a pyridyloxy (thio) alkanoic acid amide derivative having a novel and excellent bactericidal activity.
本発明者らは、 ピリジルォキシ （チォ） アルカン酸アミ ド誘導体を種々合成 し、 その生理活性について検討したところ、 本発明化合物が幅広い殺菌スぺク 卜 ラムを有し、 特にいもち病に対し極めて優れた殺菌活性を有するとともに、 有用 作物に対して何等の害も及ぼさないことを見 、だし、 本発明を完成した。  The present inventors have synthesized various pyridyloxy (thio) alkanoic acid amide derivatives and examined the physiological activities thereof. It has been found that it has a bactericidal activity and does not cause any harm to useful crops, and thus completed the present invention.
[発明の開示]  [Disclosure of the Invention]
即ち、 本発明は、 （1 ) 一般式 [ I ]  That is, the present invention provides:
Figure imgf000003_0001
Figure imgf000003_0001
[式中、 Xは水素原子、 C i C。アルキル基、 c i c 4ハ口アルキル基、 C l C 6アルコキシ基、 C i C 4ハ口アルコキシ基、 C 9 C 6アルケニル ォキシ基、 c 9 c アルキニルォキシ基、 c i c 6アルキルチオ基、 丄〜 じ 4ハロアルキルチオ基、 ハロゲン原子、 アミノ基、 ニトロ基、 シァノ基、 フエ ニル基 （該基は c丄〜c 6アルキル基、 c 〜c 4ハ口アルキル基、 c1〜c6 アルコキシ基又はハロゲン原子によって置換されていてもよい。 ） 又はフニノキ シ基 （該基は c 1 〜C アルキル基、 C 丄〜C ハロアルキル基、 C ] 〜C pァ ルコキン基又はハロゲン原子によって置換されてもよい。 ) を表し、 nは 1〜4 の整数を表し、 R 1は水素原子、 じ 丄〜じ アルキル基、 C 。〜C Pシクロアル キル基又は C 丄〜C 4ハ口アルキル基を表し、 R 2及び R 3はそれぞれ独立し て、 C j C gアルキル基、 C 0〜C ァルケニル基、 c3〜cハシクロアルキ ル基 （該基はハロゲン原子又は C 丄〜C 6アルキル基によって置換されていても よい。 ） 、 C 3〜c シクロアルキル C 丄〜C Pアルキル基又は C ， 〜C ノヽロ アルキル基を表すか、 あるいは R 2と R 3はこれらが結合している炭素原子と共 に 5員〜 7員環のシクロアルキル基 （該基は C ， 〜C アルキル基によって置換 されていてもよい。 ） を形成し、 Qは C 2〜C pアルキル基、 ェチニル基、 基— COR4 (R 4は C i〜C 6アルキル基、 C：。〜 C シクロアルキル基 （該基は ハロゲン原子、 C J〜C 6アルキル基によって置換されてもよい。 ） 又はじェ〜 C 4ハ口アルキル基を表す。 ） 又は基一 CH (OH) R 5 (尺 ^ま 丄〜 ァ ルキル基、 C 3〜c pシクロアルキル基 （該基はハロゲン原子、 】〜。 アル キル基によって置換されてもよい。 ） 又は C 〜C 4ハ口アルキル基を表す。 ） を表し、 Aは酸素原子又は硫黄原子を表す。 ] にて示されるピリジルォキシ （チ ォ） アル力ン酸ァミ ド誘導体。 [Where X is a hydrogen atom, C i C. Alkyl group, cic 4 Ha port alkyl, C l C 6 alkoxy groups, C i C 4 C port alkoxy, C 9 C 6 alkenyl Okishi group, c 9 c Arukiniruokishi group, cic 6 alkylthio group,丄~ Ji 4 Haloalkylthio group, halogen atom, amino group, nitro group, cyano group, phen An aryl group (the group may be substituted by a C 丄 -C 6 alkyl group, a C 4 -C 4 alkyl group, a C 1 -C 6 alkoxy group or a halogen atom) or a funinoxy group (the group is c 1 -C alkyl group, C 1 -C haloalkyl group, C] -C p -alkoxy group or a halogen atom.), n represents an integer of 1-4, and R 1 represents hydrogen. Atom, di-alkyl group, C. Represents ~CP a cycloalkyl group or a C丄-C 4 Ha port alkyl group, R 2 and R 3 are each independently, C j C g alkyl group, C 0 -C Arukeniru group, c 3 to c Hashikuroaruki Le group (This group may be substituted by a halogen atom or a C 丄 -C 6 alkyl group.), A C 3 -c cycloalkyl C 丄 -CP alkyl group or a C, -C nodroalkyl group, or R 2 and R 3 together with the carbon atom to which they are attached form a 5- to 7-membered cycloalkyl group (the group may be substituted by a C 1 to C 4 alkyl group); Q is a C 2 -C p alkyl group, ethynyl group, group — COR 4 (R 4 is a C i -C 6 alkyl group, C: -C cycloalkyl group (the group is a halogen atom, a CJ -C 6 alkyl group Or a C 4 -C 4 alkyl group.) Or a group CH (OH ) R 5 (size: alkyl group, C 3 -cp cycloalkyl group (the group is a halogen atom,), which may be substituted by an alkyl group) or C 4 -C 4 alkyl group A) represents an oxygen atom or a sulfur atom. A pyridyloxy (thio) alnic acid amide derivative represented by the formula:
(2) これらのピリジルォキシ （チォ） アルカン酸アミ ド誘導体を有効成分と して含有する農園芸用殺菌剤である。  (2) A fungicide for agricultural and horticultural use containing these pyridyloxy (thio) alkanoic acid amide derivatives as active ingredients.
まず、 本明細書において用いられる用語について、 以下説明する。 なお、 本明 細書における、 例えば 「c i〜c6」 等の表記は、 これに続く置換基の炭素数 力、 この場合では 1乃至 6であることを示している。 First, terms used in the present specification will be described below. In this specification, for example, notations such as “ci to c 6 ” indicate that the number of carbon atoms of the subsequent substituent is 1 to 6, in this case.
C 1〜C 6アルキル基とは、 直鎖又は分岐鎖状のアルキル基を示し、 例えばメ チル基、 ェチル基、 n—プロピル基、 イソプロピル基、 n—ブチル基、 イソブチ ル基、 s e c—ブチル基、 t e r t—ブチル基、 n—ペンチル基、 イソペンチル 基、 ネオペンチル基、 n—へキシル基、 イソへキシル基、 3， 3—ジメチルブチ ル基等を挙げることができる。 99/33810 c 3〜c 6シクロアルキル基とは、 例えばシクロプロピル基、 シクロペンチル 基、 シクロへキシル基等を挙げることができる。 The C. 1 to C 6 alkyl group, a linear or indicates branched alkyl group, for example, methylation group, Echiru group, n- propyl group, an isopropyl group, n- butyl group, Isobuchi Le group, sec- butyl Group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, 3,3-dimethylbutyl group and the like. The 99/33810 c 3 ~c 6 cycloalkyl group includes for example cyclopropyl group, a cyclopentyl group, cyclohexylene a cyclohexyl group.
c。〜c ハシクロアルキル c i〜c 6アルキル基とは、 例えばシクロプロピル メチル基、 シクロペンチルメチル基、 シクロへキシルメチル基等を挙げること力、' できる。 c. The ~c Ha cycloalkyl Ci～c 6 alkyl group, for example, cyclopropylmethyl group, cyclopentylmethyl group, forces include cyclohexylmethyl group or the like cyclohexane, can be '.
c i〜c 4ハ口アルキル基とは、 ハロゲン原子によって置換された、 直鎖また は分岐鎖状のアルキル基を示し、 例えばフルォロメチル基、 クロロメチル基、 ブ ロモメチル基、 ジフルォロメチル基、 ジクロロメチル基、 ジブロモメチル基、 卜 リフルォロメチル基、 クロロジフルォロメチル基、 ペンタフルォロェチル基等を 挙げることができる。 The Ci～c 4 Ha port alkyl group, substituted by a halogen atom, a linear or represents a branched alkyl group, for example Furuoromechiru group, chloromethyl group, blanking Romomechiru group, Jifuruoromechiru group, dichloromethyl group, Examples thereof include a dibromomethyl group, a trifluoromethyl group, a chlorodifluoromethyl group, and a pentafluoroethyl group.
ハロゲン原子とは、 フッ素原子、 塩素原子、 臭素原子及びヨウ素原子を示す。 Halogen atom means fluorine atom, chlorine atom, bromine atom and iodine atom.
C 1〜c 6アルコキシ基とは、 直鎖又は分岐鎖状のアルコキシ基を示し、 例え ばメ トキシ基、 エトキシ基、 n —プロポキシ基、 イソプロポキシ基、 n—ブトキ シ基、 ィソブトキシ基、 s e c —ブトキシ基、 t e r t —ブトキン基、 n —ペン チルォキシ基、 イソペンチルォキシ基、 n -へキシルォキシ基等を挙げることが できる。 The C. 1 to c 6 alkoxy group, a linear or branched alkoxy group, for example if main butoxy group, an ethoxy group, n - propoxy group, isopropoxy group, n- butoxy sheet group, Isobutokishi group, sec —Butoxy group, tert-butyne group, n-pentyloxy group, isopentyloxy group, n-hexyloxy group and the like.
c 2〜c 6アルケニルォキシ基とは、 直鎖又は分岐鎖状のアルケニルォキシ基 を示し、 例えばァリルォキシ基、 イソプロぺニルォキシ基、 2—ブテニルォキシ 基等を挙げることができる。 The term “c 2 -c 6 alkenyloxy group” refers to a linear or branched alkenyloxy group, and examples thereof include an aryloxy group, an isopropyloxy group, a 2-butenyloxy group and the like.
c 2〜c 6アルキニルォキシ基とは、 直鎖又は分岐鎖状のアルキニルォキシ基 を示し、 例えば 2—プロピニルォキシ基、 2 —プチニルォキシ基、 3 —プチニル ォキシ基等を挙げることができる。 The term “c 2 -c 6 alkynyloxy group” refers to a linear or branched alkynyloxy group, and examples thereof include a 2-propynyloxy group, a 2-butynyloxy group, and a 3-butynyloxy group. .
C：〜c 4ハロアルコキシ基とは、 ハロゲン原子によって置換された、 直鎖又 は分岐鎖状のアルコキシ基を示し、 例えばフルォロメ トキシ基、 ジフルォロメ 卜 キシ基、 トリフルォロメ トキシ基、 ペンタフルォロエトキシ基等を挙げることが できる。 C: to c and 4 haloalkoxy groups, substituted by halogen atoms, Chokukusarimata represents a branched chain alkoxy group, for example Furuorome butoxy group, Jifuruorome Bok alkoxy group, Torifuruorome butoxy group, penta full O b ethoxy And the like.
c i〜c 6アルキルチオ基とは、 直鎖又は分岐鎖状のアルキルチオ基を示し、 例えばメチルチオ基、 ェチルチオ基、 n —プロピルチオ基、 イソプロピルチオ 基、 n—プチルチオ基、 イソプチルチオ基、 s e c—プチルチオ基、 t e r t - プチルチオ基、 n—へキシルチオ基等を挙げることができる。 The ci- 6 alkylthio group is a linear or branched alkylthio group, for example, a methylthio group, an ethylthio group, an n-propylthio group, an isopropylthio group, an n-butylthio group, an isobutylthio group, a sec-butylthio group, tert- Examples thereof include a butylthio group and an n-hexylthio group.
C 丄〜C 4ハロアルキルチオ基とは、 ハロゲン原子によって置換された、 直鎖 又は分岐鎖状のアルキルチオ基を示し、 例えばフルォロメチルチオ基、 ジフルォ ロメチルチオ基、 トリフルォロメチルチオ基、 ペンタフルォロェチルチオ基等を 挙げることができる。 The C丄-C 4 haloalkylthio group, substituted by a halogen atom, a linear or branched shows an alkylthio group, for example, full-O b methyl thio group, Jifuruo Romechiruchio group, triflate Ruo b methylthio group, Pentafuruo And a loethylthio group.
一般式 [ I ] で表される本発明化合物の中には、 分子内に 1個又は 2個以上の 不斉炭素原子を有しているものもあり、 そのような化合物には光学異性体が存在 する。 純粋な個々のジァステレオマー、 ェナンチォマー及びこれらの混合物も本 発明化合物に含まれる。  Some of the compounds of the present invention represented by the general formula [I] have one or more asymmetric carbon atoms in the molecule, and such compounds have optical isomers. Exists. Pure individual diastereomers, enantiomers and mixtures thereof are also included in the compounds of the present invention.
一般式 [ I ] で表される本発明化合物の好ましい化合物としては、 Xがメチル 基、 トリフルォロメチル基、 塩素原子、 臭素原子又はヨウ素原子で R 1が水素原 子、 メチル基又はェチル基で、 R 2が水素原子， メチル基、 ェチル基又は n—プ 口ピル基で、 R 3がメチル基、 ェチル基、 n —プロピル基、 イソプロピル基、 t e r t —ブチル基、 シクロプロピル基、 シクロペンチル基またはジクロロメチ ル基で、 Qがェチニル基、 ァセチル基、 プロピオニル基、 シクロプロピルカルボ ニル基又は 1 ―ヒ ドロキシェチル基である化合物を挙げることができる。 Preferred compounds of the compound of the present invention represented by the general formula [I] include X is a methyl group, trifluoromethyl group, chlorine atom, bromine atom or iodine atom and R 1 is a hydrogen atom, methyl group or ethyl group. And R 2 is a hydrogen atom, a methyl group, an ethyl group or an n-propyl group, and R 3 is a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a cyclopropyl group, a cyclopentyl group Or a compound in which Q is an ethynyl group, an acetyl group, a propionyl group, a cyclopropylcarbonyl group or a 1-hydroxyxethyl group in a dichloromethyl group.
次に、 一般式 [ I ] で表される本発明化合物の具体例を表 1〜表 6に示すが、 これらに限られるものではない。  Next, specific examples of the compound of the present invention represented by the general formula [I] are shown in Tables 1 to 6, but are not limited thereto.
表中の記号はそれぞれ以下の意味を示す。 M eとはメチル基を示し、 E tとは ェチル基を示し、 P rとは n—プロピル基を示し、 P r— i とはイソプロピル基 を示し、 B uとは n —ブチル基を示し、 B u— i とはイソブチル基を示し、 B u — t とは t e r t —ブチル基を示し、 P r— c y cとはシクロプロピル基を示 し、 P e n— c y cとはシクロペンチル基を示し、 P hとはフエ二ル基を示す。 また、 例えば P h ( 4 - C 1 ) とは 4 _クロ口フエ二ル基を示す。 (表 1 ) The symbols in the table have the following meanings. Me represents a methyl group, Et represents an ethyl group, Pr represents an n-propyl group, Pri represents an isopropyl group, and Bu represents an n-butyl group. , Bu-i represents an isobutyl group, Bu-t represents a tert-butyl group, Pr-cyc represents a cyclopropyl group, Pen-cyc represents a cyclopentyl group, and P-cyc represents a cyclopentyl group. h represents a phenyl group. Further, for example, P h (4-C 1) represents a 4_chlorophenyl group. (table 1 )
* *— * * —
i
Figure imgf000007_0001
i
Figure imgf000007_0001
H n υ we DU I し UM6  H n υ we DU I shi UM6
U we Μβ Γ 1 し iwfle o» **， «J, u し丄 π n  U we Μβ Γ 1 and iwfle o »**,« J, u and π n
U  U
4 we _ 1 L = Ui4 we _ 1 L = Ui
U ΙΠβ Mハ ~1 U ΙΠβ M C ~ 1
4 し liMe ； p し丄 o " π U we θ ΓΓ - 1 一 ， ， o し i g， o r u η_ ■  4 liMe; p shu o "π U we θ ΓΓ-1,, o ig, oru η_ ■
we β ΓΓ - 1 し UMe we β ΓΓ-1 Shi UMe
Q A c J;一 nし丄 3 u ivie Me rr-i Q A c J; one n shu 3 u ivie Me rr-i
o, 4, 0 し丄 3 u Me ht hi C = CH o, 4, 0 sh 3 u Me ht hi C = CH
3. 4, 5-Cl3 U Me e Bu- L— CH3. 4, 5-Cl 3 U Me e Bu- L— CH
3, 4, 5-Cl3 c 3, 4, 5-Cl 3 c
Μβ me ΓΓ - 1 し =し H Μβ me ΓΓ-1 si = shi H
3, 4， 5-Cl3 π we ： 3, 4, 5-Cl 3 π we:
Μθ ΓΓ~1 し UMe Μθ ΓΓ ~ 1 then UMe
3. 4, 5-Cl3 π β τ?+ 3. 4, 5-Cl 3 π β τ? +
Μ bt し UMe Μ bt then UMe
3, 4， 5-Cl3 π U we MC DU t しリ Me3, 4, 5-Cl 3 π U we MC DU t
3, 4, 5-Cl3 c Mo 3, 4, 5-Cl 3 c Mo
IV16 1 し υΜΘ IV16 1 υΜΘ
3, 5-Cl„ U u 3, 5-Cl „U u
Π Μθ 1 し UM6 u n Me Me ΓΓ_ 1 し =LH u W6 we 1 し UMeΠ Μθ 1 UM6 un Me Me _ _ 1 = = LH u W6 we 1 U UMe
3, 5-Cl2 n u CI Ιτΐθ ΓΓ 1 し UMe3, 5-Cl 2 nu CI Ιτΐθ ΓΓ 1 then UMe
3, 5-Cl2 n u Mo IK1o6 し 3, 5-Cl 2 nu Mo IK1o6
o l MliC し L o し uri し し o l MliC then L o uri
3， 5-Cl2 s Me Me Pr-i COMe3, 5-Cl 2 s Me Me Pr-i COMe
3, 5-Cl2 0 Me Et Et C≡CH 3, 5-Cl 2 0 Me Et Et C≡CH
0 Me Me Bu- 1 C≡CH 0 Me Me Bu- 1 C≡CH
3, 5-Cl 0 Me Et Et COMe3, 5-Cl 0 Me Et Et COMe
3. 5-Cl 0 Me Me Bu-t COMe3.5-Cl 0 Me Me Bu-t COMe
3. 5-Cl? s Pr-cyc Et Et COMe s CHF2 Et Et COMe s Me Me CHC12 COMe d aw 3K S 3W-9 13-5 'ε 3. 5-Cl? S Pr- cyc Et Et COMe s CHF 2 Et Et COMe s Me Me CHC1 2 COMe d aw 3K S 3W-9 13-5 'ε
0 9W-9 π-s 'ε  0 9W-9 π-s' ε
9W03 3 ;3 0 iD-s 'ε 9W03 3; 3 0 iD-s' ε
3 Wcl 0 9K-9 i3-s 'ε  3 Wcl 0 9K-9 i3-s' ε
H3≡D I --id 9W 3W 0 9W-9 iD- 'ε H3≡D I --id 9W 3W 0 9W-9 iD- 'ε
Figure imgf000008_0001
Figure imgf000008_0001
9K03 \ aw S 9W-9 ^g-s 'ε 9K03 \ aw S 9W-9 ^ g-s' ε
o i-ng 0 - 9 •tg-9 'ε o i-ng 0-9tg-9 'ε
Figure imgf000008_0002
Figure imgf000008_0002
0 -9 ュ 8-s 'ε  0 -9 new 8-s' ε
H。≡：) ト ng aw 0 9W-9 'ε H. ≡ :) g ng aw 0 9W-9 'ε
Figure imgf000008_0003
Figure imgf000008_0003
Η3≡3 0 9W-9  Η3≡3 0 9W-9
9W03 ト · aw 3W s  9W03 G · aw 3W s
■3 -ng aw 9W 0 - i3-s 'ε  ■ 3 -ng aw 9W 0-i3-s' ε
3W03 ^3 9W 0 - iD-s 'ε  3W03 ^ 3 9W 0-iD-s' ε
903 9W 9W 0 3W-i^ i3-s 'ε  903 9W 9W 0 3W-i ^ i3-s' ε
Η3≡3 3W 9W s i3-s 'ε  Η3≡3 3W 9W s i3-s' ε
Η0≡3 9W 3W 0 - ΪΟ-S 'ε  Η0≡3 9W 3W 0-ΪΟ-S 'ε
Η3≡3 3N 0 D- s 'ε  Η3≡3 3N 0 D- s' ε
Η3≡3 d 0 D-s 'ε  Η3≡3 d 0 D-s' ε
d 9W 0 z HN-i' -s 'ε  d 9W 0 z HN-i '-s' ε
養 ト jj 0 3W - Η3≡3 トュ d 8W a« 0 J9-s 'ε
Figure imgf000008_0004
Nutrition jj 0 3W-Η3≡3 Tu d 8W a «0 J9-s' ε
Figure imgf000008_0004
aw a« 0  aw a «0
H3≡3 ト ng a 0 jg-s 'ε H3≡3 ng a 0 jg-s' ε
Figure imgf000008_0005
Figure imgf000008_0005
HD≡3 0 ュ g - s 'ε HD≡30 0 g-s' ε
o 9W 0 iD-s 'ε  o 9W 0 iD-s' ε
9W03 '( )- 0 1D-9 'C  9W03 '()-0 1D-9' C
9W03 '(( ) - 0 D - S'£  9W03 '(()-0 D-S' £
9W03 3K s iD-s 'ε  9W03 3K s iD-s' ε
H  H
ε' Z a a  ε 'Z a a
ΐ  ΐ
9l8S0/86df/13d 0i8ee/66OW (表 3 ) 9l8S0 / 86df / 13d 0i8ee / 66OW (Table 3)
,2 3 ,twenty three
Xn R Q Xn R Q
4, 5- (CFつ)。 0 Me Me Pr-i C≡CH 4, 5-(CF )0 0 Me Et Et C≡CH 4.5-(CFJ9 0 Me Me Bu-t C≡CH 4.5-(CF )ヮ 0 Me Et Bu-t COMe 4.5-(CFn)9 0 Me Me Pr-i COMe 4, 5-(CFJ9 0 Me Et Et COMe 4, 5-(CFJ9 0 Me Me Bu-t COMe 3-Br, 5-Me 0 Me Me Pr-i C≡CH 3-Br, 5-Me 0 Me Et Et C≡CH 3-Br, 5-Me 0 Me Me Bu-t C≡CH 3-Br, 5-Me 0 Me Me Pr-i COMe 3-Br.5-Me 0 Me Et Et COMe 3-Br, 5-Me 0 Me Me Bu-t COMe 3-CF3 0 Me Me Pr-i COMe 3-CF3, 5-Cl 0 Me Me Pr-i C≡CH 3-CF3> 5-Cl 0 Me Et Et C≡CH 3-CF3, 5- CI 0 Me Me Bu-t C≡CH 3- CF3, 5-Cl 0 Me Me Pr-i COMe 3-CF3, 5-Cl 0 Me Et Et COMe 3-CF3> 5-Cl 0 Me Me Bu-t COMe 3-CF3> 5-Cl s Me Me Pr-i COMe 3-Cl 0 Me Me Pr-i COMe4, 5- (CF). 0 Me Me Pr-i C≡CH 4, 5- (CF) 0 0 Me Et Et C≡CH 4.5- (CFJ 90 Me Me Bu-t C≡CH 4.5- (CF) ヮ 0 Me Et Bu-t COMe 4.5- (CF n ) 90 Me Me Pr-i COMe 4, 5- (CFJ 90 Me Et Et COMe 4, 5- (CFJ 90 Me Me Bu-t COMe 3-Br, 5-Me 0 Me Me Pr-i C≡CH 3-Br, 5-Me 0 Me Et Et C≡CH 3-Br, 5-Me 0 Me Me Bu-t C≡CH 3-Br, 5-Me 0 Me Me Pr-i COMe 3-Br.5-Me 0 Me Et Et COMe 3-Br, 5-Me 0 Me Me Bu-t COMe 3-CF 3 0 Me Me Pr-i COMe 3-CF 3 ,, 5-Cl 0 Me Me Pr -i C≡CH 3-CF 3> 5-Cl 0 Me Et Et C≡CH 3-CF 3 , 5- CI 0 Me Me Bu-t C≡CH 3- CF 3 , 5-Cl 0 Me Me Pr- i COMe 3-CF 3 , 5-Cl 0 Me Et Et COMe 3-CF 3> 5-Cl 0 Me Me Bu-t COMe 3-CF 3> 5-Cl s Me Me Pr-i COMe 3-Cl 0 Me Me Pr-i COMe
3- CI.5- Br 0 Me Me Pr-i C≡CH 3-Cl.5- CF 0 Me Me Pr-i C≡CH3- CI.5- Br 0 Me Me Pr-i C≡CH 3-Cl.5- CF 0 Me Me Pr-i C≡CH
3-C1.5-CF 0 Me Et Et C≡CH 3-Cl, 5- CF 0 Me Me Bu-t C≡CH 3-Cl, 5-Br 0 Me Me Pr-i COMe 3-C1.5-CF 0 Me Me Pr-i COMe 3-C1.5-CF 0 Me Et Et COMe 3-C1.5-CF 0 Me Me Bu-t COMe 3-C1.5-CF 0 H Me Pr-i C≡CH 3-C1.5-CF 0 H Me Bu-t C≡CH 3-Cl, 5- CF 0 H Et Et C≡CH 3-C1.5-CF 0 H Me Pr-i COMe (表 4 ) 3-C1.5-CF 0 Me Et Et C≡CH 3-Cl, 5- CF 0 Me Me Bu-t C≡CH 3-Cl, 5-Br 0 Me Me Pr-i COMe 3-C1.5- CF 0 Me Me Pr-i COMe 3-C1.5-CF 0 Me Et Et COMe 3-C1.5-CF 0 Me Me Bu-t COMe 3-C1.5-CF 0 H Me Pr-i C≡CH 3-C1.5-CF 0 H Me Bu-t C≡CH 3-Cl, 5- CF 0 H Et Et C≡CH 3-C1.5-CF 0 H Me Pr-i COMe (Table 4)
Xn R QXn R Q
3-Cl. 5-CF 0 H Me Bu- COMe 3-Cl, 5-CF 0 H Et Et COMe 3-Cl, 5-CF 0 Me _ (CH2) 4- COMe 3-Cl, 5-CF 0 Me COMe 3-Cl. 5-CF 0 H Me Bu- COMe 3-Cl, 5-CF 0 H Et Et COMe 3-Cl, 5-CF 0 Me _ (CH 2 ) 4 -COMe 3-Cl, 5-CF 0 Me COMe
一 (CH2) 5— One (CH 2) 5 —
3-Cl, 5-CF 0 Me p Γr I  3-Cl, 5-CF 0 Me p Γr I
3-Cl. 5-CF 0 Me Γ 1 uri 3-Cl. 5-CF 0 Me we Γ 1 jrr eye 3-Cl. 5-CF 0 Me we r Γ 1 il
Figure imgf000010_0001
3-Cl. 5-CF 0 Me Γ 1 uri 3-Cl. 5-CF 0 Me we Γ 1 jrr eye 3-Cl. 5-CF 0 Me wer Γ 1 il
Figure imgf000010_0001
3-Cl, 5-CF S Me M ΜcΘ Dli I ΓΠ LiΜWlοfci 3-Cl . 5-CF s Me Mo Ρτ I— 1 ΓΠΜΡ
Figure imgf000010_0002
3-Cl, 5-CF S Me M ΜcΘ Dli I ΓΠ LiΜWlοfci 3-Cl .5-CF s Me Mo Ρτ I— 1
Figure imgf000010_0002
3-CN 0 Me  3-CN 0 Me
3 - Me, 5-Br 0 Me Mo 1 一 Π 3- Me. 5-Br 0 Me r—一 ru
Figure imgf000010_0003
3-Me, 5-Br 0 Me Mo 1 1 Π 3-Me. 5-Br 0 Mer r- 1 ru
Figure imgf000010_0003
3- Me, 5-Cl 0 Me Mp Pr- i C≡CH 3- Me, 5-Cl 0 Me Et Et C≡CH 3 - Me. 5-Cl 0 Me Me Bu-t C≡CH 3- Me, 5- Br 0 Me Me Pr - i し UM6 3- Me, 5-Br 0 Me Et Et COMe 3 - Me, 5- Br 0 Me Me Bu-t COMe 3- Me, 5- CI 0 Me Me Pr-i COMe 3- Me. 5- CI 0 Me Et Et COMe 3- e. 5-Cl 0 Me Me Bu-t COMe 3-N02 0 Me Me Pr-i COMe 3-N02, 4-Me 0 Me Me Pr- i COMe 3- N02. 5 - Br 0 Me Me Pr-i COMe 3 - N02, 5-Cl 0 Me Me Pr-i COMe3-Me, 5-Cl 0 Me Mp Pr- i C≡CH 3-Me, 5-Cl 0 Me Et Et C≡CH 3-Me. 5-Cl 0 Me Me Bu-t C≡CH 3- Me, 5- Br 0 Me Me Pr-i UM6 3- Me, 5-Br 0 Me Et Et COMe 3-Me, 5- Br 0 Me Me Bu-t COMe 3- Me, 5- CI 0 Me Me Pr-i COMe 3- Me. 5- CI 0 Me Et Et COMe 3- e. 5-Cl 0 Me Me Bu-t COMe 3-N0 2 0 Me Me Pr-i COMe 3-N0 2, 4-Me 0 Me Me Pr -. i COMe 3- N0 2 5 - Br 0 Me Me Pr-i COMe 3 - N0 2, 5-Cl 0 Me Me Pr-i COMe
3- N02, 6-OMe 0 Me Me Pr- i COMe3- N0 2 , 6-OMe 0 Me Me Pr- i COMe
4-Ph 0 Me Me Pr- i COMe4-Ph 0 Me Me Pr- i COMe
4- Ph (4-Me) 0 Me Me Me COMe (表 5 ) 4- Ph (4-Me) 0 Me Me Me COMe (Table 5)
Xn A R1 R2 QXn AR 1 R 2 Q
4-Ph (4-0Me) 0 Me Me Me COMe4-Ph (4-0Me) 0 Me Me Me COMe
4-Ph (4-Cl) 0 Me Me Me CO e4-Ph (4-Cl) 0 Me Me Me CO e
4-Ph (4-CF3) 0 Me Me Me COMe4-Ph (4-CF 3 ) 0 Me Me Me COMe
4-0Ph 0 Me Me Pr-i COMe4-0Ph 0 Me Me Pr-i COMe
4-0Ph (4-Me) 0 Me Me Bu COMe4-0Ph (4-Me) 0 Me Me Bu COMe
4 - 0Ph(4- OMe) 0 Me Me Bu-i COMe4-0Ph (4- OMe) 0 Me Me Bu-i COMe
4-0Ph (4-Cl) 0 Me Me Me COMe4-0Ph (4-Cl) 0 Me Me Me COMe
4-0Ph (4-CF3) 0 Me Me Me COMe4-0Ph (4-CF 3 ) 0 Me Me Me COMe
4, 6- (CF3) 2 0 Me Me Pr-i COMe4, 6- (CF 3) 20 Me Me Pr-i COMe
4 - CF3 0 Me Me Pr-i COMe4-CF 30 Me Me Pr-i COMe
4- CI 0 Me Me Pr-i COMe4- CI 0 Me Me Pr-i COMe
4-Ph 0 Et Me Pr-i COMe4-Ph 0 Et Me Pr-i COMe
5-Br 0 Me Me Pr-i COMe5-Br 0 Me Me Pr-i COMe
5-CF^ 0 Me Me Pr-i C≡CH5-CF ^ 0 Me Me Pr-i C≡CH
5— CF3 0 Me Me Pr-i COMe5— CF 30 Me Me Pr-i COMe
5 - CF3 0 Me Me CH2CH=CH2 COMe5-CF 30 Me Me CH 2 CH = CH 2 COMe
5- CF3 0 Me Me Pen - eye COMe5- CF 30 Me Me Pen-eye COMe
5- CF3 0 Me Me - ] COMe 5- CF 30 Me Me-] COMe
Me  Me
5- CF Me Me COMe  5- CF Me Me COMe
5 - CF3 0 Me Me Bu-t C≡CH 5-CF3 0 Me Et Et C≡CH 5-CF3 0 Me Me Bu-t COMe 5-CF 30 Me Me Bu-t C≡CH 5-CF 30 Me Et Et C≡CH 5-CF 30 Me Me Bu-t COMe
0 Me Et Et COMe 0 Me Et Et COMe
5- CF3 0 Me Me CH2Pr-cyc COMe5- CF 3 0 Me Me CH 2 Pr-cyc COMe
5-OCH CH=CH2 0 Me Me Pr-i COMe 5-OCH C≡CH 0 Me Me Pr-i COMe5-OCH CH = CH 2 0 Me Me Pr-i COMe 5-OCH C≡CH 0 Me Me Pr-i COMe
5-OCHF, 0 Me Me Pr-i COMe 5-OCHF: 0 Me Et Et COMe 5 - (OF 0 Me Me Bu-t COMe 5-OCHF S Me Me Pr-i COMe 5-SCHF 0 Me Me Pr-i COMe 5-SCHF 0 Me Et Et COMe L05-OCHF, 0 Me Me Pr-i COMe 5-OCHF: 0 Me Et Et COMe 5-(OF 0 Me Me Bu-t COMe 5-OCHF S Me Me Pr-i COMe 5-SCHF 0 Me Me Pr-i COMe 5-SCHF 0 Me Et Et COMe L0
(表 6 (Table 6
11
n A R1 RJ Qn AR 1 R J Q
5 - SCHF„ 0 Me Me Bu-t CO e 5-SCHF „0 Me Me Bu-t CO e
S Me Me Pr-i COMe S Me Me Pr-i COMe
5-SMe 0 Me Me Pr-i COMe -Cl 0 Me Me Pr-i COMe5-SMe 0 Me Me Pr-i COMe -Cl 0 Me Me Pr-i COMe
5 - CI 0 Me Et Et COMe5-CI 0 Me Et Et COMe
5- CI 0 Me Me Bu-t COMe5- CI 0 Me Me Bu-t COMe
5-C1 s Me Me Pr-i COMe5-C1 s Me Me Pr-i COMe
5- NO 0 Me Me Pr-i COMe 2 5- NO 0 Me Me Pr-i COMe 2
6-CF 0 Me Me Pr-i COMe 3  6-CF 0 Me Me Pr-i COMe 3
6-Ph 0 Me Me Pr-i COMe 6-Ph 0 Me Me Pr-i COMe
3, 5 - (CF^)„ 0 Me Me Pr-i C≡CH 3 2 3, 5-(CF ^) „0 Me Me Pr-i C≡CH 3 2
3, 5- (CF ) n 0 Me Me Pr-i COMe 3 2 3, 5- (CF) n 0 Me Me Pr-i COMe 3 2
3- CI, 5 - CF s Me Me Pr-i C≡CH  3- CI, 5-CF s Me Me Pr-i C≡CH
3  Three
3- CFQ 0 Me Me Pr-i C≡CH 3 3- CF Q 0 Me Me Pr-i C≡CH 3
4-CF„ 0 Me Me Pr-i C≡CH 3  4-CF „0 Me Me Pr-i C≡CH 3
3.5- (CFJ .6- CI 0 Me Me Pr-i C≡CH 3 2  3.5- (CFJ .6- CI 0 Me Me Pr-i C≡CH 3 2
3.5 - CF 6- CI 0 Me Me Pr-i COMe 3 2  3.5-CF 6- CI 0 Me Me Pr-i COMe 32
5- CF .6 - CI 0 Me Me Pr-i C≡CH 3  5- CF .6-CI 0 Me Me Pr-i C≡CH 3
5-CF0, 6- CI 0 Me Me Pr-i COMe 3 5-CF 0 , 6- CI 0 Me Me Pr-i COMe 3
3-CN 0 Me Me Pr-i C≡CH 3-CN 0 Me Me Pr-i C≡CH
5-N0 0 Me Me Pr-i C≡CH 2 5-N0 0 Me Me Pr-i C≡CH 2
3, 5-Cl„ 0 Me Me Pr-i CH(0H) e ί  3, 5-Cl „0 Me Me Pr-i CH (0H) e ί
3- CF 0 Me Me Pr-i CH(0H)Me 3- CF 0 Me Me Pr-i CH (0H) Me
4 - CF3 0 Me Me Pr-i CH (OH) Me4-CF 30 Me Me Pr-i CH (OH) Me
3, 5 - CF 2, 6- CI 0 Me Me Pr-i CH(0H)Me3, 5-CF 2, 6- CI 0 Me Me Pr-i CH (0H) Me
5-CF , 6-Cl 0 Me Me Pr-i CH(0H)Me5-CF, 6-Cl 0 Me Me Pr-i CH (0H) Me
3-CN 0 Me Me Pr-i CH(0H)Me3-CN 0 Me Me Pr-i CH (0H) Me
5-NOq 0 Me Me Pr-i CH(0H) e5-NOq 0 Me Me Pr-i CH (0H) e
5-Me 0 Me Me Pr-i C≡CH5-Me 0 Me Me Pr-i C≡CH
6-F 0 Me Me Pr-i C≡CH6-F 0 Me Me Pr-i C≡CH
6 - F 0 Me Me Pr-i COMe6-F 0 Me Me Pr-i COMe
3, o-Cl0, 6 - Me 0 Me Me Pr-i CH(0H)Me3, o-Cl 0 , 6-Me 0 Me Me Pr-i CH (0H) Me
5-Br, 6 - Me 0 Me Me Pr-i COMe5-Br, 6-Me 0 Me Me Pr-i COMe
3-Cl, 5-CF3 0 H Me Bu-t CH (OH) Me 3-Cl, 5-CF 3 0 H Me Bu-t CH (OH) Me
13(H0)HD 0 ε - s Ί3-ε 13 (H0) HD 0 ε -s Ί3-ε
養 0)H3 Wd 3W 0 - s Ίο-ε  Nutrition 0) H3 Wd 3W 0-s Ίο-ε
13 ig 3W 0  13 ig 3W 0
嚷 0)H3 8W 9W 0  嚷 0) H3 8W 9W 0
8W(H0)H3 トュ d 3K 9W 0
Figure imgf000013_0001
8W (H0) H3 Tu d 3K 9W 0
Figure imgf000013_0001
SW(H0)HD ト W aw 0 z(¾-9 'ε SW (H0) HD G W aw 0 z (¾-9 'ε
■3 Wd 3W 0  ■ 3 Wd 3W 0
HD≡D 0 ζ(¾-9'ε aw (HO) HO 3W aw 0 0Ν-ε HD≡D 0 ζ (¾-9'ε aw (HO) HO 3W aw 0 0Ν-ε
D  D
2 a ) ττ  2 a) ττ
9l8S0/86df/lDd 0l8£e/66 OW (表 8 ) 9l8S0 / 86df / lDd 0l8 £ e / 66 OW (Table 8)
Figure imgf000014_0001
Figure imgf000014_0001
Xn A R R R QXn A R R R Q
2 - Br 0 Me Me Pr-i C≡CH2-Br 0 Me Me Pr-i C≡CH
2 - Br 0 Me Me Bu-t C≡CH2-Br 0 Me Me Bu-t C≡CH
2 - CI 0 Me Me Pr-i C≡CH2-CI 0 Me Me Pr-i C≡CH
2 - CI 0 Me Me Bu-t C≡CH2-CI 0 Me Me Bu-t C≡CH
5-C1 0 Me Me Pr-i C≡CH5-C1 0 Me Me Pr-i C≡CH
5 - CI 0 Me Me Bu-t C≡CH5-CI 0 Me Me Bu-t C≡CH
2-Cl, 6 - Br 0 Me Me Pr-i C≡CH2-Cl, 6-Br 0 Me Me Pr-i C≡CH
2-Cl, 6 - Br 0 Me Me Bu-t C≡CH2-Cl, 6-Br 0 Me Me Bu-t C≡CH
2 - CI, 6 - Br 0 Me Et Et C≡CH2-CI, 6-Br 0 Me Et Et C≡CH
2-Cl, 6 - Me 0 Me Me Pr-i C≡CH2-Cl, 6-Me 0 Me Me Pr-i C≡CH
2 - CI, 6 - Me 0 Me Me Bu-t C≡CH2-CI, 6-Me 0 Me Me Bu-t C≡CH
2-Cl, 6 - Me 0 Me Et Et C≡CH
Figure imgf000014_0002
2-Cl, 6-Me 0 Me Et Et C≡CH
Figure imgf000014_0002
2, 6-Br2 0 Me -CH?CH2CH?CH (CHJ - C≡CH2, 6-Br 2 0 Me -CH ? CH 2 CH ? CH (CHJ-C≡CH
2， 6-Br2 0 Me Me Bu-t C≡CH2, 6-Br 2 0 Me Me Bu-t C≡CH
2, 6-Cl 0 Me Et Et C≡CH
Figure imgf000014_0003
2, 6-Cl 0 Me Et Et C≡CH
Figure imgf000014_0003
2, -Clg 0 Me Me Pr-i C≡CH 2, -Clg 0 Me Me Pr-i C≡CH
2, -Clg s Me Me Pr-i C≡CH2, -Clg s Me Me Pr-i C≡CH
2- 1, 6-Me 0 Me Me Pr-i C≡CH2- 1, 6-Me 0 Me Me Pr-i C≡CH
2- 1. 6- Me 0 Me Me Bu-t C≡CH2-1.6-Me 0 Me Me Bu-t C≡CH
6-Ph 0 Me Me Pr-i C≡CH6-Ph 0 Me Me Pr-i C≡CH
6-Ph s Me Me Pr- i C≡CH6-Ph s Me Me Pr- i C≡CH
H 0 Me Me Bu- t COMeH 0 Me Me Butt COMe
H 0 Me Me Pr-i COMeH 0 Me Me Pr-i COMe
2- Br 0 Me Me Pr- i COMe2- Br 0 Me Me Pr- i COMe
2-Br 0 Me Me Bu-t COMe (表 9 2-Br 0 Me Me Bu-t COMe (Table 9
2 3 twenty three
Xn R R R Q Xn R R R Q
2-Cl 0 Me Me Pr-i COMe 2-Cl 0 Me Me Bu-t COMe 5 - CI 0 Me Me Pr-i COMe 5-C1 0 Me Me Bu-t COMe2-Cl 0 Me Me Pr-i COMe 2-Cl 0 Me Me Bu-t COMe 5-CI 0 Me Me Pr-i COMe 5-C1 0 Me Me Bu-t COMe
2-Cl, 6-Br 0 Me Me Pr-i COMe 2-Cl, 6-Br 0 Me Me Bu-t COMe 2-Cl. 6-Br 0 Me Et Et COMe 2-Cl. 6-Me 0 Me Me Pr-i COMe 2-Cl, 6-Me 0 Me Me Bu-t COMe 2-Cl. 6-Me 0 Me Et Et COMe 2, 6-Br, 0 H Me Pr - COMe2-Cl, 6-Br 0 Me Me Pr-i COMe 2-Cl, 6-Br 0 Me Me Bu-t COMe 2-Cl. 6-Br 0 Me Et Et COMe 2-Cl. 6-Me 0 Me Me Pr-i COMe 2-Cl, 6-Me 0 Me Me Bu-t COMe 2-Cl. 6-Me 0 Me Et Et COMe 2, 6-Br, 0 H Me Pr-COMe
2, 6- Br 0 Me Me Pr - COMe 2. 6 - Br 0 Et Me Pr - COMe2, 6- Br 0 Me Me Pr-COMe 2. 6-Br 0 Et Me Pr-COMe
2, 6- (OMe) 0 Me Me Pr- COMe 2, 6- (OMe) 0 Me Me Pr- COMe
2  Two
2, 6- Br, 0 Me Me Pr- COEt 2, 6- Br, 0 Me Me Pr- COEt
2 Two
2, 6-Br 0 Me Me Pr- COPr-cyc 2  2, 6-Br 0 Me Me Pr- COPr-cyc 2
2. 6-Br s Me Me Pr- COMe 2  2. 6-Br s Me Me Pr- COMe 2
2. 6-Br 0 Me Et Et COMe 2  2. 6-Br 0 Me Et Et COMe 2
2, 6-Br 0 Me Me Bu-t COMe 2  2, 6-Br 0 Me Me Bu-t COMe 2
2, 6-Br 0 Me - (CH2) 4- COMe 2 2, 6-Br 0 Me-(CH 2) 4 -COMe 2
2, 6-Br 0 Me - (CH2) 5 - COMe 2 2, 6-Br 0 Me- ( CH 2) 5 -COMe 2
2, 6-Br 0 Me Et Bu-t COMe 2  2, 6-Br 0 Me Et Bu-t COMe 2
2, 6-Cl 0 Me Et Et COMe 2  2, 6-Cl 0 Me Et Et COMe 2
2, 6-Cl 0 Me Me Bu-t COMe 2  2, 6-Cl 0 Me Me Bu-t COMe 2
2, 6-Cl 0 Me Me Pr-i COMe 2  2, 6-Cl 0 Me Me Pr-i COMe 2
2, 6-Cl Me Pr-i COMe 2 s Me  2, 6-Cl Me Pr-i COMe 2 s Me
2-1, 6-Me 0 Me Me Pr-i COMe 2 - 1, 6-Me 0 Me Me Bu-t COMe 6-Ph 0 Me Me Pr-i COMe 6-Ph s Me Me Pr-i COMe 6-Me 0 Me Me Pr- i C≡CH 6 - Me 0 Me Me Pr- i COMe 2-1, 6-Me 0 Me Me Pr-i COMe 2-1, 6-Me 0 Me Me Bu-t COMe 6-Ph 0 Me Me Pr-i COMe 6-Ph s Me Me Pr-i COMe 6- Me 0 Me Me Pr- i C≡CH 6-Me 0 Me Me Pr- i COMe
2- N02, 6-Me 0 Me Me Pr-i COMe 2- N02, 6-Me 0 Me Me Pr- i CH (OH) Me (表 1 0 ) n A R1 R2 R3 Q2- N0 2 , 6-Me 0 Me Me Pr-i COMe 2- N0 2 , 6-Me 0 Me Me Pr- i CH (OH) Me (Table 10) n AR 1 R 2 R 3 Q
5 - CI 0 Me Et Et Et5-CI 0 Me Et Et Et
5- CI 0 Me Me Pr-i Et5- CI 0 Me Me Pr-i Et
5- CI 0 Me Me Pr-i CH(OH)Me5- CI 0 Me Me Pr-i CH (OH) Me
6-OMe 0 Me Me Pr-i COMe6-OMe 0 Me Me Pr-i COMe
6-OMe 0 Me Me Pr-i CH (OH) e6-OMe 0 Me Me Pr-i CH (OH) e
6-Cl 0 Me Me Pr-i COMe6-Cl 0 Me Me Pr-i COMe
6 - CI 0 Me Me Pr-i CH (OH)Me6-CI 0 Me Me Pr-i CH (OH) Me
5, 6-Cl9 0 Me Me Pr-i COMe 2 5, 6-Cl 9 0 Me Me Pr-i COMe 2
5, 6-Clつ 0 Me Me Pr-i C嚷) Me 2  5, 6-Cl 0 Me Me Pr-i C 嚷) Me 2
2, 5-Cl„ 0 Me Me Pr-i COMe 2  2, 5-Cl „0 Me Me Pr-i COMe 2
2, 5-Cl2 0 Me Me Pr-i CH (OH) Me2, 5-Cl 2 0 Me Me Pr-i CH (OH) Me
5 - Br 0 Me Me Pr - 1 COMe5-Br 0 Me Me Pr-1 COMe
5 - Br 0 Me Me Pr-i CH (OH)Me5-Br 0 Me Me Pr-i CH (OH) Me
5- Br, 6-Cl 0 Me Me Pr-i COMe5-Br, 6-Cl 0 Me Me Pr-i COMe
5- Br, 6- CI 0 Me Me Pr-i CH (OH)Me5-Br, 6- CI 0 Me Me Pr-i CH (OH) Me
5-Br 0 Me Me Bu-t COMe5-Br 0 Me Me Bu-t COMe
5-Cl 0 Me Me Bu-t CH (OH)Me5-Cl 0 Me Me Bu-t CH (OH) Me
5-Br 0 Me Me Bu-t CH (OH) Me 5-Br 0 Me Me Bu-t CH (OH) Me
(表 1 1 ) (Table 11)
Figure imgf000017_0001
Figure imgf000017_0001
2 3 twenty three
Xn R R R Q Xn R R R Q
H 0 Me Me Bu-t COMe H S Me Me Bu-t COMeH 0 Me Me Bu-t COMe H S Me Me Bu-t COMe
2 - CI 0 Me Me Pr-i COCF3 2-C1 0 Me Me Bu-t COMe 2 - CI 0 Me Et Et COMe 2, 6 - Br 0 Me Me Pr-i C≡CH 2, 6 - Br 0 Me Me Pr-i COMe 2, 6 - Br 0 Me Me Bu-t COMe 2, 6-Br 0 Me Et Et COMe2-CI 0 Me Me Pr-i COCF 3 2-C1 0 Me Me Bu-t COMe 2-CI 0 Me Et Et COMe 2, 6-Br 0 Me Me Pr-i C≡CH 2, 6-Br 0 Me Me Pr-i COMe 2, 6-Br 0 Me Me Bu-t COMe 2, 6-Br 0 Me Et Et COMe
2, 6- (OMe) S Me Me Pr-i COMe 2, 6- (OMe) S Me Me Pr-i COMe
2  Two
2, 6-Cl 0 Me Me Pr-i C≡CH 2, 6-Cl 0 Me Me Pr-i C≡CH
2, 6-Cl 0 Me Me Pr-i COMe 2, 6-Cl 0 Me Me Bu-t COMe 2, 6 - CI 0 Me Et Et COMe 2, 6-Cl S Me Me Pr-i COMe2, 6-Cl 0 Me Me Pr-i COMe 2, 6-Cl 0 Me Me Bu-t COMe 2, 6-CI 0 Me Et Et COMe 2, 6-Cl S Me Me Pr-i COMe
2, 6- (CF3)つ 0 Me Me Me COEt 2, 6-(CFJ 0 Me Me Me COPr 2.6-(CF3)0 0 Me Me Me COPr-cyc 2, 6-(CF3) 0 Me Me Pr-i C≡CH 2, 6-(CFJ 0 Me Me Pr-i COMe 2, 6- (CFゥ) 9 0 Me Me Bu-t COMe 2, 6-(CFJ 0 Me Et Et COMe 2, 6-(CF3)0 s Me Me Pr-i COMe 2, 3, 5, 6-Cl 0 Me Me Pr-i C≡CH 2, 3, 5, 6-Cl 0 Me Me Pr-i COMe 2, 3, 5, 6-Cl 0 Me Me Bu-t C≡CH 2, 3, 5, 6-Cl 0 Me Me Bu-t COMe 2-C1 0 Me Me Pr-i COMe 2- CI 0 Me Me Pr-i CH(OH) e (表 1 2) 2, 6- (CF 3 ) 0 Me Me Me COEt 2, 6- (CFJ 0 Me Me Me COPr 2.6- (CF 3 ) 0 0 Me Me Me COPr-cyc 2, 6- (CF 3 ) 0 Me Me Pr-i C≡CH 2, 6- (CFJ 0 Me Me Pr-i COMe 2, 6- (CF ゥ) 90 Me Me Bu-t COMe 2, 6- (CFJ 0 Me Et Et COMe 2, 6- (CF 3 ) 0 s Me Me Pr-i COMe 2, 3, 5, 6-Cl 0 Me Me Pr-i C≡CH 2, 3, 5, 6-Cl 0 Me Me Pr-i COMe 2, 3, 5, 6-Cl 0 Me Me Bu-t C≡CH 2, 3, 5, 6-Cl 0 Me Me Bu-t COMe 2-C1 0 Me Me Pr-i COMe 2- CI 0 Me Me Pr-i CH (OH) e (Table 1 2)
Xn A R1 R2 R3 Q Xn AR 1 R 2 R 3 Q
2, 6 - Br2 0 Me Me Pr-i CH(OH)Me 2, 6-Br 2 0 Me Me Pr-i CH (OH) Me
2, 6- Cl2 0 Me Me Pr-i CH(OH)Et 2, 6- Cl 2 0 Me Me Pr-i CH (OH) Et
2, 6- (CFg) 2 0 Me Me Pr-i CH(OH)Me 2, 6- (CFg) 20 Me Me Pr-i CH (OH) Me
2, 3, 5, 6-C1, 0 Me Me Pr-i CH (OH)Et  2, 3, 5, 6-C1, 0 Me Me Pr-i CH (OH) Et
4 一般式 [I] で示される本発明化合物は、 例えば以下に示す製造法に従って製 造することができる。  4 The compound of the present invention represented by the general formula [I] can be produced, for example, according to the following production method.
製造法 1 Manufacturing method 1
Figure imgf000018_0001
Figure imgf000018_0001
(式中、 R 1 R 、 R3、 Q、 X、 n及び Aは前記と同じ意味を表す。 ） 本発明化合物 [I] は、 一般式 [I I] で表されるピリジルォキシ （チォ） ァ ルカン酸誘導体を、 必要な場合には触媒及び 又は塩基の存在下に、 縮合剤を用 いて一般式 [I I I] で表されるアミ ン類と反応させることにより製造すること ができる。 この反応は通常、 溶媒中で行なわれる。 使用できる溶媒としては、 反応を阻害しない溶媒であればよく、 例えばペンタン、 へキサン、 ヘプタン、 シ クロへキサン、 石油エーテル、 リグ口イン、 ベンゼン、 トルエン又はキシレン等 の炭化水素類、 ジクロロメタン、 ジクロロェタン、 クロ口ホルム、 四塩化炭素、 クロ口ベンゼン又はジクロロベンゼン等のハロゲン化炭化水素類、 ジェチルェ一 テル、 ジイソプロピルエーテル、 エチレングリコールジメチルエーテル、 テ卜ラ ヒ ドロフラン又はジォキサン等のエーテル類、 アセトン、 メチルェチルケ トン、 / 10 (In the formula, R 1 R, R 3 , Q, X, n and A represent the same meaning as described above.) The compound [I] of the present invention is a pyridyloxy (thio) alkane represented by the general formula [II] The acid derivative can be produced by reacting an acid derivative with an amine represented by the general formula [III] using a condensing agent in the presence of a catalyst and / or a base, if necessary. This reaction is usually performed in a solvent. Solvents that can be used may be solvents that do not inhibit the reaction, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, rigoin, hydrocarbons such as benzene, toluene or xylene, dichloromethane, dichloroethane. Halogenated hydrocarbons such as chloroform, carbon tetrachloride, chlorobenzene, or dichlorobenzene; ethers such as ethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, or dioxane; acetone, methylethyl ketone , / Ten
17  17
メチルイソプロピルケ トン又はメチルイソブチルケ卜ン等のケトン類、 酢酸メチ ル又は酢酸ェチル等の酢酸エステル類、 ァセ トニト リル又はプロピオ二トリル等 の二卜リル類、 又はジメチルスルホキシ ド、 N , N—ジメチルホルムアミ ド又は スルホラン等の非プロ トン性極性溶媒、 あるいはこれらから選択される溶媒を組 み合わせた混合溶媒を用いることができる。 Ketones such as methyl isopropyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; ditriles such as acetonitril or propionitrile; or dimethyl sulfoxide, N, A nonprotonic polar solvent such as N-dimethylformamide or sulfolane, or a mixed solvent in which a solvent selected from these is combined can be used.
縮合剤としては、 例えば 1 一ェチル一 3— （3 —ジメチルァミノプロピル） 力 ルボジイ ミ ド '塩酸塩、 N, Ν' —ジシクロへキシルカルポジイミ ド、 カルボ二 ルジィ ミダゾ一ル、 2 —クロ口— 1， 3—ジメチルイ ミダゾリウムクロリ ド等力 挙げられる。  Examples of the condensing agent include 1-ethyl-3- (3-dimethylaminopropyl) force rubodiimide 'hydrochloride, N, Ν'-dicyclohexylcarbodiimide, carbonyldimidazole, and 2 — Black mouth—1,3-dimethylimidazolium chloride, etc.
角虫媒としては、 例えば 4ージメチルァミ ノ ピリジン、 1 ーヒ ドロキシベンゾト リアゾ一ル、 ジメチルホルムァミ ド等が挙げられる。  Examples of the hornworm medium include 4-dimethylaminopyridine, 1-hydroxybenzotriazole, dimethylformamide and the like.
塩基としては、 この型の反応に一般的に用いられるものが使用できる。 例えば 水酸化ナ卜リゥム又は水酸化力リゥム等のアル力リ金属水酸ィ匕物、 水酸化カルシ ゥム等のアル力リ土類金属水酸化物、 炭酸ナトリウム又は炭酸力リゥム等のアル カリ金属炭酸塩類、 又は卜リエチルァミ ン、 卜リメチルァミ ン、 Ν, Ν—ジメチ ルァニリ ン、 ピリジン、 Ν—メチルピペリジン、 1， 5 —ジァザビシクロ [ 4 . 3 . 0 ] ノン一 5—ェン （D B N) 又は 1， 8—ジァザビシクロ [ 5 . 4 . 0 ] 一 7—ゥンデセン （D B U) 等の有機塩基等が挙げられ、 好ましくは卜リエチル ァミ ン、 ピリジン、 Ν—メチルビペリジン等の第三級ァミ ン類が挙げられる。 反応温度は、 一 5 0。C〜 1 5 0 の範囲、 好ましくは 0 °C〜 1 0 0ての範囲に おいて行われる。 反応時間は 1〜3 0時間が好ましい。  As the base, those generally used in this type of reaction can be used. For example, alkali metal hydroxides such as sodium hydroxide or hydroxylated lime, alkaline earth metal hydroxides such as calcium hydroxide, and alkalis such as sodium carbonate or carbonated lime. Metal carbonates, or triethylamine, trimethylamine, Ν, Ν-methylylaniline, pyridine, Ν-methylpiperidine, 1,5-diazabicyclo [4.3.0] non-15-ene (DBN) or Organic bases such as 1,8-diazabicyclo [5.4.0] -17-pandacene (DBU) and the like, preferably tertiary amines such as triethylamine, pyridine and Ν-methylbiperidine Is mentioned. The reaction temperature was 150. C. is carried out in the range of 150 ° C., preferably in the range of 0 ° C. to 100 ° C. The reaction time is preferably 1 to 30 hours.
次に、 この製造法で使用する原料ィ匕合物の製造法を説明する。  Next, a method for producing the raw material conjugate used in this production method will be described.
まず、 一般式 [ I I ] で表される化合物は、 例えば以下に示す製造法に従って 製造することができる。 99/33810 First, the compound represented by the general formula [II] can be produced, for example, according to the following production method. 99/33810
18  18
Figure imgf000020_0001
Figure imgf000020_0001
[I I]  [I I]
(式中、 R 1 X、 n及び Aは前記と同じ意味を表し、 6は。 1〜じ 6ァルキ ル基を表し、 Zはハロゲン原子等の脱離基を表す。 ) (In the formula, R 1 X, n and A represent the same meaning as described above, 6 represents a 1 to 6 alkyl group, and Z represents a leaving group such as a halogen atom.)
一般式 [I I] で表されるピリジルォキシ （チォ） アルカン酸誘導体は、 例 えば一般式 [I V] 又は [V I I] で表されるピリジン誘導体を塩基の存在下に 一般式 [V] 又は [V I I I] で表されるアルカン酸エステル誘導体と反応させ 一般式 [V I] で表されるピリジルォキシ （チォ） アルカン酸エステル誘導体に 導き、 その後にピリジルォキシ （チォ） アルカン酸エステル誘導体を加水分解す ることにより製造することができる。  The pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II] can be obtained, for example, by converting a pyridine derivative represented by the general formula [IV] or [VII] in the presence of a base into the general formula [V] or [VIII] By reacting with an alkanoic acid ester derivative represented by the general formula [VI], and then hydrolyzing the pyridyloxy (thio) alkanoic acid ester derivative. be able to.
上記反応式中、 一般式 [I V] 又は [V I I ] で表されるピリジン誘導体と一 般式 [V] 又は [V I I I] で表されるエステル誘導体との反応は通常、 溶媒中 で行なわれる。 使用できる溶媒としては、 反応を阻害しない溶媒であればよく、 例えば、 ペンタン、 へキサン、 ヘプタン、 シクロへキサン、 石油エーテル、 リグ 口イン、 ベンゼン、 トルエン又はキシレン等の炭化水素類、 ジクロロメタン、 ジ クロロェタン、 クロ口ホルム、 四塩化炭素、 クロ口ベンゼン又はジクロロべンゼ ン等のハロゲン化炭化水素類、 ジェチルエーテル、 ジイソプロピルエーテル、 ェ チレングリ コールジメチルェ一テル、 テトラヒ ドロフラン又はジォキサン等の W 99/33810 In the above reaction scheme, the reaction between the pyridine derivative represented by the general formula [IV] or [VII] and the ester derivative represented by the general formula [V] or [VIII] is usually performed in a solvent. Solvents that can be used may be solvents that do not inhibit the reaction, for example, pentane, hexane, heptane, cyclohexane, petroleum ether, rig-mouth, benzene, toluene or hydrocarbons such as xylene, dichloromethane, Halogenated hydrocarbons such as chloroethane, chloroform, carbon tetrachloride, carbon benzene or dichlorobenzene, dimethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane W 99/33810
19  19
エーテル類、 アセ トン、 メチルェチルケトン、 メチルイソプロビルケ トン又はメ チルイソブチルケトン等のケ卜ン類、 酢酸メチル又は酢酸ェチル等の酢酸エステ ル類、 ァセトニトリル又はプロピオ二トリル等の二トリル類、 又はジメチルスル ホキシド、 N, N—ジメチルホルムアミ ド又はスルホラン等の非プロ トン性極性 溶媒、 あるいはこれらから選択される溶媒を組み合わせた混合溶媒を用いること ができる。 Ethers, acetone, methyl ethyl ketone, ketones such as methyl isopropyl ketone or methyl isobutyl ketone, ester acetates such as methyl acetate or ethyl acetate, nitriles such as acetonitrile or propionitrile, Alternatively, a non-protonic polar solvent such as dimethyl sulfoxide, N, N-dimethylformamide or sulfolane, or a mixed solvent obtained by combining solvents selected from these solvents can be used.
塩基としては、 この型の反応に一般的に用いられるものが使用できる。 例えば 水酸化ナト リウム、 水酸化力リウム、 炭酸ナトリウム、 炭酸力リゥム、 重炭酸ナ 卜リゥム、 水素化ナト リゥ厶又は水素ィ匕カリゥム等の無機塩基、 又はトリエチル ァミ ン、 卜リメチルァミ ン、 N， N—ジメチルァニリ ン又はピリジン等の有機塩 基等が挙げられる。  As the base, those generally used in this type of reaction can be used. For example, an inorganic base such as sodium hydroxide, sodium hydroxide, sodium carbonate, carbonated carbonate, sodium bicarbonate, sodium hydride or hydrogenated potassium, or triethylamine, trimethylamine, N , N-dimethylaniline or pyridine.
反応温度は、 一 50°C〜 1 50°Cの範囲、 好ましくは 0 °C〜 1 00 の範囲に おいて行われる。 反応時間は 1〜30時間が好ましい。  The reaction is carried out at a temperature in the range of 50 ° C to 150 ° C, preferably in the range of 0 ° C to 100 ° C. The reaction time is preferably 1 to 30 hours.
また、 一般式 [V I] で表されるピリジルォキシ （チォ） アルカン酸エステル 誘導体を酸又はアルカリ存在化で加水分解して一般式 [ I I] で表されるピリジ ルォキシ （チォ） アルカン酸誘導体を得る反応は通常、 溶媒中で行なわれる。 使 用できる溶媒としては、 反応を阻害しない溶媒であればよく、 例えば水、 メタ ノール、 エタノール又は 2—プロパノール等のアルコール類、 ジェチルエーテ ル、 ジイソプロピルエーテル、 エチレングリコ一ルジメチルエーテル、 テトラヒ ドロフラン又はジォキサン等のエーテル類、 又はァセ トン、 メチルェチルケ ト ン、 メチルイソプロピルケ トン又はメチルイソプチルケトン等のケ トン類、 ある いはこれらから選択される溶媒を組み合わせた混合溶媒を用いることができる。 一般式 [I I I] で表される化合物は、 公知の方法 〔例えば、 ジャーナル 'ォ ブ · ザ · ケ ミ カル · ソサイエティ . パーキン · ト ラ ンザク シ ョ ンズ. 1 、 J o u r n a l o f t h e C h em i c a l S o c i e t y. P e r k i n T r a n s a c t i o n s. 1 ) 、 第 8巻、 第 1 6 4 5頁 ( 1 98 5年） ；ザ ' ジャーナル 'ォブ 'オルガ二ック ' ケミス ト リ （Th e J ou r n a l o f O r g a n i c Ch em i s t r y) 、 第 49卷、 第 1 208頁 （1 984年） に記載の方法〕 あるいはそれに準じた方法で製造する ことができる Also, a reaction for hydrolyzing a pyridyloxy (thio) alkanoic acid ester derivative represented by the general formula [VI] in the presence of an acid or an alkali to obtain a pyridyloxy (thio) alkanoic acid derivative represented by the general formula [II] Is usually performed in a solvent. Any solvent that does not inhibit the reaction may be used, for example, water, alcohols such as methanol, ethanol or 2-propanol, getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane. Ethers, ketones such as acetone, methylethylketone, methylisopropylketone or methylisobutylketone, or a mixed solvent obtained by combining solvents selected from these. The compound represented by the general formula [III] can be prepared by a known method [for example, Journal of the Chemical Society. Parkin Transaction Society. 1, Journal of Chemical Society]. y. Perkin Transaction s. 1), Vol. 8, pp. 1645 (1998); The 'Journal' Ob '' Organic 'Chemistry (The Journal of O.) rganic Chemistry), vol. 49, p. 1208 (1 984)] or a method analogous thereto. be able to
製造法 2 Manufacturing method 2
Figure imgf000022_0001
Figure imgf000022_0001
(式中、 R 1 R 、 R 3、 Q、 X、 n、 A及び Zは前記と同じ意味を表す。 ） 本発明化合物 [ I ] は、 一般式 [V I I ] で表されるピリ ジン誘導体を塩基の 存在下に、 一般式 [ I X] で表されるアルカン酸アミ ド誘導体と反応させること により製造することができる。 この反応は通常、 溶媒中で行われる。 使用できる 溶媒としては、 反応を阻害しない溶媒であればよく、 例えばペンタン、 へキサ ン、 ヘプタン、 シクロへキサン、 石油エーテル、 リグ口イン、 ベンゼン、 トルェ ン又はキシレン等の炭化水素類、 ジクロロメタン、 ジクロロェタン、 クロ口ホル ム、 四塩化炭素、 クロ口ベンゼン又はジクロロベンゼン等のハロゲン化炭化水素 類、 ジェチルエーテル、 ジイソプロピルエーテル、 エチレングリコ一ルジメチル エーテル、 テトラヒ ドロフラン又はジォキサン等のエーテル類、 アセトン、 メチ ルェチルケ トン、 メチルイソプロピルケトン又はメチルイソブチルケ 卜ン等のケ トン類、 酢酸メチル又は酢酸ェチル等の酢酸エステル類、 ァセトニトリル又はプ 口ピオ二トリル等の二トリル類、 又はジメチルスルホキシ ド、 N， N—ジメチル ホルムアミ ド又はスルホラン等の非プロ トン性極性溶媒、 あるいはこれらから選 択される溶媒を組み合わせた混合溶媒を用いることができる。 (Wherein, R 1 R, R 3 , Q, X, n, A, and Z have the same meanings as described above.) The compound [I] of the present invention is a pyridine derivative represented by the general formula [VII] It can be produced by reacting with an alkanoic acid amide derivative represented by the general formula [IX] in the presence of a base. This reaction is usually performed in a solvent. As a solvent that can be used, any solvent that does not inhibit the reaction may be used.Examples include pentane, hexane, heptane, cyclohexane, petroleum ether, rigoin, hydrocarbons such as benzene, toluene, and xylene, dichloromethane, and the like. Halogenated hydrocarbons such as dichloroethane, chloroform, carbon tetrachloride, cyclobenzene or dichlorobenzene, ethers such as getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, acetone, methyl Ketones such as rutile ketone, methyl isopropyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; nitriles such as acetonitrile or pentionitrile; or dimethyl sulfoxide, N Non pro ton polar solvents such as N- dimethyl formamide or sulfolane, or may be a mixed solvent combining solvents selected from these.
塩基としては、 この型の反応に一般的に用いられるものが使用できる。 例えば 7K酸化ナトリウム、 水酸化力リゥム、 炭酸ナトリウム、 炭酸力リゥム、 重炭酸ナ トリウム、 水素化ナトリゥム又は水素化力リゥム等の無機塩基、 又はトリェチル ァミ ン、 卜リメチルァミ ン、 N , N—ジメチルァニリン又はピリ ジン等の有機塩 基等が挙げられる。 As the base, those generally used in this type of reaction can be used. For example, inorganic bases such as 7K sodium oxide, hydroxylated lime, sodium carbonate, carbonated lime, sodium bicarbonate, sodium hydride or hydrogenated lime, or triethylamine, trimethylamine, N, N-dimethyl Organic salts such as aniline or pyridine And the like.
反応温度は、 — 50 °C〜 1 50°Cの範囲、 好ましくは 0 °C〜 100 °Cの範囲に おいて行われる。 反応時間は 1〜30時間が好ましい。  The reaction temperature is in the range of —50 ° C. to 150 ° C., preferably 0 ° C. to 100 ° C. The reaction time is preferably 1 to 30 hours.
この反応において一般式 [ I X] で表される化合物は、 例えばハロゲン化アル カン酸ハライ ド類と一般式 [I I I] で表されるァミ ン誘導体とを反応させるこ とで製造することができる。  In this reaction, the compound represented by the general formula [IX] can be produced, for example, by reacting a halogenated alkanoic acid halide with an amide derivative represented by the general formula [III]. .
製造法 3 Manufacturing method 3
Q
Figure imgf000023_0001
Q
Figure imgf000023_0001
(式中、 R 1 R2、 R 、 Q、 X、 n及び Zは前記と同じ意味を表す。 ) 本発明化合物 [I] は、 一般式 [I V] で表されるピリジン誘導体を塩基の存 在下に、 一般式 [X] で表されるアルカン酸アミ ド誘導体と反応させることによ り製造することができる。 この反応は通常、 溶媒中で行われる。 使用できる溶媒 としては、 製造法 2と同様な反応を阻害しない溶媒であればよい。 (In the formula, R 1 R 2 , R, Q, X, n, and Z represent the same meaning as described above.) The compound [I] of the present invention is obtained by converting a pyridine derivative represented by the general formula [IV] into a base In the presence, the compound can be produced by reacting with an alkanoic acid amide derivative represented by the general formula [X]. This reaction is usually performed in a solvent. As a solvent that can be used, any solvent that does not inhibit the same reaction as in Production Method 2 may be used.
塩基としては、 製造法 2と同様に一般的に用いられるものが使用できる。 反応温度は、 — 50 °C〜 150ての範囲、 好ましくは 0 °C〜 100 °Cの範囲に おいて行われる。 反応時間は 1〜30時間が好ましい。  As the base, those commonly used as in Production method 2 can be used. The reaction is carried out at a temperature ranging from −50 ° C. to 150, preferably from 0 ° C. to 100 ° C. The reaction time is preferably 1 to 30 hours.
この反応において一般式 [X] で表される化合物は、 例えば、 一般式 [I X] で表されるハロゲン化アルカン酸ァミ ド誘導体と酢酸ナトリウムとを反応させて 得られるァセトキシアルカン酸アミ ド誘導体を脱ァシル化することで製造するこ とができる。  In this reaction, the compound represented by the general formula [X] is obtained, for example, by reacting the halogenated alkanoic acid amide derivative represented by the general formula [IX] with sodium acetate. It can be produced by deacylation of a derivative.
製造法 4 R 1 o R2 Manufacturing method 4 R 1 o R2
Xn—一 斗 A - CH - C一 NH - Cc一 - C≡CH  Xn—one A-CH-C one NH-Cc one-C≡CH
R3  R3
[ I - I ] 一 Me
Figure imgf000024_0001
[I-I] One Me
Figure imgf000024_0001
(式中、 R 1 R 2、 R 3、 X、 n及び Aは前記と同じ意味を表す。 ） 本発明化合物 Π — I I ] は一般式 [ I— I ] で表されるピリジルォキシ （チ ォ） アルカン酸アミ ド誘導体を、 酸の存在下に水和反応を行うことにより製造す ることができる。 この反応は無溶媒、 又は溶媒中で行なわれる。 使用できる溶媒 としては、 反応を阻害しない溶媒であればよく、 例えばジェチルエーテル、 ジィ ソプロピルエーテル、 エチレングリコ一ルジメチルエーテル、 テトラヒ ドロフラ ン又はジォキサン等のエーテル類、 アセトン、 メチルェチルケトン、 メチルイソ プロピルケトン又はメチルイソブチルケトン等のケトン類、 酢酸メチル又は酢酸 ェチル等の酢酸エステル類、 ァセトニトリル又はプロピオ二トリル等の二卜リル 類、 又はジメチルスルホキシ ド、 N， N—ジメチルホルムアミ ド又はスルホラン 等の非プロトン性極性溶媒、 あるいはこれらから選択される溶媒を組み合わせた 混合溶媒を用いることができる。 (In the formula, R 1 R 2 , R 3 , X, n and A represent the same meaning as described above.) The compound of the present invention Π—II] is a pyridyloxy (thio) represented by the general formula [II] The alkanoic acid amide derivative can be produced by performing a hydration reaction in the presence of an acid. This reaction is performed without a solvent or in a solvent. Solvents that can be used may be any solvents that do not inhibit the reaction, such as ethers such as getyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran or dioxane, acetone, methyl ethyl ketone, and methyl iso- Ketones such as propyl ketone or methyl isobutyl ketone; acetates such as methyl acetate or ethyl acetate; nitriles such as acetonitrile or propionitrile; or dimethyl sulfoxide, N, N-dimethylformamide or sulfolane Or a mixed solvent obtained by combining solvents selected from these aprotic polar solvents.
酸としては、 例えば硫酸、 塩酸、 ギ酸等が挙げられる。  Examples of the acid include sulfuric acid, hydrochloric acid, formic acid and the like.
反応温度は、 0て〜 1 5 0 °Cの範囲、 好ましくは 2 0 〜 1 0 0 °Cの範囲にお いて行われる。 反応時間は 1〜1 0時間が好ましい。  The reaction is carried out at a temperature in the range of 0 to 150 ° C, preferably in the range of 20 to 100 ° C. The reaction time is preferably 1 to 10 hours.
製造法 5
Figure imgf000025_0001
Manufacturing method 5
Figure imgf000025_0001
1 2 3 5  1 2 3 5
(式中、 R R R R X、 n及び Aは前記と同じ意味を表す。 ） 本発明化合物 [ I — I V] は、 一般式 [ I— I I I ] で示されるピリジルォキ シ （チォ） アルカン酸アミ ド誘導体を還元剤と反応させることにより製造するこ とができる。 この反応は通常、 溶媒中で行われる。 使用できる溶媒としては、 反 応を阻害しない溶媒であればよく、 例えば、 ペンタン、 へキサン、 ヘプタン、 シ クロへキサン、 石油エーテル、 リグ口イン、 ベンゼン、 トルエン、 キシレン等の 炭^ f匕水素類、 ジクロロメタン、 ジクロロェタン、 クロ口ホルム、 四塩化炭素、 ク ロロベンゼン、 ジクロロベンゼン等のハロゲン化炭化水素類、 ジェチルェ一テ ル、 ジイソプロピルエーテル、 エチレングリコ一ルジメチルェ一テル、 テトラヒ ドロフラン、 ジォキサン等のエーテル類、 メタノール、 エタノール、 2—プロパ ノール等のアルコール類又は、 水とアルコール類との混合溶媒を用いることがで さる c (Wherein, RRRRX, n and A represent the same meaning as described above.) The compound [I-IV] of the present invention reduces the pyridyloxy (thio) alkanoic acid amide derivative represented by the general formula [I-III]. It can be produced by reacting with an agent. This reaction is usually performed in a solvent. As a solvent that can be used, any solvent that does not inhibit the reaction may be used. For example, pentane, hexane, heptane, cyclohexane, petroleum ether, lignin, benzene, toluene, xylene, etc. , Halogenated hydrocarbons such as dichloromethane, dichloroethane, chloroform, carbon tetrachloride, chlorobenzene, dichlorobenzene, ethers such as dimethyl ether, diisopropyl ether, ethylene glycol dimethyl ether, tetrahydrofuran, dioxane, etc. , methanol, ethanol, 2-alcohols such as propanol or water and it is in monkey c a mixed solvent of alcohol
還元剤としては、 この型の反応に一般的に用いられるものが使用できる。 例え ば、 K素化ホウ素リチウム、 水素化ホウ素ナトリウム、 水素化ホウ素カリウム、 トリアルキル水素化ホウ素リチウム、 トリアルキル水素化ホウ素ナトリゥム又は シァノ水素化ホウ素ナトリウム等が挙げられ、 好ましくは水素化ホウ素ナトリゥ ムが挙げられる。  As the reducing agent, those generally used in this type of reaction can be used. Examples include lithium borohydride, sodium borohydride, potassium borohydride, lithium trialkylborohydride, sodium trialkylborohydride or sodium cyanoborohydride, and preferably sodium borohydride. Is mentioned.
反応温度は、 一 7 0 °C〜 1 5 0 °Cの範囲、 好ましくは— 2 0 °C〜 5 0 °Cの範囲 において行われる。 反応時間は 1〜3 0時間が好ましい。  The reaction is carried out at a temperature in the range of 170 ° C. to 150 ° C., preferably in the range of −20 ° C. to 50 ° C. The reaction time is preferably 1 to 30 hours.
[発明を実施するための最良の形態]  [Best Mode for Carrying Out the Invention]
次に、 本発明化合物の製造法を具体的に説明する。  Next, a method for producing the compound of the present invention will be specifically described.
〈製造例 1〉 2— ( 4， 5 —ジトリフルォロメチルピリジン一 2 —ィルォキシ） 一 N— （ 1 —イソプロピル一 1 ーメチルー 2—ォキソプロビル） プロピオンアミ ド （化合物番号 A 1 0 ) の製造 <Production Example 1> 2- (4,5-Ditrifluoromethylpyridine-1-2-yloxy) Preparation of 1N— (1—isopropyl-1-methyl-2-oxoprovir) propionamide (Compound No.A10)
ジクロロメタン 5 0 m 1 に 2— ( 4 , 5—ジトリフルォロメチルピリジン一 2 一ィルォキン） プロビオン酸 1 . 0 g、 1ーェチルー 3— （3 —ジメチルァミ ノ プロピル） カルボジィミ ド '塩酸塩 1 . 1 gを加えた。 室温で 3 0分間攪拌後、 3 —アミ ノー 3 , 4 —ジメチル一 2 —ペンタノン '塩酸塩 0 . 8 g、 トリェチル アミン 0 . 5 gを加えた。 この混合物を室温で 1 2時間撹拌し、 水にあけ、 ジク ロロメタンで抽出した。 ジクロロメタン層を無水硫酸マグネシウムで乾燥し、 減 圧下、 ジクロロメタンを留去した。 残渣をシリ力ゲル力ラムクロマトグラフィー で精製し、 目的物 5 gを得た。 融点 1 2 7〜1 3 0 °C  2- (4,5-ditrifluoromethylpyridine-121-loquinine) propionic acid in 50 ml of dichloromethane 1.0 g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide 'hydrochloride 1.1 g was added. After stirring at room temperature for 30 minutes, 0.8 g of 3-amino-3,4-dimethyl-12-pentanone 'hydrochloride and 0.5 g of triethylamine were added. The mixture was stirred at room temperature for 12 hours, poured into water and extracted with dichloromethane. The dichloromethane layer was dried over anhydrous magnesium sulfate, and dichloromethane was distilled off under reduced pressure. The residue was purified by silica gel gel chromatography to obtain 5 g of the desired product. Melting point 1 27-130 ° C
〈参考例 1 一 a〉 メチル 2— （ 4， 5 —ジトリフルォロメチルピリジン一 2— ィルォキシ） プロピオネートの製造  <Reference Example 1-a> Production of methyl 2- (4,5-ditrifluoromethylpyridine-2-yloxy) propionate
6 0 %水素化ナトリウム 1 . 1 gをへキサンで洗浄し、 テ トラヒ ドロフラン 5 0 m 1 に懸濁した。 この懸濁液に乳酸メチル 2 . 9 gを氷冷下で滴下した。 室 温で 1時間撹拌後、 2 —クロ口— 4， 5—ジトリフルォロメチルピリジン 5 . 8 gを滴下した。 この混合物を室温で 3時間撹拌し、 水にあけ、 酢酸ェチルで抽 出した。 酢酸ェチル層を無水硫酸マグネシウムで乾燥し、 減圧下、 酢酸ェチルを 留去し、 油状の目的物 7 . 2 gを得た。  1.1 g of 60% sodium hydride was washed with hexane and suspended in 50 ml of tetrahydrofuran. 2.9 g of methyl lactate was added dropwise to the suspension under ice cooling. After stirring at room temperature for 1 hour, 5.8 g of 2-chloro-4,5-ditrifluoromethylpyridine was added dropwise. The mixture was stirred at room temperature for 3 hours, poured into water, and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure to obtain 7.2 g of an oily target compound.
〈参考例 1— b〉 2— ( 4 , 5 —ジ卜リフルォロメチルピリジン一 2—ィルォキ シ） プロピオン酸の製造  <Reference Example 1-b> Production of 2- (4,5-ditrifluoromethylpyridine-12-yloxy) propionic acid
ジォキサン 5 O m 1にメチル 2— （4， 5—ジトリフルォロメチルピリジ ンー 2 —ィルォキン） プロピオネート 7 . 2 gを溶解した。 この溶液に水酸化ナ トリウム 1 . 2 gを水 2 O m 1に溶解したものを滴下した。 この混合物を室温で 1 0時間撹拌し、 水にあけ、 クェン酸で酸性にし、 酢酸ェチルで抽出した。 酢酸 ェチル層を無水硫酸マグネシウムで乾燥し、 減圧下、 酢酸ェチルを留去した。 残 渣をへキサンで洗浄し、 目的物 4 . 9 を得た。 融点 1 0 6〜 1 0 9 °C 7.2 g of methyl 2- (4,5-ditrifluoromethylpyridin-2-ylokine) propionate was dissolved in dioxane 5 Om1. A solution of 1.2 g of sodium hydroxide in 2 Om1 of water was added dropwise to this solution. The mixture was stirred at room temperature for 10 hours, poured into water, acidified with citric acid and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was washed with hexane to obtain the desired product 4.9. Melting point 106-109 ° C
〈製造例 2〉 2— （ 3—クロ口— 5 —トリフルォロメチルピリジン一 2 —ィルォ キシ） 一 N— （1 , 1 ージェチル一 2 —ォキソプロピル） プロピオンアミ ド （ィ匕 合物番号 A - 3 ) の製造 ァセトニトリル 4 0m l に 2— （3—クロ口— 5— トリフルォロメチルピリ ジ ンー 2—ィルォキシ） 一 N— ( 1， 1 —ジェチルー 2—プロピニル） プロピオン アミ ド 0. 7 g、 1 0 %塩酸 1 0m lを加えた。 この混合物を室温で 3時間撹拌 し、 水にあけ、 炭酸水素ナトリウムで中性にし、 酢酸ェチルで抽出した。 酢酸ェ チル層を無水硫酸マグネシウムで乾燥し、 減圧下、 酢酸ェチルを留去した。 浅渣 をへキサンで洗浄し、 目的物 0. 6 gを得た。 融点 1 32〜 1 3 5°C <Production Example 2> 2- (3-chloro-opening-5-trifluoromethylpyridine-12-yloxy) -1-N- (1,1-dimethyl-1-2-oxopropyl) propionamide (Compound A- 3) Manufacture Acetonitrile in 40 ml of 2- (3-chloro- mouth-5-trifluoromethylpyridin-2-yloxy) -N- (1,1-Jetyl-2-propynyl) propionamide 0.7 g, 10% 10 ml of hydrochloric acid were added. The mixture was stirred at room temperature for 3 hours, poured into water, neutralized with sodium hydrogen carbonate, and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. The shallow residue was washed with hexane to obtain 0.6 g of the desired product. Melting point 1 32 to 1 3 5 ° C
〈製造例 3〉 2— ( 3—クロ口一 5— トリフルォロメチルピリジン一 2—ィルォ キシ） 一 N— ( 1， 1 —ジェチルー 2—プロピニル） プロピオンアミ ド （化合物 番号 A_ 2) の製造  <Production Example 3> Production of 2- (3-chloromethyl-1-trifluoromethylpyridine-2-yloxy) -1-N- (1,1-ethyl-2-propynyl) propionamide (Compound No. A_2)
テトラヒ ドロフラン 20m lに 2— （3—クロロー 5— ト リフルォロメチルピ リジン一 2—ィルォキシ） プロピオン酸 1. 0 gを溶解し、 1ーェチルー 3— (3—ジメチルァミノプロビル） カルポジイミ ド '塩酸塩 1. 1 gを加えた。 室 温で 3 0分間攪拌後、 1, 1—ジェチル— 2—プロピニルァミン 0. 4 gを加え た。 この混合物を室温で 3時間撹拌し、 水にあけ、 酢酸ェチルで抽出した。 酢酸 ェチル層を無水硫酸マグネシウムで乾燥し、 減圧下、 酢酸ェチルを留去した。 残 渣をシリカゲルカラムクロマトグラフィーで精製し、 目的物 1. 0 gを得た。 融 点 1 0 5〜 1 06 °C  In 20 ml of tetrahydrofuran, dissolve 1.0 g of 2- (3-chloro-5-trifluoromethylpyridine-l- 2-yloxy) propionic acid, and add 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide. 'Hydrochloride 1.1 g was added. After stirring at room temperature for 30 minutes, 0.4 g of 1,1-getyl-2-propynylamine was added. The mixture was stirred at room temperature for 3 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.0 g of the desired product. Melting point 105 to 106 ° C
〈製造例 4〉 2— ( 3—クロロー 5— トリフルォロメチルピリジン一 2—ィルチ ォ） 一 N— （1 _イソプロピル一 1ーメチルー 2—ォキソプロピル） プロピオン ァミ ド （化合物番号 A - 1 6 ) の製造  <Production Example 4> 2- (3-chloro-5-trifluoromethylpyridine-12-ylthio) -1-N- (1-isopropyl-1--1-methyl-2-oxopropyl) propionamide (Compound No. A-16) Manufacturing of
6 0 %水素化ナトリウム 0. 3 gをへキサンで洗浄し、 ジメチルホルムアミ ド 2 0m 1 に懸濁した。 この懸濁液に 3—クロ口- 5 _ トリフルォロメチル一 2 一メルカプトピリジン 1. 5 gを滴下した。 室温で 1時間撹拌後、 N— ( 1—ィ ソプロピル一 1 _メチル— 2—ォキソプロピル） 一 2—ブロモプロピオンアミ ド 1. 7 gを滴下した。 この混合物を室温で 2時間撹拌し、 水にあけ、 酢酸ェチル で抽出した。 酢酸ェチル層を無水硫酸マグネシウムで乾燥し、 减圧下、 酢酸ェチ ルを留去した。 残渣をシリ力ゲルカラムクロマ卜グラフィ一で精製し、 目的物 1. 3 を得た。 融点 1 1 4〜 1 1 7 °C  0.3% of 60% sodium hydride was washed with hexane and suspended in 20 ml of dimethylformamide. To this suspension was added dropwise 1.5 g of 3-chloro-5-5-trifluoromethyl-2-mercaptopyridine. After stirring at room temperature for 1 hour, 1.7 g of N- (1-isopropyl-1-methyl-2-oxopropyl) -12-bromopropionamide was added dropwise. The mixture was stirred at room temperature for 2 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain the desired product 1.3. Melting point 1 14 to 1 17 ° C
〈製造例 5〉 2 - ( 3, 5—ジクロロピリジン— 2—ィルォキシ） — N— ( 1 - イソプロピル— 1 —メチル一 2—ォキソプロピル） プロピオンアミ ド （化合物番 号 A— 8 ) の製造 <Production Example 5> 2- (3,5-dichloropyridine-2-yloxy) — N— (1- Production of isopropyl-1-methyl-2-oxopropyl) propionamide (Compound No. A-8)
テ 卜ラヒ ドロフラン 3 0 m l に N— ( 1—イソプロピル一 1 ーメチルー 2—ォ キソプロピル） — 2 —ヒ ドロキンプロピオンアミ ド 0 . 7 gを溶解した。 この溶 液に 6 0 %水素化ナト リウム 0 . 1 5 gを加えた。 室温で 3 0分攪拌後、 2 , 3 , 5 —トリクロ口ピリジン 0 . 7 gを加えた。 この混合物を室温で 6時間撹拌 し、 水にあけ、 酢酸ェチルで抽出した。 酢酸ェチル層を無水硫酸マグネシウムで 乾燥し、 減圧下、 酢酸ェチルを留去した。 残渣をシリカゲルカラムクロマトグラ フィ一で精製し、 目的物 1 . 0 gを得た。 融点 1 2 3〜 1 2 5 °C  In 30 ml of tetrahydrofuran, 0.7 g of N— (1-isopropyl-1-methyl-2-oxopropyl) —2-hydroquinopropionamide was dissolved. To this solution was added 0.15 g of 60% sodium hydride. After stirring at room temperature for 30 minutes, 0.7 g of 2,3,5-triclomouth pyridine was added. The mixture was stirred at room temperature for 6 hours, poured into water and extracted with ethyl acetate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and ethyl acetate was distilled off under reduced pressure. The residue was purified by silica gel column chromatography to obtain 1.0 g of the desired product. Melting point 1 2 3 to 1 2 5 ° C
〈製造例 6〉 2— ( 2 —ョ一ド— 6 —メチルピリジン一 3 —ィルォキシ） — N— ( 1 —イソプロピル一 1 _メチル— 2—プロピニル） プロピオンアミ ド （化合物 番号 B— 1 ) の製造  <Preparation Example 6> Preparation of 2- (2-node-6-methylpyridine-3-yloxy) -N- (1-isopropyl-1-methyl-2-propynyl) propionamide (Compound No. B-1) Manufacture
6 0 %水素化ナトリウム 0 . 2 gをへキサンで洗浄し、 ジメチルホルムアミ ド 2 0 m lに懸濁した。 この懸濁液に 2 —ョードー 6 —メチル— 3 —ピリジノール 1 . 0 gを滴下した。 室温で 1時間撹拌後、 N— （ 1 —イソプロピル一 1 ーメチ ルー 2—プロピニル） 一 2 —ブロモプロピオンアミ ド 1 . 1 gを商下した。 この 混合物を室温で 4時間撹拌し、 水にあけ、 ジェチルエーテルで抽出した。 ジェチ ルエーテル層を無水硫酸マグネシウムで乾燥し、 減圧下、 ジェチルエーテルを留 去した。 浅渣をへキサンで洗浄し、 目的物 8 gを得た。 融点 1 3 3〜 1 3 6 。C  0.2 g of 60% sodium hydride was washed with hexane and suspended in 20 ml of dimethylformamide. To this suspension was added dropwise 1.0 g of 2-hydroxy-6-methyl-3-pyridinol. After stirring at room temperature for 1 hour, 1.1 g of N- (1-isopropyl-1-methyl-2-propynyl) -12-bromopropionamide was sold. The mixture was stirred at room temperature for 4 hours, poured into water and extracted with getyl ether. The ethyl ether layer was dried over anhydrous magnesium sulfate, and dimethyl ether was distilled off under reduced pressure. The shallow residue was washed with hexane to obtain 8 g of the desired product. Mp 133-136. C
〈製造例 7〉 2— （2， 6 —ジトリフルォロメチルピリジン一 4 一ィルォキシ） — N— （ 1—イソプロピル一 1—メチル一 2—ォキソプロピル） プロピオンアミ ド （化合物番号 C— 2 ) の製造  <Preparation Example 7> Preparation of 2- (2,6-ditrifluoromethylpyridine-1-yloxy) -N- (1-isopropyl-1-methyl-1-oxopropyl) propionamide (Compound No. C-2) Manufacture
ァセトニトリル 4 0 m i に 2— （ 2、 6 —ジトリフルォロメチルピリジン _ 4 —ィルォキシ） — N— ( 1—イソプロピル— 1 一メチル— 2—プロピニル） プロ ピオンアミ ド 0 . 4 g、 1 0 %塩酸 1 0 m 1を加えた。 この混合物を還流下 3時 間撹拌し、 水にあけ、 酉酸ェチルで抽出した。 酢酸ェチル層を無水硫酸マグネシ ゥムで乾燥し、 減圧下、 酢酸ェチルを留去した。 残渣をへキサンで洗浄し、 目的 物 0 . 4 gを得た。 融点 1 3 0〜 1 3 2 °C 〈製造例 8〉 2— ( 3 , 5 —ジクロロピリジン— 2 —ィルォキシ） 一 N— ( 2 - ヒ ドロキシー 1 —イソプロピル— 1 —メチルプロピル） プロピオンアミ ド （化合 物番号 A— 3 7 ) の製造 Acetonitrile 40-mi in 2 -— (2,6-ditrifluoromethylpyridine_4—yloxy) —N— (1-isopropyl-1-monomethyl-2-propynyl) propionamide 0.4 g, 10% 10 ml of hydrochloric acid were added. The mixture was stirred under reflux for 3 hours, poured into water and extracted with ethyl citrate. The ethyl acetate layer was dried over anhydrous magnesium sulfate, and the ethyl acetate was distilled off under reduced pressure. The residue was washed with hexane to obtain 0.4 g of the desired product. Melting point 130 to 132 ° C <Production Example 8> Production of 2- (3,5-dichloropyridine-2-yloxy) -1-N- (2-hydroxy-1-isopropyl-1-methylpropyl) propionamide (Compound No. A-37)
メタノール 2 0 m lに 2— ( 3， 5—ジクロ口ピリジン一 2 _ィルォキシ） 一 N— （ 1 —イソプロピル— 1 一メチル一 2 —ォキソプロピル） プロピオンアミ ド 0 . 3 5 gを溶解した。 この溶液に水素化ホウ素ナトリウム 0 . 0 4 gを氷冷下 で加えた。 室温で 1時間撹拌した後、 水にあけ、 酢酸ェチルで抽出した。 酢酸ェ チル層を無水硫酸マグネシウムで乾燥した後、 減圧下、 酢酸ェチルを留去し、 目 的物 0 . 6 gを得た。 屈折率 1 . 5 3 0 4 ( 2 0 °C)  In 20 ml of methanol, 0.35 g of 2- (3,5-dichroic pyridine-12-yloxy) -N- (1-isopropyl-1-monomethyl-12-oxopropyl) propionamide was dissolved. To this solution, 0.04 g of sodium borohydride was added under ice cooling. After stirring at room temperature for 1 hour, the mixture was poured into water and extracted with ethyl acetate. After the ethyl acetate layer was dried over anhydrous magnesium sulfate, the ethyl acetate was distilled off under reduced pressure to obtain 0.6 g of the intended product. Refractive index 1.5 3 0 4 (20 ° C)
製造例 1〜 8に示した方法に準じて製造した本発明化合物の実施例を上の製造例 で示した化合物とともに表 1 3〜表 1 8に示す。 Examples of the compound of the present invention produced according to the methods shown in Production Examples 1 to 8 are shown in Tables 13 to 18 together with the compounds shown in the above Production Examples.
なお、 異'性体 Aとはジァステレオマー A、 異性体 Bとはジァステレオマ一 Bを それぞれ表し、 異性体 Mとはジァステレオマ一混合物を表す。 ジァステレオマー Aとはシリカゲルカラムクロマトダラフィ一又は高速液体ク口マトグラフィ一等 によって分離された低極性のジァステレオマ一を示し、 ジァステレオマ一 Bとは 同様に分離された高極性のジァステレオマ一を示す。 The isomer A represents diastereomer A, the isomer B represents diastereomer B, and the isomer M represents diastereomer mixture. Diastereomer A indicates a low-polarity diastereomer separated by silica gel column chromatography or high performance liquid chromatography, and diastereomer B indicates a similarly separated high-polarity diastereomer.
Figure imgf000030_0001
Figure imgf000030_0001
(表 1 4 ) (Table 14)
化合物 融点 (。C) Compound Melting point (.C)
1 9  1 9
番号 Xn A R1 Q 又は 性 屈折率（n^) 体Number Xn AR 1 Q or property
A - 28 3. 5- (CF3) o2, 6 - CI 0 Me Me Pr-i COMe 134-136 MA-28 3.5-(CF 3 ) o 2 , 6-CI 0 Me Me Pr-i COMe 134-136 M
A - 29 5-CFr 6-Cl 0 Me Me Pr-i C≡CH 129-131 MA-29 5-CF r 6-Cl 0 Me Me Pr-i C≡CH 129-131 M
A-30 0 Me Me Pr-i COMe 135-138 MA-30 0 Me Me Pr-i COMe 135-138 M
A - 31 3-CN 0 Me Me Pr-i C≡CH 97-100 MA-31 3-CN 0 Me Me Pr-i C≡CH 97-100 M
A - 32 3-CN 0 Me Me Pr-i COMe 162-165 MA-32 3-CN 0 Me Me Pr-i COMe 162-165 M
A- 33 5-N02 0 Me Me Pr-i C≡CH 73-76A- 33 5-N0 20 Me Me Pr-i C≡CH 73-76
A-34 0 Me Me Pr-i COMe 91-94 MA-34 0 Me Me Pr-i COMe 91-94 M
A - 35 5-CF3 0 Me Me Bu-t C≡CH 1. 4789 MA-35 5-CF 30 Me Me Bu-t C≡CH 1.4789 M
A-36 5-CF3 0 Me Me Bu-t COMe 127-130 MA-36 5-CF 3 0 Me Me Bu-t COMe 127-130 M
A-37 3, 5-Cl2 0 Me Me Pr-i CH (0H)Me 1. 5304 MA-37 3, 5-Cl 2 0 Me Me Pr-i CH (0H) Me 1.5304 M
A-38 3- 3 0 Me Me Pr-i CH (0H) Me 1. 4777 MA-38 3- 30 Me Me Pr-i CH (0H) Me 1.4777 M
A- 39 0 Me Me Pr-i CH (0H)Me 1. 4781 MA- 39 0 Me Me Pr-i CH (0H) Me 1.4781 M
A- 40 3. 5- (CF3) 2, 6-Cl 0 Me Me Pr-i CH (0H)Me 1. 4624A- 40 3.5- (CF 3 ) 2 , 6-Cl 0 Me Me Pr-i CH (0H) Me 1. 4624
A- 41 5- CF3, 6-Cl 0 Me Me Pr-i CH(0H)Me 1. 4861 MA- 41 5-CF 3 , 6-Cl 0 Me Me Pr-i CH (0H) Me 1.4861 M
A- 42 3-CN 0 Me Me Pr-i CH (0H)Me 1. 5189 MA- 42 3-CN 0 Me Me Pr-i CH (0H) Me 1.5189 M
A- 43 5-N02 0 Me Me Pr-i CH (0H)Me 1. 5299 MA-43 5-N0 20 Me Me Pr-i CH (0H) Me 1.5299 M
A- 44 5- Me 0 Me Me Pr-i C≡CH 1. 5051 MA-44 5-Me 0 Me Me Pr-i C≡CH 1.5051 M
A- 45 6-F 0 Me Me Pr-i C≡CH 94-97A- 45 6-F 0 Me Me Pr-i C≡CH 94-97
A- 46 6-F 0 Me Me Pr-i COMe 92-93 MA- 46 6-F 0 Me Me Pr-i COMe 92-93 M
A-47 0 Me Me Pr-i C≡CH 80-83 MA-47 0 Me Me Pr-i C≡CH 80-83 M
A- 48 3， 5-Cl?, 6-Me 0 Me Me Pr-i COMe 127-130 MA- 48 3, 5-Cl ?, 6-Me 0 Me Me Pr-i COMe 127-130 M
A- 49 0 Me Me Pr-i CH (OH) Me 1. 5197 MA- 49 0 Me Me Pr-i CH (OH) Me 1.5197 M
A-50 5 - Br, 6-Me 0 Me Me Pr-i COMe 133-135 MA-50 5-Br, 6-Me 0 Me Me Pr-i COMe 133-135 M
3 - Me, 5 - Br u Me Me rr l し UMe ^ n c 3-Me, 5-Br Me Me rr l then UMe ^ n c
丄 -，" o b M 丄-, "ob M
A - 52 3-Cl. 5-CF 0 H Me Bu-t C≡CH 72-75A-52 3-Cl. 5-CF 0 H Me Bu-t C≡CH 72-75
A- 53 3-Cl, 5 - CF。 0 H Me Bu-t COMe 130-133A-53 3-Cl, 5-CF. 0 H Me Bu-t COMe 130-133
A-54 3-Cl, 5-CFg 0 H Me Bu-t CH (0H) Me 109-112 BA-54 3-Cl, 5-CFg 0 H Me Bu-t CH (0H) Me 109-112 B
A-55 3-Cl. 5-CF. 0 Me Me Pr-i C≡CH 101-103A-55 3-Cl. 5-CF. 0 Me Me Pr-i C≡CH 101-103
A- 56 3- 02 0 Me Me Pr-i COMe 154-157 MA- 56 3- 0 2 0 Me Me Pr-i COMe 154-157 M
A-57 3-N02 0 Me Me Pr-i CH (0H)Me 1. 5143 MA-57 3-N0 20 Me Me Pr-i CH (0H) Me 1.5143 M
A-58 3. 6- (CF3) 2 0 Me Me Pr-i C≡CH 63-66 M (表 1 5 ) A-58 3.6- (CF 3 ) 20 Me Me Pr-i C≡CH 63-66 M (Table 15)
化合物 融点 （て） Compound melting point
Xn A R1 R2 R3 Q 又は 性 屈折率 (n Q) 体Xn AR 1 R 2 R 3 Q or Refractive index ( n Q )
A-59 3, 6-(CF3)2 0 Me Me Pr- i COMe 132-135 MA-59 3, 6- (CF 3 ) 20 Me Me Pr-i COMe 132-135 M
A- 60 3, 6 - (CF3)2 0 Me Me Pr- i CH(0H)Me 1.4469 MA- 60 3, 6-(CF 3 ) 20 Me Me Pr- i CH (0H) Me 1.4469 M
A-61 3, 5-Br9 0 Me Me Pr- i COMe 134-137 MA-61 3, 5-Br 9 0 Me Me Pr- i COMe 134-137 M
A - 62 3-Cl, 5-CF, 0 Me Et Et Et 137-140A-62 3-Cl, 5-CF, 0 Me Et Et Et 137-140
A - 63 3-Cl, 5-CF 0 Me Me Pr - i Et 113-116 MA-63 3-Cl, 5-CF 0 Me Me Pr-i Et 113-116 M
A-64 3, 5- CI 4- Me 0 Me Me Pr- i COMe 172-175 MA-64 3, 5- CI 4-Me 0 Me Me Pr- i COMe 172-175 M
A - 65 3, 5- Cl2, 4 - Me 0 Me Me Pr- ■i CH(0H)Me L.5239 MA-65 3, 5- Cl 2 , 4-Me 0 Me Me Pr- i CH (0H) Me L.5239 M
A-66 3-Cl, 5-CF 0 Me Me Pr -i CH(0H)Me 85-88A-66 3-Cl, 5-CF 0 Me Me Pr -i CH (0H) Me 85-88
A- 67 0 Me Et Et Et 121-124 A- 67 0 Me Et Et Et 121-124
(表 1 6) (Table 16)
Figure imgf000033_0001
lLa
Figure imgf000033_0001
lLa
p3  p3
¾F η A K K K y 乂は 性  ¾F η A K K K y
?n 屈折率（nD ) 体 ΰ - 1 2 - 1, 6 - Me 0 Me Me Pr-i 133-136 M ~Δ b-Me u Me Me rr-i し UMe , メ 物 M 0 -し 1 b - Me u Me Me rr-i し UMe ァメ状物質 ΰ - 4 0 Me Me rr-i し CJMe 1. ϋάόυ M? n the refractive index (n D) body ΰ - 1 2 - 1, 6 - Me 0 Me Me Pr-i 133-136 M ~ Δ b-Me u Me Me rr-i to UME, main product M 0 - tooth 1 b-Me u Me Me rr-i then UMe 状 4-40 Me Me rr-i then CJMe 1.ϋάόυ M
2 - CI 0 Me Me Pr-i CO e 1.5196 M2-CI 0 Me Me Pr-i CO e 1.5196 M
5 - CI 0 Me Me Pr-i し (Me 68-71 M Me 0 Me Me Pr-i し =ϋ! ol-o4 M b - Me u Me Me rr-i し UMe (ώ M -y NO , 6- Me 0 Me Me Pr - 1 lU e lUo-lU4 M NO 6-Me 0 Me Me Pr-i し H υη) Me 1. ΟάΌό M -11 5 -し i 0 Me ht Et l -1^4 β —し u e Me r-i by- / 1 M _i q c pi 5-CI 0 Me Me Pr-i then (Me 68-71 M Me 0 Me Me Pr-i then = ϋ! Ol-o4 Mb-Me u Me Me rr-i then UMe (ώ M -y NO, 6 -Me 0 Me Me Pr-1 lU e lUo-lU4 M NO 6-Me 0 Me Me Pr-i then H υη) Me 1.ΟάΌό M -11 5 -shi i 0 Me ht Et l -1 ^ 4 β — Ue Me ri by- / 1 M _i qc pi
5 u Me Me rr-i し H \)n) Μθ i i. coc M υινΐΘ u e we rr  5 u Me Me rr-i shi H \) n) Μθ i i.coc M υινΐΘ u e we rr
Uivie υ we Me rr H Uil ίτΙΘ  Uivie υ we Me rr H Uil ίτΙΘ
B - 16 6-Cl 0 Me Me Pr-i COMe 86-89 M B-16 6-Cl 0 Me Me Pr-i COMe 86-89 M
B-17 6-Cl 0 Me Me Pr-i CH(0H) e 1.5239 MB-17 6-Cl 0 Me Me Pr-i CH (0H) e 1.5239 M
B-18 5, 6-Cl 0 Me Me Pr-i COMe 76-78 MB-18 5, 6-Cl 0 Me Me Pr-i COMe 76-78 M
B-19 5, 6-C 0 Me Me Pr-i CH(0H)Me 1.5339B-19 5, 6-C 0 Me Me Pr-i CH (0H) Me 1.5339
B-20 2, 5-Cl 0 Me Me Pr-i COMe 94-96 MB-20 2, 5-Cl 0 Me Me Pr-i COMe 94-96 M
B- 21 2, 5-Cl2 0 Me Me Pr-i CH(0H)Me 1.5295 MB- 21 2, 5-Cl 2 0 Me Me Pr-i CH (0H) Me 1.5295 M
B-22 5-Br 0 Me Me Pr-i COMe 64-67 MB-22 5-Br 0 Me Me Pr-i COMe 64-67 M
B-23 5 - Br 0 Me Me Pr-i CH(0H)Me 1.5354 MB-23 5-Br 0 Me Me Pr-i CH (0H) Me 1.5354 M
B-24 5-Br, 6-Cl 0 Me Me Pr-i COMe 1.5413 MB-24 5-Br, 6-Cl 0 Me Me Pr-i COMe 1.5413 M
B - 25 5-Br, 6 - CI 0 Me Me Pr-i CH(0H)Me 1.5401 MB-25 5-Br, 6-CI 0 Me Me Pr-i CH (0H) Me 1.5401 M
B-26 5- CI 0 Me Me Bu-t COMe 1.5248 MB-26 5- CI 0 Me Me Bu-t COMe 1.5248 M
B- 27 5-Br 0 Me Me Bu - 1 COMe 1.5349 M (表 1 7) B- 27 5-Br 0 Me Me Bu-1 COMe 1.5349 M (Table 17)
化合物 融点 （°C) 異 番号 Xn A R1 R2 R3 Q 又は 性 Compound Melting point (° C) Different number Xn AR 1 R 2 R 3 Q or property
屈折率（n^) 体  Refractive index (n ^) body
B - 28 5-C1 0 Me Me Bu-t CH (OH) Me 1.5282 M  B-28 5-C1 0 Me Me Bu-t CH (OH) Me 1.5282 M
B-29 5- Br 0 Me Me Bu-t CH (OH) Me 1.5411  B-29 5- Br 0 Me Me Bu-t CH (OH) Me 1.5411
(表 1 8 (Table 18
QQ
Figure imgf000034_0001
化合物 融点 （°c) 異 番号 Xn A R1 R2 R3 Q 又は 性
Figure imgf000034_0001
Compound Melting point (° c) Different number Xn AR 1 R 2 R 3 Q or property
20  20
屈折率（n u) 体 Refractive index ( nu ) body
C-l 2, 6-(CF3)2 0 Me Me Pr- C≡CH 126-128 M Cl 2, 6- (CF 3 ) 20 Me Me Pr- C≡CH 126-128 M
C-2 2,6-(CF3)2 0 Me Me Pr- COMe 130-132 M C-2 2,6- (CF 3 ) 20 Me Me Pr- COMe 130-132 M
C-3 2, 3.5, 6-C1, 0 Me Me Pr- C≡CH 92-95 M  C-3 2, 3.5, 6-C1, 0 Me Me Pr- C≡CH 92-95 M
4  Four
C-4 2, 3.5.6- C 0 Me Me Pr- COMe 109-112  C-4 2, 3.5.6- C 0 Me Me Pr- COMe 109-112
4  Four
C-5 2 - CI 0 Me Me Pr- COMe 1.514 M  C-5 2-CI 0 Me Me Pr- COMe 1.514 M
C-6 2 - CI 0 Me Me Pr- -i CH (OH) Me 1.5181 M  C-6 2-CI 0 Me Me Pr- -i CH (OH) Me 1.5181 M
本発明の農園芸用殺菌剤は一般式 [ I ] で示されるピリジルォキン （チォ） ァ ルカン酸アミ ド誘導体を有効成分として含有してなる。 本発明化合物を農園芸用 殺菌剤として使用する場合には、 その目的に応じて有効成分を適当な剤型で用い ることができる。 通常は有効成分を不活性な液体または固体の担体で希釈し、 必 要に応じて界面活性剤、 その他をこれに加え、 粉剤、 水和剤、 乳剤、 粒剤等の製 剤形態で使用できる。 The agricultural and horticultural fungicide of the present invention contains a pyridyloquin (thio) carboxylic acid amide derivative represented by the general formula [I] as an active ingredient. When the compound of the present invention is used as a fungicide for agricultural and horticultural use, the active ingredient can be used in an appropriate dosage form depending on the purpose. Normally, the active ingredient is diluted with an inert liquid or solid carrier, and if necessary, a surfactant and other substances can be added to the active ingredient for use in the form of powders, wettable powders, emulsions, granules, etc. .
な担体としては、 例えばタルク、 ベン 卜ナイ ト、 クレー、 カオリ ン、 珪藻 土、 ホワイ ト力一ボン、 バーミキユライ ト、 消石灰、 珪砂、 硫安、 尿素等の固体 担体、 2—プロピルアルコール、 キシレン、 シクロへキサノ ン、 メチルナフタレン 等の液体担体等があげられる。 界面活性剤及び分散剤としては、 例えばジナフチ ルメタンスルホン酸塩、 アルコール硫酸エステル塩、 アルキルァリ一ルスルホン 酸塩、 リ グニンスルホン酸塩、 ポリオキシエチレングリコールエーテル、 ポリオ キシエチレンアルキルァリールエーテル、 ポリオキンエチレンソルビ夕ンモノア ルキレート等があげられる。 補助剤としてはカルボキシメチルセルロース等があ げられる。 これらの製剤を適宜な濃度に希釈して散布するか、 または直接施用す る。 Suitable carriers include, for example, talc, bentonite, clay, kaolin, diatoms Examples include solid carriers such as soil, white water, vermiculite, slaked lime, silica sand, ammonium sulfate, and urea, and liquid carriers such as 2-propyl alcohol, xylene, cyclohexanone, and methylnaphthalene. Examples of surfactants and dispersants include dinaphthyl methanesulfonate, alcohol sulfate, alkylaryl sulfonate, lignin sulfonate, polyoxyethylene glycol ether, polyoxyethylene alkylaryl ether, and polyoxyethylene. Sorbi monoalkylate and the like. Auxiliary agents include carboxymethylcellulose and the like. These preparations are diluted to an appropriate concentration and sprayed or applied directly.
本発明の農園芸用殺菌剤は茎葉散布、 育苗箱施用、 土壌施用または水面施用等 により使用することができる。 有効成分の配合割合は必要に応じ適宜選ばれる が、粉剤及び粒剤とする場合は 0.1〜20 % (重量)、 また乳剤及び水和剤とする場 合は 5〜80 % (重量） が適当である。  The fungicide for agricultural and horticultural use of the present invention can be used by foliage application, nursery box application, soil application or water surface application. The compounding ratio of the active ingredient is appropriately selected as required, but is preferably 0.1 to 20% (by weight) in the case of powders and granules, and 5 to 80% (by weight) in the case of emulsions and wettable powders. It is.
本発明の農園芸用殺菌剤の施用量は、 使用される化合物の種類、 対象病害、 発 生傾向、 被害の程度、 環境条件、 使用する剤型などによって変動する。 例えば粉 剤及び粒剤のようにそのまま使用する場合には、 有効成分で 10アール当り O.lg 〜5kg、 好ましくは lg〜lkgの範囲から適苴選ぶのがよい。 また、 乳剤及び水和 剤のように液状で使用する場合には、 0.1ppm〜10，000ppm、 好ましくは 1〜3， OOOppmの範囲から適宜選ぶのがよ 、。  The application rate of the agricultural and horticultural fungicide of the present invention varies depending on the type of the compound used, the target disease, the tendency to occur, the degree of damage, the environmental conditions, the dosage form used, and the like. For example, when used as such as powders and granules, it is advisable to select a suitable amount from the range of O.lg to 5 kg, preferably lg to lkg, per 10 ares of the active ingredient. When used in the form of a liquid such as an emulsion and a wettable powder, it is appropriate to appropriately select from the range of 0.1 ppm to 10,000 ppm, preferably 1 to 3, OOO ppm.
本発明による化合物は上記の施用形態により、 藻菌類 （Oomycetes)、 子嚢菌 類 （ Ascomycetes )、 不完全菌類 （ Deuteromycetes )、 及び担子菌類 (Basidiomycetes) に属する菌に起因する植物病を防除できる。 次に具体的な菌 名を非限定例としてあげる。 シュウ ドべロノスポラ （Pseudoperonospora) 属、 伊 jんはべ と两 gi Pseudoperonospora cubensis ) 、 ス フ エ ロ テ カ (Sphaerotheca) 属、 例えばうどんこ病菌 (Sphaerotheca fuliginea)、 ベンチ ユリア (Venturia)属、例えば黒星病菌 (Venturis inaequalis) . ピリキユラり ァ （Pyricularia ) 属、 例えばいもち病菌 (Pyricularia oryzae )、 ジペレラ ( Gibberella ) 属、 例えばばか苗病菌 ( Gibberella fujikuroi ) , ボトリチス ( Botrytis j 属、 例えば灰色かび病菌 （Botrytis cinerea )、 アルタナ リ ア (Alternaria)属、例えばコマツナ黒すす病菌 (Alternaria brassicicola)、 リゾ ク トニア （Rhizoctonia)属、例えば紋枯病菌 (Rhizoctonia solani)、 パクシ二 ァ (Puccinia) 属、 伊 Jえばさび丙菌 (Puccinia recondita 。 The compound according to the present invention can control plant diseases caused by fungi belonging to algal fungi (Oomycetes), ascomycetes (Ascomycetes), incomplete fungi (Deuteromycetes), and basidiomycetes (Basidiomycetes) by the above-mentioned application forms. Next, specific bacterial names are given as non-limiting examples. Pseudoperonospora, Pseudoperonospora cubensis, Sphaerotheca, for example Sphaerotheca fuliginea, Venturia, for example Genus Pyricularia, for example, Pyricularia oryzae, Gibberella, for example, Gibberella fujikuroi, Botrytis j, Botrytis j ), Altana Ria (Alternaria) genus, for example, Komatsuna black spot fungus (Alternaria brassicicola), Rhizoctonia (Rhizoctonia) genus, such as Rhizoctonia solani, Puccinia genus, and I J Palladium recondita (Puccinia recondita) .
さらに、 本発明の化合物は必要に応じて殺虫剤、 他の殺菌剤、 除草剤、 植物生 長調節剤、 肥料等と混用してもよい。 次に本発明の農園芸用殺菌剤の代表的な製 剤例をあげて製剤方法を具体的に説明する。 以下の説明において 「％」 は重量百 分率を示す。  Further, the compound of the present invention may be mixed with an insecticide, other fungicides, herbicides, plant growth regulators, fertilizers and the like, if necessary. Next, the formulation method will be specifically described with reference to typical examples of the agricultural and horticultural fungicides of the present invention. In the following description, “%” indicates weight percentage.
製剤例 1 粉剤 Formulation Example 1 Powder
化合物（A— 1 ) 2 %、珪藻土 5 %及びクレー 93 %を均一に混合粉砕して粉剤と した。  2% of the compound (A-1), 5% of diatomaceous earth and 93% of clay were uniformly mixed and pulverized to obtain a powder.
製剤例 2 水和剤 Formulation Example 2 wettable powder
化合物 （A— 1) 50 %、珪藻土 45 %、 ジナフチルメ夕ンジスルホン酸ナ卜リゥ ム 2 %及びリグニンスルホン酸ナトリウム 3 %を均一に混合粉砕して水和剤とし た。  50% of the compound (A-1), 45% of diatomaceous earth, 2% of sodium dinaphthylmethyldisulfonate and 3% of sodium ligninsulfonate were uniformly mixed and pulverized to obtain a wettable powder.
製剤例 3 乳剤 Formulation Example 3 Emulsion
化合物 （A — 1) 30 %、 シクロへキサノン 20 %、 ポリオキシエチレンアルキル ァリールエーテル 11 %、 アルキルベンゼンスルホン酸カルシウム 4 %及びメチル ナフタリ ン 35 %を均一に溶解して乳剤とした。  Emulsion was prepared by uniformly dissolving 30% of compound (A-1), 20% of cyclohexanone, 11% of polyoxyethylene alkylaryl ether, 4% of calcium alkylbenzenesulfonate and 35% of methylnaphthalene.
製剤例 4 粒剤 Formulation Example 4 Granules
化合物（A— 1) 5 %、 ラウリルアルコール硫酸エステルのナトリウム塩 2 %、 リ グニンスルホン酸ナ ト リウム 5 %、 カルボキシメチルセルロース 2 %及びクレ一 86 %を均一に混合粉砕する。 この混合物に水 20 %を加えて練合し、 押出式造粒 機を用いて 14〜32メッシュの粒状に加工したのち、 乾燥して粒剤とした。  5% of compound (A-1), 2% of sodium salt of lauryl alcohol sulfate, 5% of sodium ligninsulfonate, 2% of carboxymethylcellulose and 86% of clay are uniformly mixed and pulverized. The mixture was kneaded with 20% of water, kneaded, processed into granules of 14 to 32 mesh using an extrusion granulator, and dried to obtain granules.
[発明の効果]  [The invention's effect]
本発明化合物は、 イネいもち病などに対して高い防除効果を有し、 しかも、 作 物に薬害を生ずることなく、 残効性、 耐雨性に優れるという特徴をも併せ持って いるため、 農園芸用殺菌剤として有用である。  The compound of the present invention has a high control effect against rice blast and the like, and also has characteristics that it does not cause phytotoxicity to crops and has excellent residual effect and rain resistance. Useful as a fungicide.
次に本発明の農園芸用殺菌剤の奏する効果を試験例をあげて具体的に説明す る n 試験例 1 イネいもち病予防効果試験 Then we specifically described by way of Test Examples effects of the agricultural and horticultural fungicide of the present invention n Test example 1 Rice blast prevention effect test
直径 7cmの素焼鉢に水稲種子（品種：愛知旭）約 15粒ずつ播種し、温室内で 2 〜3週間育成した。 第 4葉が完全に展開したイネ苗に製剤例 2に準じて調製した 水和剤を有効成分濃度が 500ppmになるように水で «し、 1鉢当り 10ml散布し た。 風乾後、 イネいもち病菌（Pyricularia oryzae) の分生胞子懸濁液を噴霧接 種し、直ちに 25。Cの湿室内に 24時間入れた。 その後温室内に移し、接種 5日後に 第 4葉の病斑数を調査した。 数 1により防除価を求め、表 19の基準により評価し た結果を表 20〜表 23に示した。  Approximately 15 rice seeds (variety: Asahi Aichi) were sown in unglazed pots with a diameter of 7 cm, and grown in a greenhouse for 2-3 weeks. A wettable powder prepared according to Formulation Example 2 was sprayed with water on a rice seedling having the fourth leaf completely developed so that the active ingredient concentration became 500 ppm, and 10 ml per pot was sprayed. After air-drying, a conidia suspension of rice blast fungus (Pyricularia oryzae) was spray-inoculated and immediately 25. C was placed in a moist chamber for 24 hours. Then, they were transferred to a greenhouse, and the number of lesions on the fourth leaf was examined 5 days after inoculation. The control value was determined by the formula 1, and the results of evaluation based on the criteria in Table 19 are shown in Tables 20 to 23.
(数 1) 処理区の病斑数 (Equation 1) Number of lesions in the treatment area
防除価 （％) = (1 ) 100  Control value (%) = (1) 100
無処理区の病斑数  Lesion count in untreated area
(表 1 9 ) 評 価 防 除 価 (Table 19) Evaluation control
. A 1 0 0 %の防除価  A 100% control value
B 1 0 0 %未満〜 8 0. 0 %以上の防除価  B 100% to less than 8.0%
C 8 0. 0 %未満〜 5 0. 0 %以上の防除価  C 80.0% to less than 50.0%
D 5 0. 0 %未満の防除価 Control value less than D 50.0%
(表 20) (Table 20)
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化合物番号 評価 Compound number Evaluation
A一 1 AA-1 A
A- 2 BA- 2 B
A - 3 AA-3 A
A - 4 AA-4 A
A - 5 AA-5 A
A - 6 BA-6 B
A- 7 BA- 7 B
A- 8 AA- 8 A
A - 9 AA-9 A
A- 10 AA- 10 A
A - 1 1 BA-1 1 B
A- 12 AA- 12 A
A - 13 BA-13 B
A- 14 AA- 14 A
A- 1 5 AA- 15 A
A- 1 6 AA- 16 A
A- 17 AA- 17 A
A- 18 BA- 18 B
A- 1 9 AA- 1 9 A
A - 20 AA-20 A
A- 23 B A- 23 B
B  B
A- 25 B A- 25 B
A - 26 AA-26 A
A- 27 BA- 27 B
A - 28 AA-28 A
A - 29 AA-29 A
A - 30 AA-30 A
A - 3 1 BA-3 1 B
A - 32 AA-32 A
A - 33 AA-33 A
A - 34 A (表 2 1 ) A-34 A (Table 21)
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化合物D C番号 評価 Compound D C number Evaluation
A- 3 O 5 BA- 3 O 5 B
A- 36 AA- 36 A
A - 37 AA-37 A
A - 38 BA-38 B
A - 39 BA-39 B
A— 40 BA— 40 B
A 41 AA 41 A
A- 42 BA- 42 B
A- 43 BA- 43 B
A— 44 AA— 44 A
A- 45 BA- 45 B
A - 46 AA-46 A
A - 47 AA-47 A
A— 48 AA— 48 A
A- 49 AA- 49 A
A - 50 AA-50 A
A- 51 AA- 51 A
A- 52 BA- 52 B
A - 53 AA-53 A
A- 54 BA- 54 B
A- 55 BA- 55 B
A- 56 BA- 56 B
A- 57 BA- 57 B
A- 58 BA- 58 B
A— 59 B A— 59 B
B  B
A- 6 1 A A- 6 1 A
A- 62 BA- 62 B
A- 63 B A- 63 B
A  A
A- 65 A A- 65 A
A- 66 A (表 2 2 ) 化合物番号 評価A- 66 A (Table 22) Compound number Evaluation
A - 6 7 BA-6 7 B
B - 1 BB-1 B
B - 2 BB-2 B
B 3 AB 3 A
B - 4 BB-4 B
B - 5 BB-5 B
B - 6 AB-6 A
B - 7 BB-7 B
B - 8 BB-8 B
B - 9 BB-9 B
B - 1 0 BB-1 0 B
B - 1 1 BB-1 1 B
B - 1 2 AB-1 2 A
B - 1 3 BB-1 3 B
B - 1 4 BB-1 4 B
B - 1 5 BB-1 5 B
B - 1 6 AB-16 A
B - 1 7 BB-1 7 B
B - 1 8 AB-18 A
B - 1 9 BB-1 9 B
B - 2 0 AB-20 A
B - 2 1 AB-2 1 A
B - 2 2 AB-2 2 A
B - 2 3 AB-2 3 A
B - 2 4 AB-24 A
B - 2 5 BB-2 5 B
B 2 6 AB 2 6 A
B - 2 7 AB-2 7 A
B - 2 8 BB-2 8 B
B - 2 9 BB-2 9 B
C一 1 BC-1 B
C一 2 A (表 2 3 ) C-1 2 A (Table 23)
Figure imgf000041_0001
試験例 2 イネいもち病水面施用試験
Figure imgf000041_0001
Test example 2 Rice blast surface application test
直径 9 c mの白磁鉢に 1 . 5葉期の水稲 （品種：愛知旭） 稚苗を 3本ずつ 4力 所に移植し、 温室内で育成した。 2 . 5葉期に製剤例 2に準じて調製した水和剤 を有効成分濃度が 1 0アールあたり 3 0 0 gになるように鉢に水面施用処理をし た。 処理 1 0 日後に、 イネい も ち病菌 （ P y r i c u 1 a r i a o r y z a e ) の分生胞子懸濁液を噴霧接種し、 直ちに 2 5ての湿室内に 2 4時 間入れた。 その後、 温室内に移し、 接種 5日後に接種時の最高位葉の病斑数を調 査した。 数 1により防除価を求め、 表 1 9の基準により評価した結果を表 2 4〜 表 2 5に示した。 Rice seedlings in the 1.5 leaf stage (variety: Asahi Aichi) were transplanted into four white spots at a height of 9 cm in white porcelain pots and raised in a greenhouse. The wettable powder prepared according to Formulation Example 2 at the 2.5 leaf stage was subjected to water application to the pot such that the active ingredient concentration was 300 g per 10 ares. Ten days after the treatment, a conidia suspension of the rice blast fungus (Pyricu 1 ariaoryzae) was inoculated by spraying and immediately placed in 25 wet chambers for 24 hours. Then, they were transferred to a greenhouse, and 5 days after the inoculation, the number of lesions on the highest leaf at the time of the inoculation was examined. The control value was determined by Equation 1, and the results of evaluation based on the criteria in Table 19 are shown in Tables 24 to 25.
8 - a a ε - a a A 9 - v8-a a ε-a a A 9-v
V 9 9 - vV 9 9-v
H S 9 - VH S 9-V
V 9一 V e ΐ 9一 V a V 9-1 V e ΐ 9-1 V a
a  a
V ΐ 9 - V V ΐ 9-V
V 0 9 - V e 6 t - VV 0 9-V e 6 t-V
V 8 ー V e ΐ ー VV 8 ー V e ΐ ー V
V 6 ε - vV 6 ε-v
V I ε - νV I ε-ν
V 9 ε - ν fl 00 ε - νV 9 ε-ν fl 00 ε-ν
V ο ε - νV ο ε-ν
V 9 s - < V a ο s - V a 6 ΐ - VV 9 s-<V a ο s-V a 6 ΐ-V
V 8 ΐ - V a Ζ ΐ - V a t ΐ - VV 8 ΐ-V a Ζ ΐ-V a t ΐ-V
V S ΐ - V a a 0 ΐ - VV S ΐ-V a a 0 ΐ-V
V 6 - VV 6-V
V 8 - VV 8-V
9 9 - V9 9-V
V δ - νV δ-ν
V ΐ - V m V ΐ-V m
9l8S0/86diV丄：) d 0 I8e£/66 O (表 2 5 ) 化合物番号 評価9l8S0 / 86diV 丄 :) d 0 I8e £ / 66 O (Table 25) Compound number Evaluation
B - 5 ΒB-5 Β
B - 6 AB-6 A
B - 1 8 AB-18 A
Β— 1 9 BΒ— 1 9 B
Β - 2 4 AΒ-24 A
Β - 2 5 AΒ-25 A
Β - 2 6 BΒ-2 6 B
Β - 2 7 BΒ-2 7 B
C一 2 B C-1 2 B

Claims

請求の範囲 The scope of the claims
1. 一般式 [ I ]  1. General formula [I]
Figure imgf000044_0001
Figure imgf000044_0001
[式中、 Xは水素原子、 C Ceアルキル基、 c丄〜c 4ハ口アルキル基、 c i〜C 6アルコキシ基、 c ,〜c ハロアルコキシ基、 cり〜 アルケニル ォキシ基、 Cり〜c アルキニルォキシ基、 C丄〜cハアルキルチオ基、 。 〜 C Λハロアルキルチオ基、 ハロゲン原子、 アミ ノ基、 ニトロ基、 シァノ基、 フエ ニル基 （該基は c 1 c 6アルキル基、 c i c 4ハ口アルキル基、 c丄〜c 6 アルコキシ基又はハロゲン原子によって置換されていてもよい。 ） 又はフ Xノキ シ基 （該基は c 1〜c 6アルキル基、 c ]〜C jハロアルキル基、 C丄〜c ァ ルコキシ基又はハロゲン原子によって置換されてもよい。 ） を表し、 nは 1〜4 の整数を表し、 R 1は水素原子、 C i C eアルキル基、 C 3〜C Pシクロアル キル基又は C 2 〜C 4ハ口アルキル基を表し、 R 2及び R はそれぞれ独立し て、 C i〜c6アルキル基、 c2〜c6アルケニル基、 C Q 〜C Pシクロアルキ ル基 （該基はハロゲン原子又は C j〜c 6アルキル基によって置換されていても よい。 ） 、 c 3〜c 6シクロアルキル c ,〜c アルキル基又は c i〜c 4ハ口 アルキル基を表すか、 あるいは R 2と R。はこれらが結合している炭素原子と共 に 5員〜 7員環のシクロアルキル基 （該基は C λ〜C 6アルキル基によって置換 されていてもよい。 ） を形成し、 Qは C 2〜C pアルキル基、 ェチニル基、 基一 COR4 (！^ ^まじ 丄〜 ハアルキル基、 C 3〜C シクロアルキル基 （該基は ハロゲン原子、 C J c アルキル基によって置換されてもよい。 ） 又は c iWherein X is a hydrogen atom, a C Ce alkyl group, a c-c 4 alkyl group, a c- C 6 alkoxy group, a c, -c haloalkoxy group, a c-alkenyloxy group, a C- c alkynyloxy, C 丄 -calkylthio, ~ C lambda haloalkylthio group, a halogen atom, an amino group, a nitro group, Shiano group, Hue alkenyl group (said group c 1 c 6 alkyl group, cic 4 Ha port alkyl group, c丄to c 6 alkoxy group or a halogen Or a substituted oxy group (the group may be a C 1 -C 6 alkyl group, a c] -C j haloalkyl group, a C 丄 -C alkoxy group, or a halogen atom. Wherein n represents an integer of 1 to 4, R 1 represents a hydrogen atom, a C i C alkyl group, a C 3 -CP cycloalkyl group or a C 2 -C 4 alkyl group; R 2 and R are each independently a C i -c 6 alkyl group, a c 2 -c 6 alkenyl group, a C Q -CP cycloalkyl group (the group is substituted by a halogen atom or a C j -c 6 alkyl group). even though it may.), c 3 ~c 6 cycloalkyl c, to c alkyl group or Ci～c 4 Represent a mouth alkyl group, or R 2 and R. Form a cycloalkyl group having 5-membered to 7-membered ring carbon atom co which they are attached (said group may be substituted by C lambda -C 6 alkyl group.), Q is C 2 -C p alkyl group, ethynyl group, group-COR 4 (! ^^ ハ -alkyl group, C 3 -C cycloalkyl group (the group may be substituted by a halogen atom or a CJ c alkyl group)) or ci
C 4ハ口アルキル基を表す。 ） 又は基— CH (OH) R （R5は C j Cハァ ルキル基、 c 3〜c 6シクロアルキル基 （該基はハロゲン原子、 c 1〜c6アル キル基によって置換されてもよい。 ) 又は C丄〜c ,ハ口アルキル基を表す。 ) を表し、 Aは酸素原子又は硫黄原子を表す。 ] にて示されるピリジルォキシ (チ ォ） アルカン酸アミ ド誘導体。 Represents a C 4 alkyl group. ) Or a group - CH (OH) R (R 5 is C j C huh alkyl group, c 3 to c 6 cycloalkyl (in which the group halogen atom, may be substituted by c 1 to c 6 Al kill group. ) Or C 丄 -c, which represents an alkyl group, and A represents an oxygen atom or a sulfur atom. A pyridyloxy (thio) alkanoic acid amide derivative represented by the formula:
2 - 一般式 [ I ] 2-general formula [I]
Figure imgf000045_0001
Figure imgf000045_0001
[式中、 Xは C丄〜C 6アルキル基、 C j〜C 4ハ口アルキル基、 C C gT ルコキシ基、 C 〜c 4ハ口アルコキシ基、 C j〜C ハロアルキルチオ基、 ハ ロゲン原子、 アミノ基、 ニト口基、 シァノ基、 フエニル基 （該基は c i〜c ァ ルキル基、 C J〜C Λハロアルキル基、 C 〜C アルコキシ基又はハロゲン原 子によって置換されていてもよい。 ） 又はフエノキシ基 （該基は c i〜c 6アル キル基、 c丄〜c ハロアルキル基、 c i〜C pアルコキシ基又はハロゲン原子 によって置換されてもよい。 ） を表し、 nは 1〜4の整数を表し、 R 1は水素原 子又は C j〜C アルキル基を表し、 R 2及び Rリはそれぞれ独立して、 C ,〜 c 6アルキル基、 c2~c 6アルケニル基、 C。〜C シクロアルキル基 （該基 はハロゲン原子又は C i〜C アルキル基によって置換されていてもよい。 ） 又 は 丄〜C ハロアルキル基を表すか、 あるいは R 2と R 3はこれらが結合して いる炭素原子と共に 5員〜 7員環のシクロアルキル基 （該基は C χ〜C 6ァルキ ル基によって置換されていてもよい。 ） を形成し、 Qは C 2〜C 6アルキル基、 ェチニル基、 基— COR4 はじ 〜 アルキル基、 C 3〜C 6シクロア ルキル基 （該基はハロゲン原子、 C丄〜C アルキル基によって置換されてもよ い。 ) 又は C i〜C 4ハロアルキル基を表す。 ） 又は基— CH (OH) R 5 (R "は C χ〜C 6アルキル基、 C。〜C シクロアルキル基 （該基はハロゲン 原子、 C i〜C 6アルキル基によって置換されてもよい。 ) 又は C 1〜C tハロ アルキル基を表す。 ) を表し、 Aは酸素原子又は硫黄原子を表す。 ] にて示され るピリジルォキシ （チォ） アルカン酸アミ ド誘導体。 [Wherein, X is C丄-C 6 alkyl group, C J～C 4 Ha port alkyl group, CC gT alkoxy group, C to c 4 c port alkoxy, C J～C haloalkylthio group, Ha androgenic atom, amino group, a nitro port group, Shiano group, phenyl group (said group ci~c § alkyl group, CJ～C lambda haloalkyl group, may be substituted by C -C alkoxy group or a halogen atom.) or phenoxy represents a group (said group Ci～c 6 Al kill group, c丄~c haloalkyl group, may be substituted by Ci～C p alkoxy group or a halogen atom.), n represents an integer of 1 to 4, R 1 represents a hydrogen atom or a C j to C alkyl group; R 2 and R 1 each independently represent a C 1 to C 6 alkyl group, a c 2 to C 6 alkenyl group, or C; ~ C cycloalkyl group (The group may be substituted by a halogen atom or a Ci-C alkyl group.) Or 丄 ~ C haloalkyl group, or R 2 and R 3 are cycloalkyl group having 5-membered to 7-membered ring together with the carbon atom to which are (said group may be substituted by C chi -C 6 Aruki Le group.) to form, Q is C 2 -C 6 alkyl group, Echiniru A group, a group—a COR 4 -alkyl group, a C 3 -C 6 cycloalkyl group (the group may be substituted by a halogen atom or a C 丄 -C alkyl group) or a C i -C 4 haloalkyl group. Represent. ) Or a group - CH (OH) R 5 ( R " is C chi -C 6 alkyl group, C.～C cycloalkyl group (in which the halogen atom may be substituted by C i~C 6 alkyl group. ) Or a C 1 -C t haloalkyl group;) and A represents an oxygen atom or a sulfur atom.] A pyridyloxy (thio) alkanoic acid amide derivative represented by the formula:
3. 一般式 [I]
Figure imgf000046_0001
3. General formula [I]
Figure imgf000046_0001
[式中、 Xは C χ 〜C 6アルキル基、 c 2 〜C 4ハ口アルキル基、 c i〜c 4ハ 口アルコキシ基、 ハロゲン原子、 C i C eアルコキシ基、 ニトロ基又はシァノ 基を表し、 nは 1〜4の整数を表し、 R 1は水素原子又は C i Ceアルキル基 を表し、 R 2及び R 3はそれぞれ独立して、 じ丄〜 アルキル基、 C 3〜C 6 シクロアルキル基 （該基はハロゲン原子又は C 〜C アルキル基によって置換 されていてもよい。 ） 又は C i〜C 4ハ口アルキル基を表すか、 あるいは R と R 3はこれらが結合している炭素原子と共に 5員〜 7員環のシク口アルキル基[Wherein, X represents C chi -C 6 alkyl group, c 2 -C 4 Ha port alkyl group, Ci～c 4 Ha port alkoxy group, a halogen atom, C i C e alkoxy group, a nitro group or a Shiano group , N represents an integer of 1 to 4, R 1 represents a hydrogen atom or a C i Ce alkyl group, and R 2 and R 3 each independently represent a di-alkyl group, a C 3 -C 6 cycloalkyl group (The group may be substituted by a halogen atom or a C 1 -C 4 alkyl group.) Or a C i -C 4 alkyl group, or R and R 3 together with the carbon atom to which they are attached 5- to 7-membered cyclic alkyl group
(該基は C i〜Cハアルキル基によって置換されていてもよい。 ） を形成し、 Q は基一 C OR 4 (R 4は C丄〜Cハアルキル基を表す） 又は C H (OH) R 5 (Said group C I～C Haarukiru may be substituted by a group.) Forming a, Q is group one C OR 4 (R 4 represents a C丄~C Haarukiru group), or CH (OH) R 5
(R 5は C ， 〜C 6アルキル基を表す） を表し、 Aは酸素原子又は硫黄原子を表 す。 ] にて示されるピリジルォキシ （チォ） アルカン酸アミ ド誘導体。 (R 5 is C, represents a -C 6 alkyl group) represents, A is to display the oxygen atom or a sulfur atom. A pyridyloxy (thio) alkanoic acid amide derivative represented by the formula:
4. 請求項 1、 請求項 2又は請求項 3に記載のピリジルォキシ （チォ） アル力 ン酸ァミ ド誘導体を有効成分として含有する農園芸用殺菌剤。  4. A fungicide for agricultural and horticultural use containing the pyridyloxy (thio) amide derivative according to claim 1, 2, or 3 as an active ingredient.
PCT/JP1998/005816 1997-12-24 1998-12-22 Pyridyloxy(thio)alkanoic acid amide derivatives and agricultural/horticultural bactericides WO1999033810A1 (en)

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