JP2005213168A - Isoxazolin-3-yl derivative and herbicide containing the same as active ingredient - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an isoxazolin-3-yl derivative having an excellent herbicidal effect and excellent selectivity between crops and weeds or its pharmacologically acceptable salt. <P>SOLUTION: This herbicide contains an isoxazolin-3-yl derivative represented by general formula [I] [R<SP>1</SP>and R<SP>2</SP>are each independently H, a halogen atom, a 1 to 10C alkyl, or a 3 to 8C cycloalkyl; Q is formula Q<SP>1</SP>or formula Q<SP>2</SP>; R<SP>3</SP>is H, a halogen atom, a 1 to 10C alkyl, a 3 to 8C cycloalkyl; R<SP>4</SP>and R<SP>5</SP>are each independently H, a 1 to 10C alkyl, a 2 to 6C alkenyl or a 2 to 6C alkynyl which may be substituted; (n) is an integer of 0 to 2] or its pharmacologically acceptable salt as an active ingredient. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a novel isoxazolin-3-yl derivative and a herbicide containing it as an active ingredient.

For example, Patent Documents 1 to 7 report that isoxazolin-3-yl derivatives have herbicidal activity. However, the compounds of the present invention are not described in these documents.
JP-A-8-225548 JP-A-9-328477 Japanese Patent Laid-Open No. 9-328483 WO01 / 012613 WO02 / 062770 WO03 / 000686 Publication WO03 / 010165 publication

It is desired that the herbicide used for useful crops is an agent that is applied to soil or foliage, exhibits a sufficient herbicidal effect at a low dose, and exhibits high selectivity between crops and weeds.

In view of such circumstances, the present inventors have examined the herbicidal effect and the selectivity between crops and weeds. As a result, the novel isoxazolin-3-yl derivative has an excellent herbicidal effect and selectivity between crops and weeds. As a result, the present invention has been completed.

That is, the present invention
(1) An isoxazolin-3-yl derivative having the general formula [I] or a pharmacologically acceptable salt thereof:

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C. ₆ alkynyl group, C ₁ -C ₁₀ haloalkyl group, C ₁ -C ₁₀ alkoxy group, phenyl group optionally substituted by substituent group α, —C (═O) —Z—R ⁶ group, cyano group, C ₁ -C ₁₀ alkylthio group, C ₁ -C ₁₀ alkylsulfinyl group or C ₁ -C ₁₀ alkylsulfonyl group, and R ¹ and R ² together with these bonded carbon atoms are C ₃ -C ₇ carbocycles may form a, Q is represents a formula ^{Q 1} or formula ^{Q 2,}

R ³ is a hydrogen atom, a halogen atom, a C _{1 to} C ₁₀ alkyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{2 to} C ₆ alkenyl group, a C _{2 to} C ₆ alkynyl group, or a C _{1 to} C ₁₀ haloalkyl group. Represents a phenyl group which may be substituted with a substituent group α, a heterocyclic group which may be substituted with a substituent group α, a —C (═O) —Z—R ⁶ group or a —ZR ⁶ group. , R ⁴ and R ⁵ are each independently a hydrogen atom, a C ₁ -C ₁₀ alkyl group optionally substituted with a substituent group β, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group. , _C 3 -C ₈ cycloalkyl _group, C 1 _{-C 10} alkoxycarbonyl group, -C (= O) -Z- R 6 _group, C 1 _{-C 10} alkyl thio group may be a carboxyl group or a substituted Represents a phenyl group,
R ⁴ and R ⁵ together with these bonded carbon atoms may form a C _{3 to} C ₇ carbocycle,
Z represents O, S or NR ⁷ ;
R ⁶ and R ⁷ are independently of each other
Hydrogen _atom, C 1 _{-C 10} alkyl _group, C 3 -C ₈ cycloalkyl _group, C 2 -C ₆ alkenyl _group, C 2 -C ₆ alkynyl _group, C 1 _{-C 10} haloalkyl _group, C 1 _{-C 10} alkoxy Represents a phenyl group which may be substituted with a group or substituent group α,
n shows the integer of 0-2.
`` Substituent group α ''
A hydroxyl group, a halogen _atom, C 1 _{-C 10} alkyl groups, mono-substituted with a substituent group γ the _C 1 _{-C 10} alkyl _group, C 1 -C ₄ haloalkyl _groups, C 3 -C ₈ cycloalkyl _{group, C} 1 ~ C ₁₀ alkoxy group, C ₁ -C ₁₀ alkoxy group monosubstituted by substituent group δ, C ₁ -C ₄ haloalkoxy group, C ₃ -C ₈ cycloalkyloxy group, C ₃ -C ₈ cycloalkyl C ₁ -C ₃ alkyloxy _groups, C 1 _{-C 10} alkylthio group, mono-substituted with a substituent group δ a _C 1 _{-C 10} alkylthio _groups, C 1 -C ₄ haloalkylthio _groups, C 2 -C ₆ alkenyl groups, C ₂ -C ₆ alkenyloxy _group, C 2 -C ₆ alkynyl _group, C 2 -C ₆ alkynyloxy _group, C 1 _{-C 10} alkylsulfinyl _group, C 1 _{-C 10} alkylsulfonyl group Mono-substituted with a substituent group δ a _C 1 _{-C 10} alkylsulfonyl _group, C 1 -C ₄ haloalkylsulfonyl _group, C 1 _{-C 10} alkylsulfonyloxy _group, C 1 -C ₄ haloalkylsulfonyl group, optionally substituted An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic heterocyclic oxy group, a substituted Aromatic heterocyclic thio group which may be substituted, phenylsulfonyl group which may be substituted, aromatic heterocyclic sulfonyl group which may be substituted, phenylsulfonyloxy group which may be substituted, C ₁ -C ₆ acyl group, C ₁ -C ₄ haloalkylcarbonyl group, an optionally substituted benzylcarbonyl group, optionally substituted Which may benzoyl group, carboxyl group, C ₁ -C ₁₀ alkoxycarbonyl group, an optionally substituted benzyloxycarbonyl group, an optionally substituted phenoxycarbonyl group, a cyano group, a nitrogen atom of the carbamoyl group (said group identical or _different, C 1 _{-C 10} alkyl group or may be substituted in a phenyl group optionally _{substituted),} C 1 -C ₆ Ashiokishi _group, C 1 -C ₄ haloalkylcarbonyl group, optionally substituted Optionally substituted benzylcarbonyloxy group, optionally substituted benzoyloxy group, nitro group, amino group (nitrogen atoms of the group are the same or different, C ₁ -C ₁₀ alkyl group, optionally substituted) phenyl _group, C 1 -C ₆ acyl _group, C 1 -C ₄ haloalkylcarbonyl group, an optionally substituted benzylidene Carbonyl group, an optionally substituted benzoyl group, C ₁ -C ₁₀ alkylsulfonyl group, C ₁ -C ₄ haloalkylsulfonyl group, with an optionally substituted benzylsulfonyl group or an optionally substituted phenylsulfonyl group May be substituted)
"Substituent group β"
1 to 3 halogen atoms that are the same or different, a hydroxyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{1 to} C ₁₀ alkoxy group, a C _{1 to} C ₁₀ alkylcarbonyl group, a C _{1 to} C ₁₀ alkylthio group, C ₁ -C ₁₀ alkylsulfinyl _group, C 1 _{-C 10} alkylsulfonyl _group, C 1 _{-C 10} alkylamino group, di _(C 1 _{-C 10} alkyl) amino group, a cyano _group, C 1 _{-C 10} alkoxycarbonyl group, a carbamoyl Group, mono (C ₁ -C ₁₀ alkyl) carbamoyl group, di (C ₁ -C ₁₀ alkyl) carbamoyl group, C ₁ -C ₁₀ alkylthiocarbonyl group, carboxyl group, optionally substituted benzyloxy group, substituted Optionally substituted phenoxy group or optionally substituted phenyl group "substituent group γ"
_Hydroxyl, C 3 -C ₈ cycloalkyl group (which may be substituted with a halogen atom or a _C 1 -C ₃ alkyl _{group), C} 1 ~C ₁₀ alkoxy _group, C 1 _{-C 10} alkylthio group, _{C 1} -C ₁₀ alkylsulfonyl _group, C 1 _{-C 10} alkoxycarbonyl _group, C 2 -C ₆ haloalkenyl group, the nitrogen atom of the amino group (in which the same or _different, C 1 _{-C 10} alkyl _{group, C} 1 ~ C ₆ acyl group, C ₁ -C ₄ haloalkylcarbonyl group, C ₁ -C ₁₀ alkylsulfonyl group, optionally substituted with C ₁ -C ₄ haloalkylsulfonyl group), mono (C ₁ -C ₁₀ alkyl) carbamoyl group, di _(C 1 _{-C 10} alkyl) carbamoyl group, a carbamoyl _group, C 1 -C ₆ acyl _group, C 1 -C ₄ haloalkylcarbonyl group, _{C 1} C ₁₀ alkoxyimino group, a cyano group, a phenyl group which may be substituted, an optionally substituted phenoxy group "substituent group δ"
C ₁ -C ₁₀ alkoxycarbonyl group, optionally substituted phenyl group, optionally substituted aromatic heterocyclic group (2) The isoxazolin-3-yl derivative according to (1) or a pharmacologically acceptable salt thereof A herbicide containing a salt as an active ingredient.

  In this specification, terms used are defined below.

  A halogen atom shows a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom.

The C _{1 to} C ₁₀ alkyl group means a linear or branched alkyl group having 1 to 10 carbon atoms unless otherwise specified, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. N-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, 1-methylbutyl group, 2-methylbutyl group, 3-methylbutyl group, 1-ethylpropyl group, 1,1 -Dimethylpropyl group, 1,2-dimethylpropyl group, neopentyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1-ethylbutyl group 2-ethylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 1,3-dimethylbutyl group, 2,2-dimethylbutyl group, 2,3-dimethylbutyl group, 3,3 Dimethylbutyl group, 1,1,2-trimethylpropyl group, 1,2,2-trimethylpropyl group, 1-ethyl-1-methylpropyl group, 1-ethyl-2-methylpropyl group, heptyl group, 1-methyl Hexyl group, 5-methylhexyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 4,4-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 1,1,3 -Trimethylbutyl group, 1,2,2-trimethylbutyl group, 1,3,3-trimethylbutyl group, 2,2,3-trimethylbutyl group, 2,3,3-trimethylbutyl group, 1-propylbutyl group 1,1,2,2-tetramethylpropyl group, octyl group, 1-methylheptyl group, 3-methylheptyl group, 6-methylheptyl group, 2-ethylhexyl group, 5, -Dimethylhexyl group, 2,4,4-trimethylpentyl group, 1-ethyl-1-methylpentyl group, nonyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group, 7-methyloctyl Group, 1-ethylheptyl group, 1,1-dimethylheptyl group, 6,6-dimethylheptyl group, decyl group, 1-methylnonyl group, 2-methylnonyl group, 6-methylnonyl group, 1-ethyloctyl group, 1-ethyloctyl group, A propylheptyl group etc. can be mentioned.

The C _{3 to} C ₈ cycloalkyl group means a cyclic alkyl group having 3 to 8 carbon atoms unless otherwise specified, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. The group can be mentioned.

The C ₁ -C ₄ haloalkyl group is the same or different and represents a linear or branched alkyl group having 1 to 4 carbon atoms that is substituted with a halogen atom 1 to 9 unless otherwise specified, for example, Fluoromethyl group, chloromethyl group, bromomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, trichloromethyl group, chlorodifluoromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 1-chloroethyl group, 2 -Chloroethyl group, 1-bromoethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 1,2-dichloroethyl group, 2,2-dichloroethyl group, 2,2,2-trifluoroethyl group, 2 , 2,2-trichloroethyl group, 1,1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 2-bromo 2-chloroethyl group, 2-chloro-1,1,2,2-tetrafluoroethyl group, 1-chloro-1,2,2,2-tetrafluoroethyl group, 1-chloropropyl group, 2-chloropropyl group 3-chloropropyl group, 2-bromopropyl group, 3-bromopropyl group, 2-bromo-1-methylethyl group, 3-iodopropyl group, 2,3-dichloropropyl group, 2,3-dibromopropyl group 3,3,3-trifluoropropyl group, 3,3,3-trichloropropyl group, 3-bromo-3,3-difluoropropyl group, 3,3-dichloro-3-fluoropropyl group, 2,2, 3,3-tetrafluoropropyl group, 1-bromo-3,3,3-trifluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 2,2,2-trifluoro-1- Lifluoromethylethyl group, heptafluoropropyl group, 1,2,2,2-tetrafluoro-1-trifluoromethylethyl group, 2,3-dichloro-1,1,2,3,3-pentafluoropropyl group 2-chlorobutyl group, 3-chlorobutyl group, 4-chlorobutyl group, 2-chloro-1,1-dimethylethyl group, 4-bromobutyl group, 3-bromo-2-methylpropyl group, 2-bromo-1,1 -Dimethylethyl group, 2,2-dichloro-1,1-dimethylethyl group, 2-chloro-1-chloromethyl-2-methylethyl group, 4,4,4-trifluorobutyl group, 3,3,3 -Trifluoro-1-methylpropyl group, 3,3,3-trifluoro-2-methylpropyl group, 2,3,4-trichlorobutyl group, 2,2,2-trichloro-1,1-dimethyl Ethyl group, 4-chloro-4,4-difluorobutyl group, 4,4-dichloro-4-fluorobutyl group, 4-bromo-4,4-difluorobutyl group, 2,4-dibromo-4,4-difluoro Butyl group, 3,4-dichloro-3,4,4-trifluorobutyl group, 3,3-dichloro-4,4,4-trifluorobutyl group, 4-bromo-3,3,4,4-tetra Fluorobutyl group, 4-bromo-3-chloro-3,4,4-trifluorobutyl group, 2,2,3,3,4,4-hexafluorobutyl group, 2,2,3,4,4, 4-hexafluorobutyl group, 2,2,2-trifluoro-1-methyl-1-trifluoromethylethyl group, 3,3,3-trifluoro-2-trifluoromethylpropyl group, 2,2,3 , 3,4,4,4-heptafluorobutyl group 2,3,3,3-tetrafluoro-2-trifluoromethylpropyl group, 1,1,2,2,3,3,4,4-octafluorobutyl group, nonafluorobutyl group, 4-chloro-1 , 1, 2, 2, 3, 3, 4, 4-octafluorobutyl group and the like.

The C _{2 to} C ₆ alkenyl group means a straight or branched alkenyl group having 2 to 6 carbon atoms unless otherwise specified, and examples thereof include a vinyl group, 1-propenyl group, i-propenyl group, 2- Propenyl group, 1-butenyl group, 1-methyl-1-propenyl group, 2-butenyl group, 1-methyl-2-propenyl group, 3-butenyl group, 2-methyl-1-propenyl group, 2-methyl-2 -Propenyl group, 1,3-butadienyl group, 1-pentenyl group, 1-ethyl-2-propenyl group, 2-pentenyl group, 1-methyl-1-butenyl group, 3-pentenyl group, 1-methyl-2- Butenyl group, 4-pentenyl group, 1-methyl-3-butenyl group, 3-methyl-1-butenyl group, 1,2-dimethyl-2-propenyl group, 1,1-dimethyl-2-propenyl group, 2- Methyl-2 Butenyl group, 3-methyl-2-butenyl group, 1,2-dimethyl-1-propenyl group, 2-methyl-3-butenyl group, 3-methyl-3-butenyl group, 1,3-pentadienyl group, 1- Vinyl-2-propenyl group, 1-hexenyl group, 1-propyl-2-propenyl group, 2-hexenyl group, 1-methyl-1-pentenyl group, 1-ethyl-2-butenyl group, 3-hexenyl group, 4-hexenyl group, 5-hexenyl group, 1-methyl-4-pentenyl group, 1-ethyl-3-butenyl group, 1- (i-butyl) vinyl group, 1-ethyl-1-methyl-2-propenyl group 1-ethyl-2-methyl-2-propenyl group, 1- (i-propyl) -2-propenyl group, 2-methyl-2-pentenyl group, 3-methyl-3-pentenyl group, 4-methyl-3 -Pentenyl group, 1 3-dimethyl-2-butenyl group, 1,1-dimethyl-3-butenyl group, 3-methyl-4-pentenyl group, 4-methyl-4-pentenyl group, 1,2-dimethyl-3-butenyl group, 1 , 3-dimethyl-3-butenyl group, 1,1,2-trimethyl-2-propenyl group, 1,5-hexadienyl group, 1-vinyl-3-butenyl group, 2,4-hexadienyl group, etc. it can.

The C ₂ -C ₆ alkynyl group means a straight-chain or branched alkynyl group having 2 to 6 carbon atoms unless otherwise specified, and examples thereof include an ethynyl group, a 1-propynyl group, a 2-propynyl group, and a 1-butynyl group. Group, 1-methyl-2-propynyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-ethyl-2-propynyl group, 2-pentynyl group, 3-pentynyl group, 1-methyl-2 -Butynyl group, 4-pentynyl group, 1-methyl-3-butynyl group, 2-methyl-3-butynyl group, 1-hexynyl group, 1- (n-propyl) -2-propynyl group, 2-hexynyl group, 1-ethyl-2-butynyl group, 3-hexynyl group, 1-methyl-2-pentynyl group, 1-methyl-3-pentynyl group, 4-methyl-1-pentynyl group, 3-methyl-1-pentynyl group, 5-he Sinyl group, 1-ethyl-3-butynyl group, 1-ethyl-1-methyl-2-propynyl group, 1- (i-propyl) -2-propynyl group, 1,1-dimethyl-2-butynyl group or 2 , 2-dimethyl-3-butynyl group and the like.

The C ₂ -C ₆ haloalkenyl group is the same or different and represents a linear or branched alkenyl group having 2 to 6 carbon atoms substituted with a halogen atom 1 to 4 unless otherwise specified, for example, 2-chlorovinyl group, 2-bromovinyl group, 2-iodovinyl group, 3-chloro-2-propenyl group, 3-bromo-2-propenyl group, 1-chloromethylvinyl group, 2-bromo-1-methylvinyl group 1-trifluoromethylvinyl group, 3,3,3-trichloro-1-propenyl group, 3-bromo-3,3-difluoro-1-propenyl group, 2,3,3,3-tetrachloro-1- Propenyl group, 1-trifluoromethyl-2,2-difluorovinyl group, 2-chloro-2-propenyl group, 3,3-difluoro-2-propenyl group, 2,3,3-trichloro-2-pro Nyl group, 4-bromo-3-chloro-3,4,4-trifluoro-1-butenyl group, 1-bromomethyl-2-propenyl group, 3-chloro-2-butenyl group, 4,4,4-tri Fluoro-2-butenyl group, 4-bromo-4,4-difluoro-2-butenyl group, 3-bromo-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3,4,4 -Tribromo-3-butenyl group, 3-bromo-2-methyl-2-propenyl group, 3,3-difluoro-2-methyl-2-propenyl group, 3,3,3-trifluoro-2-methylpropenyl group 3-chloro-4,4,4-trifluoro-2-butenyl group, 3,3,3-trifluoro-1-methyl-1-propenyl group, 3,4,4-trifluoro-1,3- Butadienyl group, 3,4-dibromo-1-pe Tenenyl group, 4,4-difluoro-3-methyl-3-butenyl group, 3,3,4,4,5,5,5-heptafluoro-1-pentenyl group, 5,5-difluoro-4-pentenyl group 4,5,5-trifluoro-4-pentenyl group, 3,4,4,4-tetrafluoro-3-trifluoromethyl-1-butenyl group, 4,4,4-trifluoromethyl-3-methyl -2-butenyl group, 3,5,5-trifluoro-2,4-pentadienyl group, 4,4,5,5,6,6,6-heptafluoro-2-hexenyl group, 3,4,4, 5,5,5-hexafluoro-3-trifluoromethyl-1-pentenyl group, 4,5,5,5-tetrafluoro-4-trifluoromethyl-2-pentenyl group or 5-bromo-4,5 5-trifluoro-4-trifluoromethyl A 2-pentenyl group can be exemplified.

The C _{1 to} C ₁₀ alkoxy group means a linear or branched (alkyl) -O— group having 1 to 10 carbon atoms in which the alkyl part has the above meaning, unless specifically limited, and includes, for example, a methoxy group, Examples thereof include an ethoxy group, an n-propoxy group, an isopropoxy group, a tert-butoxy group, an n-butoxy group, a sec-butoxy group, and an isobutoxy group.

The C ₁ -C ₄ haloalkoxy group means a linear or branched (haloalkyl) -O— group having 1 to 4 carbon atoms in which the haloalkyl moiety has the above-mentioned meaning, unless specifically limited. For example, difluoromethoxy Group, trifluoromethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group and the like.

The C _{3 to} C ₈ cycloalkyloxy group means a (cycloalkyl) -O— group having 3 to 8 carbon atoms in which the cycloalkyl part has the above-mentioned meaning, unless specifically limited. For example, a cyclopropyloxy group, A cyclobutyloxy group, a cyclopentyloxy group, a cyclohexyloxy group, etc. can be mentioned.

The C ₃ -C ₈ cycloalkyl C ₁ -C ₃ alkyloxy group means a (cycloalkylalkyl) -O— group in which the cycloalkylalkyl moiety and the alkyl moiety have the above-mentioned meanings, unless otherwise specified. Propylmethoxy group, 1-cyclopropylethoxy group, 2-cyclopropylethoxy group, 1-cyclopropylpropoxy group, 2-cyclopropylpropoxy group, 3-cyclopropylpropoxy group, cyclobutylmethoxy group, cyclopentylmethoxy group or cyclohexylmethoxy Groups and the like.

The C _{2 to} C ₆ alkenyloxy group means an (alkenyl) -O— group having 2 to 6 carbon atoms in which the alkenyl part has the above meaning, unless specifically limited, and examples thereof include a 2-propenyloxy group. be able to.

The C _{2 to} C ₆ alkynyloxy group means a (alkynyl) -O— group having 2 to 6 carbon atoms in which the alkynyl moiety has the above meaning, unless specifically limited, and examples thereof include 2-propynyloxy group and the like. be able to.

The C ₁ -C ₁₀ alkoxyimino group means an (alkoxy) -N = group having 2 to 6 carbon atoms, in which the alkoxy moiety has the above-mentioned meaning, unless specifically limited. For example, a methoxyimino group or an ethoxyimino group Can be mentioned.

The C ₁ -C ₁₀ alkylthio group, the alkyl moiety having a carbon number of means described above indicates a 1 to 10 (alkyl) -S- group, such as methylthio, ethylthio group, n- propylthio group, isopropylthio group Etc.

The C ₁ -C ₁₀ alkylsulfinyl group, the alkyl moiety having a carbon number of means described above indicates a 1 to 10 (alkyl) -SO- group, for example, methylsulfinyl group, ethylsulfinyl group, n- propyl sulfinyl group Or an isopropyl sulfinyl group etc. can be mentioned.

The C ₁ -C ₁₀ alkylsulfonyl group means an (alkyl) -SO ₂ — group having 1 to 10 carbon atoms in which the alkyl portion has the above meaning, for example, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl. Group or isopropylsulfonyl group.

The C ₁ -C ₁₀ alkylsulfonyloxy group means an (alkyl) SO ₂ —O— group having 1 to 10 carbon atoms in which the alkyl portion has the above meaning, such as a methylsulfonyloxy group or an ethylsulfonyloxy group. Can be mentioned.

The C ₁ -C ₁₀ alkylcarbonyl group means an (alkyl) -C (═O) — group having 1 to 10 carbon atoms in which the alkyl portion has the above meaning, and examples thereof include an acetyl group or a methylcarbonyl group. be able to.

The C ₁ -C ₁₀ alkylamino group means an (alkyl) -NH— group having 1 to 10 carbon atoms in which the alkyl portion has the above meaning, and examples thereof include a methylamino group and an ethylamino group. .

The di (C ₁ -C ₁₀ alkyl) amino group means an (alkyl) ₂ N-group in which the alkyl portion has the above-mentioned meaning, for example, a dimethylamino group, a diethylamino group, a methylethylamino group, a dipropylamino group or A dibutylamino group etc. can be mentioned.

The C ₁ -C ₁₀ alkoxycarbonyl group refers to an (alkyl) -O (C═O) — group having 1 to 10 carbon atoms in which the alkyl portion has the above-mentioned meaning, such as a methoxycarbonyl group, an ethoxycarbonyl group, Examples thereof include an n-propoxycarbonyl group and an isopropoxycarbonyl group.

The C ₁ -C ₆ acyl group, a linear or branched aliphatic acyl group having from 1 to 6 carbon atoms, such as formyl group, acetyl group, propionyl group, isopropionyl group, butyryl group, or pivaloyl group Can be mentioned.

C ₁ -C ₆ acyloxy group means an (acyl) -O— group having 1 to 6 carbon atoms in which the acyl moiety has the above meaning, for example, an acetoxy group, a propionyloxy group, an isopropionyloxy group or a pivaloyloxy group. Etc.

The C ₁ -C ₁₀ alkylthiocarbonyl group means an (alkyl) -S (C═O) — group having 1 to 10 carbon atoms in which the alkyl portion has the above meaning, and examples thereof include a methylthio group or an ethylthio group. I can do things.

C ₁ -C ₄ haloalkylcarbonyl group means a (haloalkyl)-(C═O) — group having 1 to 4 carbon atoms in which the haloalkyl moiety has the above-mentioned meaning, for example, chloroacetyl group, trifluoroacetyl group Group, pentafluoropropionyl group, difluoromethylthio group and the like.

The C ₁ -C ₄ haloalkylthio group means a (haloalkyl) -S— group having 1 to 4 carbon atoms in which the haloalkyl portion has the above meaning, and examples thereof include a difluoromethylthio group and a trifluoromethylthio group. be able to.

The C ₁ -C ₄ haloalkylsulfonyl group means a (haloalkyl) -SO ₂ — group having 1 to 4 carbon atoms in which the haloalkyl portion has the above-mentioned meaning, for example, a chloromethylsulfonyl group, a difluoromethylsulfonyl group or trifluoro A methylsulfonyl group etc. can be mentioned.

The C ₁ -C ₄ haloalkylcarbonyloxy group means a (haloalkyl) C (═O) —O— group having 1 to 4 carbon atoms in which the haloalkyl portion has the above-mentioned meaning, for example, a chloroacetyloxy group, trifluoro An acetyloxy group etc. can be mentioned.

The C ₁ -C ₄ haloalkylsulfonyloxy group means a (haloalkyl) SO ₂ —O— group having 1 to 4 carbon atoms in which the haloalkyl moiety has the above meaning, for example, a chloromethylsulfonyloxy group or a trifluoromethylsulfonyl group. An oxy group etc. can be mentioned.

The mono (C ₁ -C ₁₀ alkyl) carbamoyl group means an (alkyl) NH—C (═O) — group having 1 to 10 carbon atoms in which the alkyl portion has the above-mentioned meaning, for example, methylcarbamoyl group, ethylcarbamoyl group Group or propylcarbamoyl group.

The di (C ₁ -C ₁₀ alkyl) carbamoyl group means an (alkyl) ₂ N—C (═O) — group in which the alkyl portion has the above-mentioned meaning, for example, a dimethylcarbamoyl group, a diethylcarbamoyl group or an ethylmethylcarbamoyl group Etc.

  Phenyl group which may be substituted, benzyloxy group which may be substituted, aromatic heterocyclic group which may be substituted, phenoxy group which may be substituted, aromatic heterocyclic oxy which may be substituted Group, optionally substituted phenylthio group, optionally substituted aromatic heterocyclic thio group, optionally substituted phenylsulfonyl group, optionally substituted phenylsulfonyloxy group, optionally substituted Good aromatic heterocyclic sulfonyl group, optionally substituted benzylcarbonyl group, optionally substituted benzylcarbonyloxy group, optionally substituted benzylsulfonyl group, optionally substituted benzoyl group, substituted Benzoyloxy group which may be substituted, benzyloxycarbonyl group which may be substituted or substituted The “optionally substituted group” in the phenoxycarbonyl group may be a halogen atom, alkyl group, haloalkyl group, alkoxyalkyl group, alkoxy group, alkylthio group, alkylsulfonyl group, acyl group, alkoxycarbonyl group, cyano group A carbamoyl group (the nitrogen atom of the group may be the same or different and may be substituted with an alkyl group), a nitro group or an amino group (the nitrogen atom of the group is the same or different, an alkyl group, an acyl group, a haloalkyl group) And a substituent such as a carbonyl group, an alkylsulfonyl group or a haloalkylsulfonyl group, which may be substituted.

  An optionally substituted aromatic heterocyclic group, an optionally substituted aromatic heterocyclic oxy group, an optionally substituted aromatic heterocyclic thio group, or an optionally substituted aromatic heterocyclic sulfonyl group The aromatic heterocycle of 5-5-membered group having 1 to 3 heteroatoms arbitrarily selected from a nitrogen atom, an oxygen atom and a sulfur atom, for example, a furyl group, a thienyl group, a pyrrolyl group, a pyrazolyl A group, isoxazolyl group, isothiazolyl group, oxazolyl group, thiazolyl group, imidazolyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrazinyl group, triazinyl group, triazolyl group, oxadiazolyl group or thiadiazolyl group.

  The pharmacologically acceptable salt is a salt or mineral of these groups and a metal or an organic base when a hydroxyl group, a carboxyl group, an amino group or the like is present in the structure of the compound having the general formula [I]. It is a salt with an acid or an organic acid. Here, the metal can include an alkali metal such as sodium or potassium, or an alkaline earth metal such as magnesium or calcium, the organic base can include triethylamine or diisopropylamine, and the mineral acid can be hydrochloric acid or Examples of the organic acid include acetic acid, methanesulfonic acid, and para-toluenesulfonic acid.

  Next, typical compound examples of the compound of the present invention represented by the general formula [I] are shown in Tables 1 to 13. However, the compound of the present invention is not limited to these.

The following notations in the tables in the present specification represent the corresponding groups as follows.
Me: methyl group Et: ethyl group,
Pr: n-propyl group Pr-i: isopropyl group Pr-c: cyclopropyl group (4-Cl) Ph: 4-chlorophenyl group When the compound of the present invention contains a hydroxyl group as a substituent, the keto-enol isomer is selected. There are compounds that have. Furthermore, in the double bond in the compound of the present invention, either E or Z isomer can be represented, and a mixture of both isomers can also be represented.

  General formula [I] which is this invention compound can be manufactured in accordance with the manufacturing method shown below, However, It is not limited to these methods.

  <Production Method 1> Step 1 to Step 5

(Wherein R ¹ , R ² , R ³ , R ⁴ , R ⁵ and Q represent the same meaning as described above, X represents a halogen atom, R ⁶ represents a C ₁ -C ₄ alkyl group, represents also be a benzyl group optionally be also a phenyl group or a substituted, L is a halogen atom, C ₁ -C ₄ alkylsulfonyl group, an optionally substituted phenylsulfonyl group or an optionally substituted benzylsulfonyl group, etc. And Y ⁺ represents a sodium cation, a potassium cation or a base-derived cation.)
Hereinafter, the said manufacturing method is explained in full detail for every process.

(Process 1)
The sulfide derivative represented by the general formula [5] includes a compound represented by the general formula [1] and sodium hydrosulfide or potassium hydrosulfide represented by the general formula [2] in a solvent or in the absence of the solvent. A salt represented by the general formula [3] that can be produced by reacting in the presence or absence of a base under the reaction system in the reaction system, and then a salt represented by the general formula [3] Can be produced by reacting with a halogen derivative represented by the general formula [4] without isolation.

  The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, and preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually completed in 0.5 to 24 hours.

  The amount of the reagent provided for the reaction is 1 to 3 equivalents of the compound represented by the general formula [2] or the compound represented by the general formula [4] with respect to 1 equivalent of the compound represented by the general formula [1]. When an equivalent and a base are used, the base is 0.5 to 3 equivalents.

  Examples of the solvent include ethers such as dioxane or tetrahydrofuran (THF), halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chlorobenzene or dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide (DMF). Or amides such as N-methyl-2-pyrrolidinone, sulfur compounds such as dimethyl sulfoxide (DMSO) or sulfolane, aromatic hydrocarbons such as benzene, toluene or xylene, methanol, ethanol, propanol, isopropanol, butanol or tert- Examples thereof include alcohols such as butanol, ketones such as acetone or 2-butanone, nitriles such as acetonitrile, water, and a mixture thereof.

  Examples of the base include metal hydrides such as sodium hydride, alkali metal amides such as sodium amide or lithium diisopropylamide, organic compounds such as pyridine, triethylamine or 1,8-diazabicyclo [5.4.0] -7-undecene. Bases, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate, Inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate, or metal salts of alcohol such as sodium methoxide or potassium tert-butoxide.

(Process 2)
In the sulfide derivative represented by the general formula [5], the mercaptan derivative represented by the general formula [7] is compared with the compound represented by the general formula [6] in a solvent or in the absence of a solvent (preferably suitable) In a simple solvent) in the presence of a base.

  The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount, etc., but is usually completed in 0.5 to 24 hours.

  The amount of the reagent used for the reaction is 1 to 3 equivalents for the compound represented by the general formula [6] and 0.5 to 3 equivalents for the base with respect to 1 equivalent of the compound represented by the general formula [7]. is there.

  Examples of the solvent include ethers such as diethyl ether, 1,2-dimethoxyethane, dioxane or tetrahydrofuran (THF), halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene or dichlorobenzene, N, Amides such as N-dimethylacetamide, N, N-dimethylformamide (DMF) or N-methyl-2-pyrrolidinone, sulfur compounds such as dimethyl sulfoxide (DMSO) or sulfolane, aromatic hydrocarbons such as benzene, toluene or xylene Alcohols such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, ketones such as acetone or 2-butanone, nitriles such as acetonitrile, water, or a mixture thereof And the like.

  Examples of the base include metal hydrides such as sodium hydride, alkali metal amides such as sodium amide or lithium diisopropylamide, organic compounds such as pyridine, triethylamine or 1,8-diazabicyclo [5.4.0] -7-undecene. Bases, hydroxides of alkali metals such as sodium hydroxide and potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide and magnesium hydroxide, carbonates of alkali metals such as sodium carbonate and potassium carbonate, Inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate, or metal salts of alcohol such as sodium methoxide or potassium tert-butoxide.

(Process 3)
The sulfoxide derivative represented by the general formula [8] can be produced by reacting the sulfide derivative represented by the general formula [5] and an oxidizing agent in a solvent in the presence or absence of a catalyst. .

  The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually completed in 1 hour to 72 hours.

  The amount of the reagent used for the reaction is 0.5 to 3 equivalents for the oxidizing agent and 0.01 to 0.5 equivalents for the catalyst with respect to 1 equivalent of the compound represented by the general formula [5].

  Examples of the solvent include halogenated hydrocarbons such as dichloromethane, chloroform, dichloroethane, carbon tetrachloride, chlorobenzene and dichlorobenzene, ethers such as dioxane, tetrahydrofuran (THF), 1,2-dimethoxyethane and diethyl ether, N, Amides such as N-dimethylacetamide, N, N-dimethylformamide (DMF) or N-methyl-2-pyrrolidinone, alcohols such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, acetone or 2-butanone Ketones such as acetonitrile, nitriles such as acetonitrile, acetic acid, water, or a mixture thereof.

Examples of the oxidizing agent include organic peroxides such as m-chloroperbenzoic acid, performic acid or peracetic acid, oxone (OXONE, trade name of DuPont, 2KHSO ₅ · KHSO ₄ · K ₂ SO ₄ ), hydrogen peroxide And inorganic peroxides such as potassium permanganate or sodium periodate.

  Examples of the catalyst include sodium tungstate.

(Process 4)
The sulfone derivative represented by the general formula [9] can be produced by reacting the sulfoxide derivative represented by the general formula [8] and an oxidizing agent in a solvent in the presence or absence of a catalyst. .

  The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually completed in 1 hour to 72 hours.

The amount of the reagent used for the reaction is 0.5 to 3 equivalents of the oxidizing agent and 0.01 to 0 of the catalyst when Q is Q ^{1 with} respect to 1 equivalent of the compound represented by the general formula [8]. .5 is equivalent, when Q is ^{Q 2,} the oxidizing agent is 0.5 to 5 equivalents, the catalyst is 0.01 to 0.5 equivalents.

  Examples of the solvent, the oxidizing agent, and the catalyst include the same ones as in step 3.

(Process 5)
The sulfone derivative represented by the general formula [9] is represented by the general formula [8] depending on the amount of the sulfide derivative represented by the general formula [5] and a suitable oxidizing agent in the presence or absence of a catalyst in a solvent. It can manufacture without isolating the sulfoxide derivative represented by these.

  The reaction temperature is any temperature from 0 ° C. to the reflux temperature in the reaction system, preferably in the temperature range of 0 ° C. to 100 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually completed in 1 hour to 72 hours.

The amount of the reagent used for the reaction is 0.5 to 3 equivalents of the oxidizing agent and 0.01 to 0 of the catalyst when Q is Q ^{1 with} respect to 1 equivalent of the compound represented by the general formula [5]. .5 is equivalent, when Q is ^{Q 2,} the oxidizing agent is 0.5 to 5 equivalents, the catalyst is 0.01 to 0.5 equivalents.
It is.

  Examples of the solvent, the oxidizing agent, and the catalyst include the same ones as in step 3.

<Production Method 2> Step 6 to Step 8
The compound represented by the general formula [4] can be produced by the following method.

(Wherein R ³ , R ⁴ , R ⁵ and X represent the same meaning as described above, and R ⁷ represents an alkyl group.)
(Step 6)
The compound represented by the general formula [11] can be produced by reacting the compound [10] with a Wittig reagent in the presence or absence of a base in a solvent. This reaction is usually at a reaction temperature of −60 to 150 ° C.

  The reaction time varies depending on the reaction temperature, reaction substrate, reaction amount and the like, but is usually completed in 10 minutes to 24 hours.

  The amount of the reagent used in the reaction is preferably 0.5 to 3 equivalents of base and 0.5 to 3 equivalents of Wittig reagent with respect to 1 equivalent of compound [10]. Can be changed.

  Examples of the base include metal hydrides such as sodium hydride, alkali metal amides such as sodium amide or lithium diisopropylamide, organic compounds such as pyridine, triethylamine or 1,8-diazabicyclo [5.4.0] -7-undecene. Bases, hydroxides of alkali metals such as sodium hydroxide or potassium hydroxide, hydroxides of alkaline earth metals such as calcium hydroxide or magnesium hydroxide, carbonates of alkali metals such as sodium carbonate or potassium carbonate, Alternatively, inorganic bases such as alkali metal bicarbonates such as sodium hydrogen carbonate or potassium hydrogen carbonate, alkyl metals such as n-butyl lithium, and metal salts of alcohol such as sodium methoxide or potassium tert-butoxide.

  Examples of the solvent include ethers such as diethyl ether, 1,2-dimethoxyethane, dioxane or tetrahydrofuran (THF), halogenated hydrocarbons such as dichloromethane, chloroform, carbon tetrachloride, dichloroethane, chlorobenzene or dichlorobenzene, N, Amides such as N-dimethylacetamide, N, N-dimethylformamide (DMF) or N-methyl-2-pyrrolidinone, sulfur compounds such as dimethyl sulfoxide (DMSO) or sulfolane, aromatic hydrocarbons such as benzene, toluene or xylene , Alcohols such as methanol, ethanol, propanol, isopropanol, butanol or tert-butanol, nitriles such as acetonitrile, water, or a mixture thereof.

  As the Wittig reagent, a commercially available reagent may be used as it is, but the method described in Maruzen Co., Ltd., Experimental Chemistry Course (4th edition), Vol. 19, Organic Synthesis I, pages 57-72 or It can be produced by a similar method.

  As the compound represented by the general formula [10], a commercially available reagent may be used as it is, but the Journal of Organic Chemistry (J. Org. Chem.) Volume 60 (8), page 2461 ( 1995), Tetrahedron Letters, 375 (1978), 3539 (1980), and 7303 (1994), Synth. Commun., 11 (12), 943 (1981), Synthesis 9, 241 (1998), Tetrahedron 52 (42), 13513 (1996) and Journal of Medicinal Chemistry (J. Med). Chem.,) 24 (4), 399 (1981), or a method analogous thereto.

(Step 7)
The compound represented by the general formula [12] can be produced by reacting the compound [11] with a reducing agent in a solvent.

  This reaction is usually carried out at a reaction temperature of −60 to 150 ° C. for 10 minutes to 24 hours.

  The amount of the reagent used for the reaction is preferably 0.5 to 2 equivalents of the reducing agent with respect to 1 equivalent of the compound [11], but can be arbitrarily changed depending on the reaction conditions.

  Examples of the reducing agent in the production of [11] to [12] include metal hydrides such as diisobutylaluminum hydride, metal hydride complex compounds such as sodium borohydride or lithium aluminum hydride, and diborane. .

  Examples of the solvent include ethers such as diethyl ether, tetrahydrofuran or dioxane, aromatic hydrocarbons such as benzene or toluene, or alcohols such as methanol or ethanol.

(Process 8)
In the compound represented by the general formula [4], the compound [12] is reacted with a halogenating agent in a solvent, or the compound [12] is reacted with carbon tetrabromide or carbon tetrachloride and triphenylphosphine in a solvent. It can be produced by reacting.

  This reaction is usually carried out at a reaction temperature of −50 to 100 ° C. for 10 minutes to 24 hours.

  The amount of the reagent used for the reaction is preferably 1 to 3 equivalents of the halogenating agent, 1 to 3 equivalents of carbon tetrabromide or carbon tetrachloride, and 1 to 3 equivalents of triphenylphosphine with respect to 1 equivalent of the compound [12]. , And can be arbitrarily changed according to the reaction situation.

  Examples of the halogenating agent include hydrogen chloride, hydrogen bromide, phosphorus trichloride, phosphorus tribromide, thionyl chloride, and the like.

Examples of the solvent include halogenated hydrocarbons such as dichloroethane and carbon tetrachloride, acids such as acetic acid, and ethers such as tetrahydrofuran.
<Production Method 3> Step 9
The compound represented by the general formula [4] can also be produced by the following method.

(In the formula, R ³ , R ⁴ , R ⁵ and X have the same meaning as described above.)
The compound represented by the general formula [4] can be produced by reacting the compound [13] with a halogenating agent in a solvent in the presence or absence of a catalyst.

  This reaction is usually carried out at a reaction temperature of 30 to 150 ° C. for 10 minutes to 24 hours.

  The amount of the reagent provided for the reaction is preferably 1 to 10 equivalents of the halogenating agent with respect to 1 equivalent of the compound [13], but can be arbitrarily changed depending on the reaction conditions. 0.5 equivalent.

  Examples of the halogenating agent include halogens such as bromine or chlorine, N-halosuccinimides such as N-bromosuccinimide, pyridine salts such as pyridinium perbromide, or 1,3-dibromo-5,5- Examples thereof include dimethylhydantoin.

  Examples of the solvent include halogenated hydrocarbons such as dichloroethane, carbon tetrachloride, chlorobenzene and dichlorobenzene, amides such as N, N-dimethylacetamide, N, N-dimethylformamide (DMF) and N-methyl-2-pyrrolidinone. And sulfur compounds such as dimethyl sulfoxide (DMSO) or sulfolane, or carboxylic acids such as formic acid or acetic acid.

  Examples of the catalyst include peroxides such as benzoyl peroxide, nitriles such as α, α-azobisisobutyronitrile, and mixtures thereof.

  The compound represented by the general formula [13] may be a commercially available reagent as it is, but is produced from the corresponding ketone body by carrying out the Wittig reaction described in Step 6 of Production Method 2. be able to.

  The herbicide of the present invention comprises an isoxazolin-3-yl derivative represented by the general formula [I] or a pharmacologically acceptable salt thereof as an active ingredient.

  In order to use the compound of the present invention as a herbicide, the compound of the present invention may be used as it is, but a carrier, a surfactant, a dispersing agent or an auxiliary agent generally used for formulation is blended, and a powder, It can also be used in the form of a wettable powder, emulsion, flowable, fine granules or granules.

  Examples of carriers used for formulation include talc, bentonite, clay, kaolin, diatomaceous earth, white carbon, vermiculite, calcium carbonate, slaked lime, silica sand, ammonium sulfate, urea and other solid carriers, isopropyl alcohol, xylene, cyclohexane or methylnaphthalene, etc. Liquid carriers and the like.

  Surfactants and dispersants include, for example, alkylbenzene sulfonic acid metal salts, dinaphthylmethane disulfonic acid metal salts, alcohol sulfate esters, alkylaryl sulfonates, lignin sulfonates, polyoxyethylene glycol ethers, polyoxyethylene alkyls. Examples thereof include aryl ether and polyoxyethylene sorbitan monoalkylate. Examples of the auxiliary agent include carboxymethyl cellulose, polyethylene glycol, gum arabic and the like. In use, dilute to an appropriate concentration and spray or apply directly.

  The herbicide of the present invention can be used by foliage application, soil application or water surface application. The blending ratio of the active ingredient is appropriately selected as necessary, but in the case of powder or granule, it is appropriately selected from the range of 0.01 to 10% (weight), preferably 0.05 to 5% (weight). It is good. In the case of using an emulsion and a wettable powder, it may be appropriately selected from the range of 1 to 50% (weight), preferably 5 to 30% (weight). Moreover, when setting it as a flowable agent, it is good to select suitably from the range of 1-40% (weight), Preferably 5-30% (weight).

  The application rate of the herbicide of the present invention varies depending on the type of compound used, the target weed, the tendency to occur, the environmental conditions and the dosage form to be used, but when used as it is like powders and granules, as an active ingredient It is appropriate to appropriately select from 1 g to 50 kg per hectare, preferably from 10 g to 10 kg. In addition, when used in a liquid state as in the case of emulsions, wettable powders and flowables, it may be appropriately selected from the range of 0.1 to 50,000 ppm, preferably 10 to 10,000 ppm.

  In addition, the herbicide of the present invention includes other known active compounds as required in addition to the compound of the present invention which is an active ingredient in the above various preparation forms, for example, insecticides, acaricides, insect growth regulators, You may mix with a nematicide, a fungicide, a herbicide, a plant growth regulator, a fertilizer, and soil improvement.

  The compound of the present invention represented by the general formula [I] is a variety of weeds that are problematic in the field, for example, broad-leaved weeds such as giant beetle, greenfish, shiroza, chickweed, tiger beetle, American stag beetle, American horned scorpion, morning glory, bat Perennial and annual perennial cyperaceae weeds such as japonica, yellowtail, cyper, and white-tailed crustaceae, flies from pre-emergence weeds of grasses such as Japanese maize, Japanese barnyardgrass, wild stag beetle, Johnsongrass, Japanese genus Teppo, wild oats, etc. Excellent herbicidal effect over a wide range. It is also possible to control annual weeds such as Tainubie, Tamagayatsuri, and Konagi that occur in paddy fields, and perennial weeds such as Urikawa, Omodaka, Mitsugayatsuri, Krogwei, Firefly, Heramodaka.

  Next, the production method, formulation method and use of the compound of the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples. In addition, the manufacturing method of the manufacturing intermediate of this invention compound is also described collectively. The compound number is referred to in the following description.

Synthesis of 3- (3-methyl-2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 001)
(1) Synthesis of ethyl 3-methyl-2-phenyl-2-butenoate 11.2 ml of n-butyllithium in a solution of 6.92 g (17.9 mmol) of isopropyltriphenylphosphonium bromide in 40 ml of tetrahydrofuran at 0 ° C. (17.9 mmol, 1.60 mol / L, n-hexane solution) was added and stirred at the same temperature for 30 minutes. Further, 3.20 g (17.9 mmol) of ethyl 2-oxo-2-phenylacetate was added to the reaction solution and stirred overnight at room temperature. After confirming the completion of the reaction, the solvent in the reaction solution was distilled off under reduced pressure. The obtained residue was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 1.32 g (yield: 36%) of ethyl 3-methyl-2-phenyl-2-butenoate.

(2) Synthesis of 3-methyl-2-phenyl-2-buten-1-ol To a solution of ethyl 3-methyl-2-phenyl-2-butenoate (1.32 g, 6.50 mmol) in tetrahydrofuran (10 ml) at room temperature. Then, 0.24 g (6.50 mmol) of lithium aluminum hydride was added, and the mixture was stirred at the same temperature for 3 hours. After confirming the completion of the reaction, water and an aqueous sodium hydroxide solution were added to the reaction solution, and insoluble matters were filtered off. The filtrate was separated, and the organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.80 g (yield: 76%) of 3-methyl-2-phenyl-2-buten-1-ol.

(3) Synthesis of 1- (1-bromo-3-methyl-2-buten-2-yl) -benzene 3-methyl-2-phenyl-2-buten-1-ol 0.80 g (5.00 mmol) To 10 ml of diethyl ether was added 0.45 g (1.65 mmol) of phosphorus tribromide at room temperature, and the mixture was stirred at the same temperature for 2 hours. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure to obtain 1.02 g (yield: 91%) of 1- (1-bromo-3-methyl-2-buten-2-yl) -benzene.

(4) Synthesis of 3- (3-methyl-2-phenyl-2-butenylthio) -5,5-dimethyl-2-isoxazoline 5,5-dimethyl-3-ethanesulfonyl-2-isoxazoline 0.86 g ( To a solution of 4.50 mmol) of N, N-dimethylformamide at room temperature was added 0.34 g of sodium hydrosulfide (purity 70%, 6.10 mmol) and 0.81 g (10.60 mmol) of anhydrous potassium carbonate. Stir for 1 hour. Further, 1.02 g (4.50 mmol) of 1- (1-bromo-3-methyl-2-buten-2-yl) -benzene was added at room temperature and stirred for 1 hour. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 0.67 g (yield: 54%) of 3- (3-methyl-2-phenyl-2-butenylthio) -5,5-dimethyl-2-isoxazoline. Got.

(5) Synthesis of 3- (3-methyl-2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline 3- (3-methyl-2-phenyl-2-butenylsulfonyl) To a solution of 0.16 g (0.58 mmol) of -5,5-dimethyl-2-isoxazoline in 5.0 ml of methanol and 5.0 ml of water was added 0.53 g (0.87 mmol) of oxone at room temperature. Stir. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and colorless crystals of 3- (3-methyl-2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (0.08 g (yield) were obtained. Rate: 45%).

¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.40 to 7.18 (m, 5H), 4.50 (s, 2H), 2.80 (s, 2H), 2.03 (S, 3H), 1.72 (s, 3H), 1.34 (s, 6H)
Melting point: 101-103 ° C

Synthesis of 3-((3,3-dimethyl-2-phenyloxiran-2-yl) methylsulfonyl) -5,5-dimethyl-2-isoxazoline (present compound number 002)
To a solution of 0.32 g (1.16 mmol) 3- (3-methyl-2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline in 5.0 ml methanol and 5.0 ml water, 1.83 g (3.00 mmol) of oxone was added at room temperature and stirred for 3 hours. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the solvent was evaporated under reduced pressure to give colorless crystals of 3-((3,3-dimethyl-2-phenyloxiran-2-yl) methylsulfonyl) -5,5-dimethyl-2-iso 0.28 g (yield: 75%) of oxazoline was obtained.

¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.37 to 7.28 (m, 5H), 4.15 (d, 1H), 4.01 (d, 1H), 3.06 (D, 1H), 2.78 (d, 1H), 1.56 (s, 3H), 1.43 (s, 3H), 1.39 (s, 3H), 0.99 (s, 3H)
Melting point: 126-127 ° C

Synthesis of 3- [3-methyl-2- (2-chlorophenyl) -2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (present compound number 003)
(1) Synthesis of ethyl 2- (2-chlorophenyl) -3-methyl-2-butenoate To a solution of 0.90 g (2.1 mmol) of isopropyltriphenylphosphonium iodide in 4.0 ml of tetrahydrofuran at −60 ° C. 1.3 ml of n-butyllithium (2.1 mmol, 1.58 mol / L, n-hexane solution) was added, and the mixture was stirred at the same temperature for 1 hour. Furthermore, 0.37 g (1.74 mmol) of ethyl 2- (2-chlorophenyl) -2-oxoacetate was added to the reaction solution, and the mixture was stirred at the same temperature for 1 hour. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.27 g (yield: 65%) of ethyl 2- (2-chlorophenyl) -3-methyl-2-butenoate.

(2) Synthesis of 2- (2-chlorophenyl) -3-methyl-2-buten-1-ol 0.27 g (1.13 mmol) of ethyl 2- (2-chlorophenyl) -3-methyl-2-butenoate To a 3.0 ml tetrahydrofuran solution was added 3.7 ml (3.40 mmol, 0.93 mol / L, toluene solution) of isobutylaluminum hydride at −50 ° C., and the mixture was stirred at the same temperature for 1 hour. After confirming the completion of the reaction, the reaction solution was poured into ice water, neutralized with concentrated hydrochloric acid, and extracted with diethyl ether. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. The insoluble material was filtered off and the next reaction was carried out as it was.

(3) Synthesis of 1- (1-bromo-3-methyl-2-buten-2-yl) -2-chlorobenzene Crude 2- (2-chlorophenyl) -3-methyl-2 obtained in (2) -To a diethyl ether solution of buten-1-ol, 0.46 g (1.70 mmol) of phosphorus tribromide was added at -20 ° C, and the mixture was stirred at the same temperature for 1 hour. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with diethyl ether. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matters were filtered off, and the solvent was distilled off under reduced pressure to obtain crude 1- (1-bromo-3-methyl-2-buten-2-yl) -2-chlorobenzene.

(4) Synthesis of 3- [2- (2-chlorophenyl) -3-methyl-2-butenylthio] -5,5-dimethyl-2-isoxazoline 5,5-dimethyl-3-ethanesulfonyl-2-isoxazoline To a solution of 0.22 g (1.13 mmol) of N, N-dimethylformamide in 2.0 ml at room temperature, sodium hydrosulfide 0.09 g (purity 70%, 1.13 mmol) and anhydrous potassium carbonate 0.19 g (1 .36 mmol) and Rongalit (HOCH ₂ SO ₂ Na.2H ₂ O) 0.21 g (1.36 mmol) were added and stirred for 1 hour. Furthermore, the crude 1- (1-bromo-3-methyl-2-buten-2-yl) -2-chlorobenzene obtained in 3) was added at room temperature and stirred for 30 minutes. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 3- [2- (2-chlorophenyl) -3-methyl-2-butenylthio] -5,5-dimethyl-2-isoxazoline (0.12 g, yield) : 34%).

(5) Synthesis of 3- [2- (2-chlorophenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline 3- [2- (2-chlorophenyl) -3- Methyl-2-butenylthio] -5,5-dimethyl-2-isoxazoline (0.12 g, 0.39 mmol) in methanol (5.0 ml) at room temperature with sodium tungstate dihydrate catalyst amount and hydrogen peroxide 0.19 g of water (purity 35%, 1.95 mmol) was added and stirred overnight. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with dichloromethane. Further, the aqueous layer was extracted with ethyl acetate. Each of the obtained organic layers was washed with water and dried over anhydrous magnesium sulfate. The insoluble material was filtered off, and the solvent was evaporated under reduced pressure to give colorless crystals of 3- [2- (2-chlorophenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline 0 .11 g (yield: 83%) was obtained.

¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.41 to 7.20 (m, 4H), 4.63 (d, 1H), 4.36 (d, 1H), 2.95 (D, 2H), 2.05 (s, 3H), 1.63 (s, 3H), 1.40 (d, 6H)
Melting point: 82-83 ° C

Synthesis of methyl (2Z) -4- (5,5-dimethylisoxazolin-3-ylsulfonyl) -3-phenyl-2-butenoate (Compound No. 004 of the present invention)
(1) Synthesis of methyl (2Z) -3-phenyl-2-butenoate In a 25 ml toluene solution of 2.00 g (16.7 mmol) of acetophenone, 6.12 g (18. 3 mmol) was added and stirred under reflux for 3 days. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography to obtain 0.44 g (yield: 14%) of methyl (2Z) -3-phenyl-2-butenoate.

(2) Synthesis of methyl (2Z) -3-bromomethyl-2-phenyl-2-butenoate 0.42 g (2.32 mmol) of methyl (2Z) -3-phenyl-2-butenoate in 10 ml of carbon tetrachloride To this, 0.41 g (2.32 mmol) of N-bromosuccinimide was added at room temperature, and the mixture was stirred under reflux for 5 hours. After confirming the completion of the reaction, insoluble matters were filtered off, and the solvent was distilled off under reduced pressure. The obtained crude methyl (2Z) -3-bromomethyl-2-phenyl-2-butenoate was used as such for the next reaction.

(3) Synthesis of methyl (2Z) -4- (5,5-dimethylisoxazolin-3-ylthio) -3-phenyl-2-butenoate 5,5-dimethyl-3-ethanesulfonyl-2-isoxazoline 0 .44 g (2.32 mmol) of N, N-dimethylformamide in 5.0 ml solution at room temperature 0.19 g of sodium hydrosulfide (purity 70%, 2.32 mmol) and 0.38 g of anhydrous potassium carbonate (2. 72 mmol) was added and stirred for 1 hour. Further, the crude methyl 3-bromomethyl-2-phenyl-2-butenoate obtained in 2) was added at room temperature and stirred for 30 minutes. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with ethyl acetate. The obtained organic layer was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure. The obtained residue was purified by silica gel column chromatography, and 0.31 g of methyl (2Z) -4- (5,5-dimethylisoxazolin-3-ylthio) -3-phenyl-2-butenoate (yield: 44%).

(4) Synthesis of methyl (2Z) -4- (5,5-dimethylisoxazolin-3-ylsulfonyl) -3-phenyl-2-butenoate (2Z) -4- (5,5-dimethylisoxazoline- To a solution of 0.31 g (1.02 mmol) of methyl 3-ylthio) -3-phenyl-2-butenoate in 5.0 ml of methanol, a sodium tungstate dihydrate catalyst amount and a hydrogen peroxide solution of 0. 51 g (purity 35%, 5.10 mmol) was added and stirred overnight. After confirming the completion of the reaction, the reaction solution was poured into ice water and extracted with dichloromethane. Further, the aqueous layer was extracted with ethyl acetate. Each of the obtained organic layers was washed with water and dried over anhydrous magnesium sulfate. Insoluble matter was filtered off, and the solvent was distilled off under reduced pressure to give 0.23 g of methyl (2Z) -4- (5,5-dimethylisoxazolin-3-ylsulfonyl) -3-phenyl-2-butenoate as colorless crystals. (Yield: 67%) was obtained.

¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.54 to 7.42 (m, 5H), 6.44 (s, 1H), 5.36 (s, 2H), 3.80 (S, 3H), 2.99 (s, 3H), 1.40 (d, 6H)
Melting point: 107-108 ° C

Synthesis of 3- (allylsulfonyl) -5,5-dimethyl-2-isoxazoline (present compound number 005)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 5.92 (m, 1H), 5.54 (m, 2H), 4.09 (d, 2H), 3.09 (s, 1H ), 1.49 (s, 6H)
Melting point: 64-65 ° C

3-((E) -2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 006)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 6.07 to 5.89 (m, 1H), 5.59 to 5.48 (m, 1H), 4.14 to 4.11 ( dd, 2H), 3.08 (d, 2H), 1.80 (dd, 3H), 1.49 (s, 6H)

3- (cinnamylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 007)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.43 to 7.30 (m, 5H), 6.76 (d, 1H), 6.26 to 6.18 (m, 1H) , 4.24 (d, 2H), 3.07 (s, 2H), 1.46 (s, 6H)
Melting point: 145-146 ° C

3-((E) -4,4,4-trifluoro-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 008)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 6.43 (m, 1H), 6.07 (m, 1H), 4.20 (d, 2H), 3.09 (s, 2H) ), 1.50 (s, 6H)
Melting point: 111-112 ° C

3- [2- (3-Chlorophenyl) -allylsulfonyl] -5,5-dimethyl-2-isoxazoline (the present compound number 009)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.61 (s, 1H), 7.46 to 7.30 (m, 3H), 5.84 (s, 1H), 5.50 (S, 1H), 4.51 (s, 2H), 3.06 (s, 2H), 1.43 (s, 6H)
Refractive index (n ^D ₂₀ ): 1.5641

3- [2- (4-Chlorophenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (present compound number 010)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.31 (d, 2H), 7.14 (d, 2H), 4.48 (s, 2H), 2.88 (s, 2H) ), 2.02 (s, 3H), 1.71 (s, 3H), 1.38 (s, 6H)
Refractive index (n ^D ₂₀ ): 1.5420

3- [2- (2-Fluorophenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (present compound number 011)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.33 to 7.03 (m, 4H), 4.49 (s, 2H), 2.92 (s, 2H), 2.04 (S, 3H), 1.71 (s, 3H), 1.39 (s, 6H)
Refractive index (n ^D ₂₀ ): 1.5248

3- [2- (3-Chlorophenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (the present compound number 012)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.31 to 7.19 (m, 3H), 7.10 (d, 1H), 4.48 (s, 2H), 2.91 (S, 2H), 2.02 (s, 3H), 1.72 (s, 3H), 1.39 (s, 6H)

3- [3-Methyl-2- (2-trifluoromethylphenyl) -2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (present compound number 013)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.67 (d, 1H), 7.56 to 7.38 (m, 2H), 4.74 (d, 1H), 4.17 (D, 1H), 3.02 (s, 2H), 2.04 (s, 3H), 1.53 (s, 3H), 1.42 (d, 6H)
Melting point: 87-88 ° C

3- [2- (2-Ethoxyphenyl) -3-methyl-2-butenylsulfonyl] -5,5-dimethyl-2-isoxazoline (present compound number 014)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.22 (d, 1H), 7.12 (d, 1H), 6.90 (m, 2H), 4.57 (d, 2H) ), 4.04 (m, 2H), 2.74 (s, 2H), 2.02 (s, 3H), 1.70 (s, 3H), 1.38 (t, 3H), 1.32 (D, 6H)
Melting point: 112-113 ° C

3- {2- [2- (2,2,2-trifluoroethoxy) phenyl] -3-methyl-2-butenylsulfonyl} -5,5-dimethyl-2-isoxazoline (present compound number 015)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.28 (m, 1H), 7.22 (d, 1H), 7.05 (t, 1H), 6.86 (d, 1H ), 4.51 (q, 2H), 4.34 (q, 2H), 2.84 (s, 2H), 2.02 (s, 3H), 1.67 (s, 3H), 1.32 (D, 6H)
Melting point: 84-85 ° C

3- (2-cyclohexyl-3-methyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 016)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 4.30 (s, 2H), 3.12 (s, 2H), 2.51 (m, 1H), 1.84 to 1.19 (M, 22H)
Melting point: 52-54 ° C

3-((Z) -2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 017)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.40 to 7.24 (m, 5H), 6.33 (q, 1H), 4.61 (s, 2H), 2.83 (S, 2H), 2.00 (d, 3H), 1.32 (s, 6H)

3-((E) -2-phenyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 018)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.41 to 7.24 (m, 5H), 6.11 (q, 1H), 4.38 (s, 2H), 2.85 (S, 2H), 1.75 (d, 3H), 1.36 (s, 6H)
Melting point: 80-81 ° C

3-((EZ) -2-phenyl-2-pentenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 019)
Melting point: 54-57 ° C

3- (2-Phenyl-2-hexenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 020)
Melting point: 37-38 ° C

3-((Z) -2,3-diphenylallylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 021)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.52 to 7.32 (m, 10H), 7.16 (s, 1H), 4.81 (s, 2H), 2.67 (S, 2H), 1.29 (s, 6H)
Melting point: 123-125 ° C

3-((E) -2,3-diphenylallylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 022)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 7.32 to 6.99 (m, 10H), 6.88 (s, 1H), 4.53 (s, 2H), 2.91 (S, 2H), 1.38 (s, 6H)
Melting point: 152-154 ° C

3- (3-Methyl-2-phenyl-2-pentenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 023)
Refractive index (n ^D ₂₀ ): 1.5365

3- (2-Methyl-3-phenylallylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 024)
Refractive index (n ^D ₂₀ ): 1.5441

(2Z) -4-[(5,5-Dimethylisoxazolin-3-ylsulfonyl) methyl] -3-phenylacrylate (present invention compound number 025)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 8.14 (s, 1H), 7.63 to 7.42 (m, 5H), 4.62 (s, 2H), 4.31 (M, 2H), 3.14 (s, 2H), 1.51 (s, 6H), 1.37 (t, 3H)
Melting point: 125-127 ° C

3-((2E, 4E) -2,4-hexadienylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 026)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 6.34 (m, 1H), 6.10 (m, 1H), 5.84 (m, 1H), 5.54 (m, 1H) ), 4.07 (d, 2H), 3.06 (s, 1H), 1.78 (d, 3H), 1.47 (s, 6H)
Melting point: 48-51 ° C

3- (3-Methyl-2-butenylsulfonyl) -5,5-dimethyl-2-isoxazoline (the present compound number 027)
¹ H-NMR value (CDCl ₃ / TMS δ (ppm)): 5.30 (m, 1H), 4.08 (d, 2H), 3.08 (s, 2H), 1.84 (s, 3H) ), 1.76 (s, 3H), 1.49 (s, 6H)
Melting point: 33-35 ° C
Next, the preparation method will be specifically described with reference to typical preparation examples. The types and compounding ratios of the compounds and additives are not limited to these and can be changed in a wide range. In the following description, “parts” means parts by weight.

Wettable agent 10 parts of Compound No. 1 of the present invention are 0.5 parts of polyoxyethylene octylphenyl ether, 0.5 parts of β-naphthalenesulfonic acid formalin condensate sodium salt, 13 parts of diatomaceous earth, and 69 parts of clay. The mixture was pulverized to obtain a wettable powder.

Flowable Agent 13 parts of Compound No. 1 of the present invention are dispersed in 69 parts of water, 4 parts of polyoxyethylene styrenated phenyl ether sulfate and 7 parts of ethylene glycol are added, and silicone AF-111N (Asahi Kasei Kogyo Co., Ltd.) is formulated. 130 ppm was added to the mixture, mixed for 30 minutes with a high-speed stirrer, and then pulverized with a wet pulverizer to obtain a flowable agent.

Emulsion 60 parts of an equivalent mixture of xylene and isophorone, 10 parts of a mixture of surfactant polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl polymer and alkylaryl sulfonate were added to 30 parts of the compound No. 1 of the present invention. An emulsion was obtained by stirring well.

Granules 10 parts of Compound No. 1 of the present invention, 80 parts of extender in which talc and bentonite are mixed at a ratio of 1: 3, 5 parts of white carbon, surfactant polyoxyethylene sorbitan alkylate, polyoxyethylene alkylaryl 10 parts of water was added to 5 parts of the mixture of polymer and alkylaryl sulfonate, and the mixture was well kneaded into a paste to be extruded through a sieve hole with a diameter of 0.7 mm, dried, and then cut to a length of 0.5 to 1 mm. And obtained granules.

  Next, effects of the compound of the present invention will be described with reference to test examples.

<Test example 1> Herbicidal effect test by paddy field soil treatment Paddy field soil was filled in a 100 cm ² plastic pot, and after seeding, Tainubie and Konagi seeds were sown and submerged to a depth of 3 cm. The next day, the wettable powder prepared according to Example 28 was diluted with water and dropped on the surface of the water. The application rate was 1000 g per hectare of active ingredient. Then, it grew in the greenhouse and investigated the herbicidal effect according to the criteria of Table 14 on the 21st day after the treatment. The results are shown in Table 15.

<Test Example 2> Herbicidal effect test by field soil treatment An 80 cm ² plastic pot was filled with field soil, and seeds of Inobiae and Enokorogusa were sown and covered with soil. The wettable powder prepared according to Example 28 was diluted with water, and 1000 l per hectare was uniformly sprayed on the soil surface with a small sprayer so that the active ingredient was 1000 g per hectare. Then, it grew in the greenhouse and investigated the herbicidal effect according to the criteria of Table 14 on the 21st day of treatment. The results are shown in Table 16.

<Test Example 3> Herbicidal effect test by upland foliage treatment 80 cm ² plastic pot is filled with sand, seeds of Inobiae and Enokorogusa are sown, grown in a greenhouse for 2 weeks, and prepared in accordance with Example 28 Was diluted with water, and 1000 l per hectare was sprayed onto the whole plant from above with a small sprayer so that the active ingredient was 1000 g per hectare. Then, it grew in the greenhouse and investigated the herbicidal effect according to the standard of Table 14 on the 14th day of treatment. The results are shown in Table 17.

Claims (2)

Isoxazolin-3-yl derivatives having the general formula [I] or pharmacologically acceptable salts thereof:

In the formula, R ¹ and R ² are each independently a hydrogen atom, a halogen atom, a C ₁ -C ₁₀ alkyl group, a C ₃ -C ₈ cycloalkyl group, a C ₂ -C ₆ alkenyl group, or a C ₂ -C. ₆ alkynyl group, C ₁ -C ₁₀ haloalkyl group, C ₁ -C ₁₀ alkoxy group, phenyl group optionally substituted by substituent group α, —C (═O) —Z—R ⁶ group, cyano group, C ₁ -C ₁₀ alkylthio group, C ₁ -C ₁₀ alkylsulfinyl group or C ₁ -C ₁₀ alkylsulfonyl group, and R ¹ and R ² together with these bonded carbon atoms are C ₃ -C ₇ carbocycles May form,
Q represents a formula ^{Q 1} group or wherein ^{Q 2} group,

R ³ is a hydrogen atom, a halogen atom, a C _{1 to} C ₁₀ alkyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{2 to} C ₆ alkenyl group, a C _{2 to} C ₆ alkynyl group, or a C _{1 to} C ₁₀ haloalkyl group. Represents a phenyl group which may be substituted with a substituent group α, a heterocyclic group which may be substituted with a substituent group α, a —C (═O) —Z—R ⁶ group or a —ZR ⁶ group. ,
R ⁴ and R ⁵ are each independently a hydrogen atom, a C ₁ -C ₁₀ alkyl group optionally substituted with a substituent group β, a C ₂ -C ₆ alkenyl group, a C ₂ -C ₆ alkynyl group, C ₃ -C ₈ cycloalkyl _group, C 1 _{-C 10} alkoxycarbonyl group, -C (= O) -Z- R 6 _group, C 1 _{-C 10} alkyl thio group, which may be a carboxyl group or a substituted phenyl Represents a group,
R ⁴ and R ⁵ together with these bonded carbon atoms may form a C _{3 to} C ₇ carbocycle,
Z represents O, S or NR ⁷ ;
R ⁶ and R ⁷ are each independently a hydrogen atom, a C _{1 to} C ₁₀ alkyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{2 to} C ₆ alkenyl group, a C _{2 to} C ₆ alkynyl group, or C _1. -C represents ₁₀ haloalkyl _group, C 1 _{-C 10} alkoxy group or substituted with a substituent group α which may be a phenyl group,
n shows the integer of 0-2.
`` Substituent group α ''
A hydroxyl group, a halogen _atom, C 1 _{-C 10} alkyl groups, mono-substituted with a substituent group γ the _C 1 _{-C 10} alkyl _group, C 1 -C ₄ haloalkyl _groups, C 3 -C ₈ cycloalkyl _{group, C} 1 ~ C ₁₀ alkoxy group, C ₁ -C ₁₀ alkoxy group monosubstituted by substituent group δ, C ₁ -C ₄ haloalkoxy group, C ₃ -C ₈ cycloalkyloxy group, C ₃ -C ₈ cycloalkyl C ₁ -C ₃ alkyloxy _groups, C 1 _{-C 10} alkylthio group, mono-substituted with a substituent group δ a _C 1 _{-C 10} alkylthio _groups, C 1 -C ₄ haloalkylthio _groups, C 2 -C ₆ alkenyl groups, C ₂ -C ₆ alkenyloxy _group, C 2 -C ₆ alkynyl _group, C 2 -C ₆ alkynyloxy _group, C 1 _{-C 10} alkylsulfinyl _group, C 1 _{-C 10} alkylsulfonyl group Mono-substituted with a substituent group δ a _C 1 _{-C 10} alkylsulfonyl _group, C 1 -C ₄ haloalkylsulfonyl _group, C 1 _{-C 10} alkylsulfonyloxy _group, C 1 -C ₄ haloalkylsulfonyl group, optionally substituted An optionally substituted phenyl group, an optionally substituted phenoxy group, an optionally substituted phenylthio group, an optionally substituted aromatic heterocyclic group, an optionally substituted aromatic heterocyclic oxy group, a substituted Aromatic heterocyclic thio group which may be substituted, phenylsulfonyl group which may be substituted, aromatic heterocyclic sulfonyl group which may be substituted, phenylsulfonyloxy group which may be substituted, C ₁ -C ₆ acyl group, C ₁ -C ₄ haloalkylcarbonyl group, an optionally substituted benzylcarbonyl group, optionally substituted Which may benzoyl group, carboxyl group, C ₁ -C ₁₀ alkoxycarbonyl group, an optionally substituted benzyloxycarbonyl group, an optionally substituted phenoxycarbonyl group, a cyano group, a nitrogen atom of the carbamoyl group (said group identical or _different, C 1 _{-C 10} alkyl group or may be substituted in a phenyl group optionally _{substituted),} C 1 -C ₆ acyloxy _group, C 1 -C ₄ haloalkylcarbonyl group, optionally substituted Optionally substituted benzylcarbonyloxy group, optionally substituted benzoyloxy group, nitro group, amino group (nitrogen atoms of the group are the same or different, C ₁ -C ₁₀ alkyl group, optionally substituted) phenyl _group, C 1 -C ₆ acyl _group, C 1 -C ₄ haloalkylcarbonyl group, optionally Ben substituted Le carbonyl group, an optionally substituted benzoyl group, C ₁ -C ₁₀ alkylsulfonyl group, C ₁ -C ₄ haloalkylsulfonyl groups, optionally substituted benzylsulfonyl group or an optionally substituted phenylsulfonyl group May be substituted)
"Substituent group β"
1 to 3 halogen atoms that are the same or different, a hydroxyl group, a C _{3 to} C ₈ cycloalkyl group, a C _{1 to} C ₁₀ alkoxy group, a C _{1 to} C ₁₀ alkylcarbonyl group, a C _{1 to} C ₁₀ alkylthio group, C ₁ -C ₁₀ alkylsulfinyl _group, C 1 _{-C 10} alkylsulfonyl _group, C 1 _{-C 10} alkylamino group, di _(C 1 _{-C 10} alkyl) amino group, a cyano _group, C 1 _{-C 10} alkoxycarbonyl group, a carbamoyl Group, mono (C ₁ -C ₁₀ alkyl) carbamoyl group, di (C ₁ -C ₁₀ alkyl) carbamoyl group, C ₁ -C ₁₀ alkylthiocarbonyl group, carboxyl group, optionally substituted benzyloxy group, substituted Optionally substituted phenoxy group or optionally substituted phenyl group "substituent group γ"
_Hydroxyl, C 3 -C ₈ cycloalkyl group (which may be substituted with a halogen atom or a _C 1 -C ₃ alkyl _{group), C} 1 ~C ₁₀ alkoxy _group, C 1 _{-C 10} alkylthio group, _{C 1} -C ₁₀ alkylsulfonyl _group, C 1 _{-C 10} alkoxycarbonyl _group, C 2 -C ₆ haloalkenyl group, the nitrogen atom of the amino group (in which the same or _different, C 1 _{-C 10} alkyl _{group, C} 1 ~ C ₆ acyl group, C ₁ -C ₄ haloalkylcarbonyl group, C ₁ -C ₁₀ alkylsulfonyl group, optionally substituted with C ₁ -C ₄ haloalkylsulfonyl group), mono (C ₁ -C ₁₀ alkyl) carbamoyl group, di _(C 1 _{-C 10} alkyl) carbamoyl group, a carbamoyl _group, C 1 -C ₆ acyl _group, C 1 -C ₄ haloalkylcarbonyl group, _{C 1} C ₁₀ alkoxyimino group, a cyano group, a phenyl group which may be substituted, an optionally substituted phenoxy group "substituent group δ"
C ₁ -C ₁₀ alkoxycarbonyl group, optionally substituted phenyl group, optionally substituted aromatic heterocyclic group   A herbicide containing the isoxazolin-3-yl derivative or pharmacologically acceptable salt thereof according to claim 1 as an active ingredient.