TW201443026A - Pyridazinone compound and herbicide containing the same - Google Patents

Abstract

A compound represented by the formula (I) is provided: wherein R1, R2, and R3 is a C1-6alkyl group; R4 and R5 is a hydrogen atom or A is a mono or dicyclic condensed ring aryl group; G is a hydrogen atom... etc.

Description

Anthrone compound and herbicide containing the same

The present invention relates to 嗒 a ketone compound and a herbicide containing the same.

Conventionally, compounds having potency of weed control have been found due to advances in the development of compounds for the active ingredients of herbicides for controlling weeds.

Herbicide known to have herbicidal activity Ketone compounds (WO 2007/119434, WO 2009/035150, WO 2009/086041, WO 2010/069525, WO 2010/069526, WO 2010/078912, WO 2010/104217, WO 2012/091156, WO 2013/160126, J. Heterocycl. Chem., vol. 42, p. 427-435, 2005, etc.).

The present invention is directed to a compound which provides excellent weed control efficacy.

As a result of careful examination by the inventors, the enthalpy represented by the following formula (I) was found. The ketone compound has excellent weed control efficacy and achieves the present invention.

That is, the present invention is as follows.

(Item 1) Formula (I) A ketone compound (hereinafter, simply referred to as a compound of the present invention.)

Wherein R ¹ represents hydrogen, C _1-6 alkyl, C _3-8 cycloalkyl, (C _3-8 cycloalkyl) C _1-6 alkyl, C _3-4 alkenyl or C _{3- 4} alkynyl, R ² represents hydrogen, halogen, cyano, nitro, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylthio, C _1-6 haloalkylsulfinyl, C _1-6 haloalkylsulfonyl, C _3-8 cycloalkyl, (C _3-8 cycloalkyl) C _1-6 alkyl, C _3-8 cycloalkoxy, (C _3-8 naphthenic) yl) C _1-6 alkoxy, (C _1-6 alkylthio) C _1-6 alkoxy, (C _1-6 alkoxy) C _1-6 alkoxy, C _3-6 alkenyloxy a group, a C _3-6 alkynyloxy group, a cyano C _1-6 alkoxy group, a (C _1-6 alkoxy)carbonyl C _1-6 alkoxy group, an amine carbaryl C _1-6 alkoxy group, {(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy, {di(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy, amine, C _1-6 An alkylamino group, a di(C _1-6 alkyl)amino group, a decylamino group, a (C _1-6 alkyl)carbonylamino group, a hydroxy C _1-6 alkyl group, a (C _1-6 alkoxy group) C _1-6 alkyl, (C _1-6 haloalkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, {(C _3-8 naphthenic) Base) C _1-6 alkoxy} C _1-6 alkane , (C _1-6 alkylthio) C _1-6 alkyl, (C _1-6 haloalkylthio) C _1-6 alkyl, cyano C _1-6 alkyl, hydroxyimino C _{1 a -6} alkyl group, a (C _1-6 alkoxy) imido C _1-6 alkyl group, a decyl group or a (C _1-6 alkyl) carbonyl group, and R ³ represents a halogen, a C _1-3 alkyl group, C _1-3 haloalkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-3 alkoxy, C _1-3 haloalkoxy or C _3-8 cycloalkyl, R ⁴ and R ⁵ may be the same or different and represents hydrogen, halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-3 alkoxy, C _1-3 haloalkoxy or C _3-8 cycloalkyl, and A represents an aryl group of a monocyclic or bicyclic condensed ring or one or more atoms selected from a group consisting of nitrogen, oxygen and sulfur. As the heteroaryl group of the monocyclic or bicyclic condensed ring of a hetero atom, the group may have one or more atoms or groups selected from the group B, and G represents hydrogen or any one represented by the following formula: Wherein L represents oxygen or sulfur, and R ⁶ represents C _1-12 alkyl, C _3-8 cycloalkyl, C _2-12 alkenyl, C _2-12 alkynyl, and may have 1 selected from group D. one or more atoms or C _6-10 aryl group, (D may have selected a group of one or more atoms or groups C _6-10 aryl) C _1-12 alkyl, C _1-12 alkoxy a C _3-8 cycloalkoxy group, a C _3-12 alkenyloxy group, a C _3-12 alkynyloxy group, a C _6-10 aryloxy group which may have one or more atoms or groups selected from the D group, (C _6-10 aryl group having 1 or more atoms or groups selected from the D group) C _1-12 alkoxy group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _{1 -6} alkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (C _{1- 6} alkylsulfinyl acyl) C _1-6 alkyl, (C _C1-6 alkylsulfonyl group) C _1-6 alkyl, (C may have a group selected from D or more atoms or groups _6-10 aryloxy) C _1-12 alkyl, (D may have selected a group of one or more atom or group of C _6-10 arylthio) C _1-12 alkyl, {(may have One or more atoms selected from group D or a C _6-10 aryl)C _1-6 alkoxy}C _1-6 alkyl group, (C _3-8 cycloalkyl) C _1-6 alkoxy group base Di (C _1-6 alkyl) amino, di (C _3-6 alkenyl) amino, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 heteroaryl And R ⁷ represents a C _1-6 alkyl group, a C _1-3 haloalkyl group, a C _6-10 aryl group or a di(C _1-6 alkyl group) which may have one or more atoms or groups selected from the D group. Amino, R ⁸ and R ⁹ may be the same or different and represent C _1-6 alkyl, C _3-8 cycloalkyl, C _6-10 aryl, C _1-6 alkoxy, C _3-8 Cycloalkoxy, C _6-10 aryloxy, (C _6-10 aryl) C _1-6 alkoxy, C _1-6 alkylthio or di(C _1-6 alkyl)amine, R ¹⁰ represents hydrogen or C _1-6 alkyl, W represents a one or more atom or group selected from the group D is phenyl, C _1-6 alkoxy, C _1-6 alkylthio, C _{1- 6} alkylsulfinyl or C _1-6 alkylsulfonyl. ^{Here, R 6, R 7, R} 8, R 9 and W is any group represented by the individual may have halogen, R C ⁶ cycloalkyl of _3-8, R ^6, R C ₃ ⁸ and R ⁹ is Any one of an aryl group of a _-8 cycloalkoxy group, a (C _1-6 alkyl)(C _6-10 aryl)amino group of R ⁸ and R ⁹ and a heteroaryl group of 5 to 6 members may have C _1-6 alkyl].

Group B: from halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy, C _3-8 cycloalkyl, C _2-4 Alkenyl, C _2-4 haloalkenyl, C _2-4 alkynyl, C _1-3 alkylthio, C _1-3 haloalkylthio, C _1-3 alkylsulfinyl, C _1-3 Haloalkylsulfinyl, C _1-3 alkylsulfonyl, C _1-3 haloalkylsulfonyl, nitro, cyano, (C _1-6 alkyl)carbonyl, (C _1-6 Alkoxy)carbonyl, aminemethanyl, (C _1-3 alkyl)aminocarbonyl, di(C _1-3 alkyl)aminocarbonyl, (C _1-6 alkyl)carbonylamino, (C _A group of a _3-8 cycloalkyl)carbonylamino group, a (C _1-6 alkoxy)carbonylamino group, and a (C _1-3 alkoxy) C _1-3 alkyl group.

Group D: from halogen, C _1-6 alkyl, C _1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy, C _1-3 alkylthio, cyano and nitrate The group formed by the base].

(Item 2) The 嗒 described in the above (Item 1) a ketone compound, wherein A represents a phenyl group, a naphthyl group, a pyridyl group, an anthracene Base, pyrimidinyl, pyridyl Benzothiazolyl, benzo Azolyl, quinolyl, cinnolinyl, quinazolinyl, quin Porphyrin or benzotrien Further, these groups may have one or more atoms or groups selected from Group B, and G represents hydrogen or any of the groups represented by the following formula: ^Wherein R ^6a represents a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, or a C _6-10 aryl group which may have one or more atoms or groups selected from the D group. a group, a C _6-10 aryl group (which may have one or more atoms or groups selected from the D group), a C _1-12 alkyl group, a C _1-12 alkoxy group, a C _3-12 alkenyloxy group, a C ₃ group _{a -12} alkynyloxy group, a C _6-10 aryloxy group having 1 or more atoms or groups selected from the D group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _1-6 Alkoxy)C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (may have a group D C _6-10 aryl group selected from one or more atom or group) C _1-12 alkyl, (which may have one or more atom or group selected from the group D C _6-10 arylthio) C _1-12 alkyl, {(C _6-10 aryl which may have 1 or more atoms selected from the D group) C _1-6 alkoxy} C _1-6 alkyl or (C _{3- 8} -cycloalkyl)C _1-6 alkoxy, R ^7a represents a C _1-6 alkyl group or a C _6-10 aryl group which may have one or more atoms or groups selected from the D group, and W ^a represents C _{1 a -3} alkoxy group or a phenyl group which may have one or more atoms or groups selected from the D group]

Group B is halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy, nitro or cyano.

(Item 3) The 嗒 described in the above (Item 2) a ketone compound, wherein R ² represents hydrogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkoxy or (C _3-8 cycloalkyl) C _1-6 alkoxy.

(Item 4) The 嗒 described in the above (Item 3) A ketone compound wherein R ¹ is a methyl group.

(Item 5) The 嗒 described in the above (Item 3) A ketone compound wherein R ² is hydrogen, methyl or methoxy.

(Item 6) The 嗒 described in the above (Item 2) a ketone compound wherein R ¹ is methyl, R ² is hydrogen, methyl or methoxy, R ³ is methyl, ethyl, propyl, cyclopropyl, halogen or halomethyl, and R ⁴ is hydrogen or Methyl, R ⁵ is hydrogen, methyl, ethyl, propyl, cyclopropyl, halogen or halomethyl.

(Item 7) The 嗒 described in the above (Item 1) a ketone compound wherein A is pyridyl, benzothiazolyl, benzo The azole group or the quinolyl group may have one or more atoms or groups selected from the group B.

(Item 8) The 嗒 described in the above (Item 6) a ketone compound wherein R ³ is methyl, ethyl, propyl or cyclopropyl, R ⁴ and R ⁵ are hydrogen, and A is pyridyl, benzothiazolyl, benzo The azole group or the quinolyl group may have one or more atoms or groups selected from the group B.

(Item 9) A herbicide comprising the hydrazine according to any one of (1) to (8) A ketone compound is used as an active ingredient.

(Item 10) A method for controlling weeds according to any one of (1) to (8) An effective amount of a ketone compound applied to the soil in which weeds or weeds grow.

(Item 11) The enthalpy according to any one of (1) to (8) The use of ketone compounds is used for the control of weeds.

The compound of the invention has weed control efficacy and can be used as effective weeding The active ingredient of the agent.

The substituents in the present invention are explained below.

Examples of the halogen include fluorine, chlorine, bromine, and iodine.

The C _1-3 alkyl group means an alkyl group having 1 to 3 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and an isopropyl group.

The C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 2,2-dimethylpropyl group, a butyl group, and an isobutyl group. , secondary butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, pentyl, hexyl and isohexyl.

The C _1-12 alkyl group means an alkyl group having 1 to 12 carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a 1-methylpropyl group, a 2-methylpropyl group, and a 1- Ethylpropyl, 2,2-dimethylpropyl, butyl, isobutyl, secondary butyl, tert-butyl, 1-methylbutyl, 2-methylbutyl, 3-methyl Butyl, 1-ethylbutyl, 1-propylbutyl, pentyl, 1-methylpentyl, 1-ethylpentyl, 2,4,4-trimethylpentyl, hexyl, heptyl , octyl, sulfhydryl, sulfhydryl, eleven and twelve bases.

The halomethyl group means a methyl group having a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethyl group, a difluoromethyl group, a bromomethyl group and a chloromethyl group.

The C _1-3 haloalkyl group means an alkyl group having 1 to 3 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethyl group, a chloromethyl group and a 2,2-difluoroethyl group. 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl and 2,2,2-trifluoro-1,1-dichloroethyl.

The C _1-6 haloalkyl group means an alkyl group having 1 to 6 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethyl group, a chloromethyl group and a 2,2-difluoroethyl group. 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trifluoro-1,1-dichloroethyl and 2,2-difluorohexyl.

The C _1-12 haloalkyl group means an alkyl group having 1 to 6 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethyl group, a chloromethyl group and a 2,2-difluoroethyl group. , 2,2,2-trichloroethyl, 2,2,2-trifluoroethyl, 2,2,2-trifluoro-I,1-dichloroethyl, 2,2-difluorohexyl and 1 , 1-difluorododecyl.

The C _3-8 cycloalkyl group means a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

(C _3-8 cycloalkyl)C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms having a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropylmethyl group and a cyclopentyl group. methyl.

The C _2-4 alkenyl group means an alkenyl group having 2 to 4 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, and a 3-butenyl group.

The C _3-4 alkenyl group means an alkenyl group having 3 to 4 carbon atoms, and examples thereof include an allyl group, a 1-butenyl group, a 2-butenyl group and a 3-butenyl group.

The C _2-12 alkenyl group means an alkenyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, and a 5-hexene group. And 11-dodecenyl.

The C _2-4 alkynyl group means an alkynyl group having 2 to 4 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a 2-butynyl group.

The C _3-4 alkynyl group means an alkynyl group having 3 to 4 carbon atoms, and examples thereof include a propargyl group and a 2-butynyl group.

The C _2-12 alkynyl group means an alkynyl group having 2 to 12 carbon atoms, and examples thereof include a vinyl group, a propargyl group, a 2-butynyl group, a 5-hexynyl group, and an 11-dodecynyl group.

The C _1-3 alkoxy group means an alkoxy group having 1 to 3 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a n-propoxy group, and an isopropoxy group.

The C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a 2-methylpropoxy group. Base, 3-methylpropoxy, tert-butoxy, pentyloxy, secondary pentyloxy, isopentyloxy, neopentyloxy, hexyloxy and isohexyloxy.

The C _1-12 alkoxy group means an alkoxy group having 1 to 12 carbon atoms, and examples thereof include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, and a 2-methylpropoxy group. Base, 3-methylpropoxy, tert-butoxy, pentyloxy, secondary pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, isohexyloxy and dodecyloxy.

The C _1-3 haloalkoxy group means an alkoxy group having 1 to 3 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethoxy group and a 2,2-difluoroethoxy group. 2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy and 3,3-difluoropropoxy.

The C _1-6 haloalkoxy group means an alkoxy group having 1 to 3 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethoxy group and a 2,2-difluoroethoxy group. 2,2,2-Trifluoroethoxy, 2,2,2-trichloroethoxy, 3,3-difluoropropoxy and 6-fluorohexyloxy.

The C _1-6 alkylthio group means an alkylthio group having 1 to 6 carbon atoms, and examples thereof include a methylthio group, an ethylthio group and an isopropylthio group.

The C _1-6 alkylsulfinyl group means an alkylsulfinyl group having 1 to 6 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and an isopropylsulfinyl group. .

The C _1-6 alkylsulfonyl group means an alkylsulfonyl group having 1 to 6 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and an isopropylsulfonyl group.

The C _1-6 haloalkylthio group means an alkylthio group having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trichloromethylthio group, a trifluoromethylthio group, and 2,2. -difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio and 3-chloropropylthio.

The C _1-6 haloalkylsulfinyl group means an alkylsulfinyl group having 1 to 6 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine. For example, trichloromethylsulfinyl, trifluoromethylsulfinyl, 2,2-difluoroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 2 , 2,2-trichloroethylsulfinyl and 3-chloropropylsulfinyl.

The C _1-6 haloalkylsulfonyl group means an alkylsulfonyl group having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include trichloromethylsulfonyl group and trifluoromethyl group. Sulfosyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl and 3-chloropropyl Sulfonyl.

The C _3-8 cycloalkoxy group means a cycloalkyloxy group having 3 to 8 carbon atoms, and examples thereof include a cyclopropoxy group, a cyclopentyloxy group, and a cyclohexyloxy group.

The (C _3-8 cycloalkyl) C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms having a cycloalkyl group having 3 to 8 carbon atoms, and examples thereof include a cyclopropylmethoxy group. 1-cyclopropylethoxy and cyclopentylmethoxy.

The (C _1-6 alkylthio) C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms bonded to an alkylthio group having 1 to 6 carbon atoms, and examples thereof include a methylthiomethoxy group. Methylthioethoxy, methylthiopropoxy, ethylthiomethoxy and ethylthioethoxy.

(C _1-6 alkoxy) C _1-6 alkoxy carbon atoms is intended to mean an alkoxy group having 1 to 6 bonded alkoxy having 1 to 6, and examples thereof include methoxymethoxy , ethoxymethoxy, n-propoxymethoxy, isopropoxymethoxy, 2-methoxyethoxy, 2-ethoxyethoxy and 3-methoxypropoxy .

The C _3-6 alkenyloxy group means an alkenyloxy group having 3 to 6 carbon atoms, and examples thereof include an allyloxy group and a 2-butenyloxy group.

It means a C _3-12 alkenyloxy group is an alkenyloxy group having 3 to 12 carbon atoms, for example, allyloxy, 2-butenyloxy, 5-hexenyloxy group and dodecene 11- .

The C _3-6 alkynyloxy group means an alkynyloxy group having 3 to 6 carbon atoms, and examples thereof include a propargyloxy group and a 2-butynyloxy group.

The C _3-12 alkynyloxy group means an alkynyloxy group having 3 to 12 carbon atoms, and examples thereof include a propargyloxy group, a 2-butynyloxy group, a 5-hexynyloxy group, and an 11-dodecynyloxy group. .

The cyano C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms having a cyano group, and examples thereof include a cyanomethoxy group, a 1-cyanomethoxy group, and a 2-cyanoethoxy group. And 3-cyanopropoxy.

The (C _1-6 alkoxy)carbonyl C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms bonded to a carbonyl group having an alkoxy group (having 1 to 6 carbon atoms), for example, Methoxycarbonylmethoxy and ethoxycarbonylmethoxy.

The amidamidyl C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms which has an amine carbenyl group, and examples thereof include an amine methyl methoxy group.

The {(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms bonded to an aminocarbonyl group having an alkyl group having 1 to 6 carbon atoms. For example, a methylaminocarbonylmethoxy group can be mentioned.

(Bis(C _1-6 alkyl)aminocarbonyl)C _1-6 alkoxy is meant to be bonded to {with (an amine group having 2 identical or different alkyl groups having 1 to 6 carbon atoms) The alkoxy group having 1 to 6 carbon atoms bonded to the carbonyl group may, for example, be dimethylaminocarbonylcarbonyl.

The C _1-6 alkylamino group means an alkylamino group having 1 to 6 carbon atoms, and examples thereof include a methylamino group, an ethylamino group and an isopropylamine group.

The bis(C _1-6 alkyl)amino group means an amine group having two identical or different alkyl groups having 1 to 6 carbon atoms, and examples thereof include a dimethylamino group, a diethylamino group and a Methylamino group.

The (C _1-6 alkyl)carbonylamino group means an amine group bonded to a carbonyl group having an alkyl group having 1 to 6 carbon atoms, and examples thereof include an ethylamine group and a acrylamide group.

The hydroxy C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having a hydroxyl group, and examples thereof include a methylol group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, and a 3-hydroxypropyl group.

The (C _1-6 alkoxy) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms bonded to an alkoxy group having 1 to 6 carbon atoms, and examples thereof include a methoxymethyl group and 1 Methoxyethyl, ethoxymethyl, propoxymethyl, butoxymethyl, 1-methyl 2-methoxyethyl and 2-ethoxyethyl.

(C _1-6 haloalkoxy) C _1-6 alkyl means a carbon number of 1 to 6 bonded to (alkoxy having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine) The alkyl group may, for example, be 2,2-difluoroethoxymethyl, 2,2,2-trifluoroethoxymethyl, 2,2-difluoroethoxyethyl and 2,2,2- Trifluoroethoxyethyl.

(C _3-8 cycloalkoxy) C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms bonded to a cycloalkyloxy group having 3 to 8 carbon atoms, and examples thereof include a cyclopropoxymethyl group. And cyclopentyloxymethyl.

{(C _3-8 cycloalkyl)C _1-6 alkoxy}C _1-6 alkyl means an alkane having 1 to 6 carbon atoms bonded to {with a cycloalkyl group of 3 to 8 carbon atoms) The alkyl group having 1 to 6 carbon atoms bonded to the oxy} group may, for example, be a cyclopropylmethoxymethyl group.

(C _1-6 alkylthio) C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms bonded to an alkylthio group having 1 to 6 carbon atoms, and examples thereof include methylthiomethyl group and 1- (Methylthio)ethyl, ethylthiomethyl, propylthiomethyl, butylthiomethyl, 1-methyl-2-(methylthio)ethyl and 2-(ethylthio)ethyl .

(C _1-6 alkylsulfinyl) C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms bonded to an alkylsulfinyl group having 1 to 6 carbon atoms, and examples thereof include a methyl group. Sulfosylmethyl and ethylsulfinylmethyl.

(C _1-6 alkylsulfonyl) C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms bonded to an alkylsulfonyl group having 1 to 6 carbon atoms, and examples thereof include methylsulfonium sulfonate. Methyl, ethylsulfonylmethyl and 2-(methylsulfonyl)ethyl.

(C _1-6 haloalkylthio) C _1-6 alkyl means a carbon number of 1 to 6 in combination with an alkylthio group having 1 to 6 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine. Examples of the alkyl group include a trifluoromethylthiomethyl group, a 2,2-difluoroethylthiomethyl group, and a 2,2,2-trifluoroethylthiomethyl group.

The cyano C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having a cyano group, and examples thereof include a cyanomethyl group, a 1-cyanoethyl group, a 2-cyanoethyl group, and a 3-cyanoethyl group.

The hydroxyimino group C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms having a hydroxyimino group, and examples thereof include a hydroxyiminomethyl group.

(C _1-6 alkoxy)imino C _1-6 alkyl means an alkyl group having 1 to 6 carbon atoms bonded to (an imine group bonded to an alkoxy group having 1 to 6 carbon atoms), For example, a methoxyiminomethyl group and an ethoxyiminomethyl group are mentioned.

The (C _1-6 alkyl)carbonyl group means a carbonyl group bonded to an alkyl group having 1 to 6 carbon atoms, and examples thereof include an ethyl group, a propyl group and a butyl group.

The aryl group of the monocyclic or bicyclic condensed ring is exemplified by a 5- or 6-membered monocyclic aryl group or a 6-membered or 6-membered bicyclic condensed ring aryl group, for example, Phenyl, naphthyl, indanyl or 1,2,3,4-tetrahydronaphthyl.

A heteroaryl group containing a monocyclic or bicyclic condensed ring in which one or more atoms selected from the group consisting of nitrogen, oxygen and sulfur are used as a hetero atom means that there are at most three in the monocyclic ring, in the second The heterocyclic group of the hetero atom selected from the group consisting of nitrogen, oxygen and sulfur in the cyclic condensed ring may be a 5- or 6-membered monocyclic heteroaryl group, or 6-6 members or 6 The heteroaryl group of the 5-membered bicyclic condensed ring may, for example, be furyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, 1,2,3-triazolyl, 1,2,4-tri Azolyl, Azolyl, different Azyl, thiazolyl, isothiazolyl, 1,2,4- Diazolyl, 1,3,4- Diazolyl, 1, 2, 5- Diazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,3,4-thiadiazolyl, 1,2,5-thiadiazolyl, pyridyl ,despair Base, pyrimidinyl, pyridyl Base, 1, 2, 3-three Base, 1, 2, 4-three Base, porphyrin group, isoindolyl group, coumarin group, 1,3,5-three Benzofuranyl, benzoisofuranyl, benzothienyl, benzisothienyl, fluorenyl, isodecyl, oxazolyl, benzothiazolyl, benzisothiazolyl, benzo Azolyl, benzimidazolyl, 2,1,3-benzo Diazolyl, quinolyl, isoquinolinyl, porphyrinyl, anthracene Phthaazinyl, quinazolinyl, quin Olinyl group, Naphthyridinyl, benzotrien Base, sulfhydryl, pteridinyl and ruthenium Indolizinyl.

The C _2-6 alkenyl group means an alkenyl group having 2 to 6 carbon atoms, and examples thereof include a vinyl group, an allyl group, a 1-buten-3-yl group, and a 3-buten-1-yl group.

The C _2-6 alkynyl group means an alkynyl group having 2 to 6 carbon atoms, and examples thereof include an ethynyl group, a propargyl group, and a 2-butynyl group.

The C _6-10 aryl group means an aryl group having 6 to 10 carbon atoms, and examples thereof include a phenyl group and a naphthyl group.

The (C _6-10 aryl) C _1-6 alkyl group means an alkyl group having 1 to 6 carbon atoms bonded to an aryl group having 6 to 10 carbon atoms, and examples thereof include a benzyl group and a phenethyl group.

(C _6-10 aryl) C _1-12 alkyl means an alkyl group having 1 to 12 carbon atoms bonded to an aryl group having 6 to 10 carbon atoms, and examples thereof include a benzyl group and a 1-phenylethyl group. Phenylethyl, 3-phenylpropyl, 6-phenylhexyl and 12-phenyldodecyl.

The C _6-10 aryloxy group means an aryloxy group having 6 to 10 carbon atoms, and examples thereof include a phenoxy group and a naphthyloxy group.

The (C _6-10 aryl) C _1-6 alkoxy group means an alkoxy group having 1 to 6 carbon atoms bonded to an aryl group having 6 to 10 carbon atoms, and examples thereof include a benzyloxy group and a phenethyloxy group. base.

(C _6-10 aryloxy) C _1-12 alkyl means an alkyl group having 1 to 12 carbon atoms bonded to an aryloxy group having 6 to 10 carbon atoms, and examples thereof include a phenoxymethyl group, 2 - phenoxyethyl, 1-methyl-2-phenoxyethyl and 3-phenoxypropyl.

(C _6-10 arylthio) C _1-12 alkyl means an alkyl group having 1 to 12 carbon atoms bonded to an arylthio group having 6 to 10 carbon atoms, and, for example, a phenylthiomethyl group , 2-phenylthioethyl, 1-methyl-2-phenylthioethyl and 3-phenylthiopropyl.

The (C _6-10 aryl) C _1-12 alkoxy group means an alkoxy group having 1 to 12 carbon atoms bonded to an aryl group having 6 to 10 carbon atoms, and examples thereof include a benzyloxy group and a phenethyloxy group. Base, 3-phenylpropoxy, 6-phenylhexyloxy and 12-phenyldodecyloxy.

{(C _6-10 aryl) C _1-6 alkoxy} C _1-6 alkyl means an alkoxy group having a carbon number of 1 to 12 bonded to {with (aryl group having 6 to 10 carbon atoms) The alkyl group having 1 to 12 carbon atoms bonded thereto may, for example, be a benzyloxymethyl group.

The bis(C _3-6 alkenyl)amino group means an amine group having two identical or different carbon atoms of 3 to 6 carbon atoms, and examples thereof include diallylamino groups and di(3-butene). Amino group.

The (C _1-6 alkyl)(C _6-10 aryl)amino group means an amine group having an alkyl group having 1 to 6 carbon atoms and a C _6-10 aryl group, and examples thereof include a methylphenylamino group. And ethylphenylamino group.

The heteroaryl group of 5 to 6 members means an aromatic 5- or 6-membered heterocyclic group having 1 to 3 hetero atoms selected from a group consisting of nitrogen, oxygen and sulfur, and examples thereof include 3-pyridyl group. , 3-thienyl and 1-pyrazolyl.

The C _2-4 haloalkenyl group means an alkenyl group having 2 to 4 carbon atoms having a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include 2,2-difluorovinyl and 2,2-dichlorovinyl. .

The C _1-3 alkylthio group means an alkylthio group having 1 to 3 carbon atoms, and examples thereof include a methylthio group, an ethylthio group and a propylthio group.

The C _1-3 haloalkylthio group means an alkylthio group having 1 to 6 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trichloromethylthio group, a trifluoromethylthio group, and 2,2. -difluoroethylthio, 2,2,2-trifluoroethylthio, 2,2,2-trichloroethylthio and 3-chloropropylthio.

The C _1-3 alkylsulfinium sulfonate means an alkylsulfinyl group having 1 to 3 carbon atoms, and examples thereof include a methylsulfinyl group, an ethylsulfinyl group, and a propylsulfinylene group.

The C _1-3 haloalkylsulfinyl group means an alkylsulfinyl group having 1 to 3 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trifluoromethylsulfinyl group.

The C _1-3 alkylsulfonyl group means an alkylsulfonyl group having 1 to 3 carbon atoms, and examples thereof include a methylsulfonyl group, an ethylsulfonyl group, and an isopropylsulfonyl group.

The C _1-3 haloalkylsulfonyl group means an alkylsulfonyl group having 1 to 6 carbon atoms which has a halogen such as fluorine, chlorine, bromine or iodine, and examples thereof include a trichloromethylsulfonyl group and a trifluoromethyl group. Sulfosyl, 2,2-difluoroethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 2,2,2-trichloroethylsulfonyl and 3-chloropropyl Sulfonyl.

The (C _1-6 alkoxy)carbonyl group means a carbonyl group bonded to (alkoxy group having 1 to 6 carbon atoms), and examples thereof include a methoxycarbonyl group, an ethoxycarbonyl group, and a n-hexyloxycarbonyl group.

The (C _1-3 alkyl)aminocarbonyl group means a carbonyl group bonded to an amine group having (alkyl group having 1 to 3 carbon atoms), and for example, a methylaminocarbonyl group can be cited.

The bis(C _1-3 alkyl)aminocarbonyl group means a carbonyl group bonded to an amine group having two identical or different alkyl groups having 1 to 3 carbon atoms, and examples thereof include a dimethylaminocarbonyl group.

The (C _3-8 cycloalkyl)carbonylamino group means a carbonylamino group bonded to a (cycloalkyl group having 3 to 8 carbon atoms), and examples thereof include a cyclopropylcarbonylamino group and a cyclohexylcarbonylamino group.

The (C _1-6 alkoxy)carbonylamino group means a carbonylamino group bonded to (alkoxy group having 1 to 6 carbon atoms), and examples thereof include a methoxycarbonylamino group.

(C _1-3 alkoxy) C _1-3 alkyl means an alkyl group having 1 to 3 carbon atoms bonded to (alkoxy group having 1 to 3 carbon atoms), and examples thereof include a methoxymethyl group. 1-methoxyethyl, ethoxymethyl and 2-ethoxyethyl.

In the compound of the present invention, the oxime represented by the formula (I) The ketone compound may be in the form of an agronomically acceptable salt with an inorganic base or an organic base, and the present invention also includes the form of the salt. Ketone compound. Examples of such a salt include an inorganic base (for example, a hydroxide, a carbonate, a hydrogencarbonate, an acetate, a hydride, or the like of an alkali metal (lithium, sodium, potassium, etc.), an alkaline earth metal (magnesium, calcium, or the like). Hydroxide, hydride, etc., ammonia, and an organic base (for example, dimethylamine, triethylamine, and piperidin) , pyrrolidine, piperidine, 2-phenylethylamine, benzylamine, ethanolamine, diethanolamine, pyridine, Colin base, etc.), metal alkoxides (for example, sodium methoxide, potassium tert-butoxide, magnesium methoxide) Etc.) Mix the resulting salt.

When the compound of the present invention has one or more asymmetric centers, the compound may have two or more stereoisomers (for example, a mirror image isomer, a non-image isomer, etc.). The compound of the present invention contains all such stereoisomers and mixtures of any two or more of these.

Further, when the compound of the present invention has geometrical isomerism based on a double bond or the like, the compound has two or more geometric isomers (for example, E/Z or reverse/cis isomers, S-anti/S-cis The presence of each isomer, etc.). The compounds of the invention comprise all of the geometries An isomer and a mixture of any two or more of these.

Examples of the compound of the present invention include the compounds shown below.

[Mode 1] 嗒 expressed by the formula (Ia) Ketone compounds: Wherein R ¹ , R ³ , R ⁴ , R ⁵ and A represent the same meaning as defined above, and R ² represents hydrogen, halogen, cyano, nitro, C _1-6 alkyl, C _1-6 halo , C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _{1 -6} haloalkylthio, C _1-6 haloalkylsulfinyl, C _1-6 haloalkylsulfonyl, C _3-8 cycloalkyl, C _3-8 cycloalkoxy, (C _{3 -8} cycloalkyl)C _1-6 alkoxy, (C _1-6 alkylthio) C _1-6 alkoxy, (C _1-6 alkoxy) C _1-6 alkoxy, C _{3 -6} -alkenyloxy, C _3-6 alkynyloxy, cyano C _1-6 alkoxy, (C _1-6 alkoxy)carbonyl C _1-6 alkoxy, amine carbaryl C _1-6 Alkoxy, {(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy, (di(C _1-6 alkyl)aminocarbonyl)C _1-6 alkoxy, amine group, C _1-6 alkylamino group, di(C _1-6 alkyl)amino group, formamidine, (C _1-6 alkyl)carbonylamino group, hydroxy C _1-6 alkyl group, (C _1-6 Alkoxy)C _1-6 alkyl, (C _1-6 haloalkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, {(C _{3- 8} -cycloalkyl)C _1-6 alkoxy}C _1-6 alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (C _1-6 haloalkylthio) C _1-6 Alkyl, cyano C _1-6 alkyl, hydroxyimino C _1-6 alkyl, (C _1-6 alkoxy) imido C _1-6 alkyl, methionyl or (C _1-6 alkyl)carbonyl, R ³ represents halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-3 alkoxy, C _1-3 haloalkoxy Or C _3-8 cycloalkyl, G ²¹ represents hydrogen or any of the groups represented by the formula:

Wherein L represents oxygen or sulfur, and R ⁶¹ represents a C _1-6 alkyl group, a C _1-3 haloalkyl group, a C _3-6 cycloalkyl group, a C _2-6 alkenyl group, a C _2-6 alkynyl group, It may have one or more atom or group selected from the group C, C _6-10 aryl group, (which may have one or more atom or group selected from the group C C _6-10 aryl) C _1-6 alkyl a group, a C _1-6 alkoxy group, a C _3-8 cycloalkoxy group, a C _3-6 alkenyloxy group, a C _3-6 alkynyloxy group, or a group having one or more atoms or groups selected from the group C; C _6-10 aryl group (the group may have selected one or more C atoms or a group of C _6-10 aryl) C _1-6 alkoxy, di (C _1-6 alkyl) amino , a di(C _3-6 alkenyl)amino group, a (C _1-6 alkyl)(C _6-10 aryl)amino group or a heteroaryl group of 5 to 6 members, and R ⁷¹ represents a C _1-6 alkyl group , C _1-3 haloalkyl, C _6-10 aryl or di(C _1-6 alkyl)amino group which may have one or more atoms or groups selected from Group C, and R ⁸¹ and R ⁹¹ may be the same Or different, meaning C _1-6 alkyl, C _3-8 cycloalkyl, C _6-10 aryl, C _1-6 alkoxy, C _3-8 cycloalkoxy, C _6-10 aryloxy a (C _6-10 aryl) C _1-6 alkoxy group, a C _1-6 alkylthio group or a di(C _1-6 alkyl)amino group, and R ¹⁰¹ represents hydrogen or a C _1-6 alkyl group. W ^{2 1} represents a phenyl group, a C _1-6 alkoxy group, a C _1-6 alkylthio group, a C _1-6 alkylsulfinyl group or a C ₁ group which may have one or more atoms or groups selected from the group C. _{a -6} alkylsulfonyl group (however, any of R ⁶¹ , R ⁷¹ , R ⁸¹ , R ⁹¹ and W ²¹ each may have a halogen, a C _3-8 cycloalkyl group, a C _6-10 aryl group, (C _6-10 aryl) aryl moiety of C _1-6 alkyl, C _3-8 cycloalkoxy, C _6-10 aryloxy, (C _6-10 aryl) C _1-6 alkoxy Any of the aryl moiety of the group, the aryl moiety of the (C _1-6 alkyl)(C _6-10 aryl)amine group, and the heteroaryl group of 5 to 6 members may have a C _1-6 alkyl group. )}

Group C represents halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-6 alkoxy or nitro]

[Mode 2] A compound wherein, in [Mode 1], R ¹ is a C _1-3 alkyl group, [Mode 3] a compound wherein, in [Mode 2], R ¹ is a methyl group, [method] 4] A compound wherein, in any one of [Mode 1] to [Mode 3], R ²¹ is hydrogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-6 alkoxy , C _1-6 haloalkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkoxy or (C _3-8 cycloalkyl) C _1-6 alkoxy, [Mode 5] a compound Wherein, in [Mode 4], R ²¹ is a C _1-3 alkyl group, [Mode 6] a compound wherein, in [Mode 5], R ²¹ is a methyl group, [Mode 7] a compound wherein In [Mode 6], R ²¹ is a C _1-6 alkoxy group, [Mode 8] a compound wherein, in [Mode 7], R ²¹ is a methoxy group, [Mode 10] a compound wherein In any one of [Mode 1] to [Mode 9], R ³ is a C _1-3 alkyl group, [Mode 11] a compound wherein, in [Mode 10], R ³ is a methyl group, [ 12 according to any embodiment] a compound wherein, in the 10], [embodiment, R ³ is ethyl, [embodiment 13] a compound wherein [embodiment 1] to [embodiment 12] one way of , R ⁴ is hydrogen, [14 embodiment] A compound wherein [Embodiment 1] to [Embodiment 13] of any one embodiment, R ⁵ is hydrogen, [Embodiment 15] A compound wherein [Embodiment 1] In any one of [Mode 14], A represents an aryl group of a monocyclic or bicyclic condensed ring, or represents 1 or 2 atoms selected from a group consisting of nitrogen, oxygen and sulfur as a hetero atom. a heteroaryl group of a monocyclic or bicyclic condensed ring, which may have one or more atoms or groups selected from the group B, [Mode 16] a compound in which [Mode 1] to [Mode 15] In any of the methods, A is a phenyl group, a naphthyl group, a pyridyl group, a fluorene group. Base, pyrimidinyl, pyridyl Benzoquinazolyl, benzo Azyl, quinolyl, porphyrin, quinazolinyl, quin Porphyrin or benzotrien Further, the group may have one or more atoms or groups selected from the group B, and [method 17] wherein, in [method 16], A may have one or more atoms selected from the group B. Or a phenyl group, [Mode 18] a compound wherein, in [Mode 17], A is 2-fluoro-4-cyanophenyl, [Mode 19] a compound wherein [Mode 17] , A is 4-trifluoromethylphenyl, [Mode 20] a compound wherein, in [Mode 17], A is 2-chloro-4-trifluoromethylphenyl, [Mode 21] a compound, In the [Mode 16], A is a pyridyl group which may have one or more atoms or groups selected from the B group, and [Mode 22] a compound in which, in [Mode 21], A is 5-three. Fluoromethylpyridin-2-yl, [Mode 23] a compound wherein, in [Mode 21], A is 2-chloro-5-trifluoromethylpyridin-2-yl, [Mode 24] a compound, Wherein, in [Mode 21], A is 2-fluoro-5-trifluoromethylpyridin-2-yl, [Mode 25] a compound wherein, in [Mode 21], A is 2-fluoro-5 -Chloromethylpyridin-2-yl, [Mode 26] a compound in which [Mode 16] In the above, A is a benzothiazolyl group which may have one or more atoms or groups selected from the group B, [Mode 27] A compound in which, in [Mode 26], A is a benzothiazolyl group, [Mode 28] A compound wherein, in [Mode 26], A is 6-chlorobenzothiazolyl, [Mode 29] a compound wherein, in [Mode 16], A is one which may be selected from Group B. Above atom or base benzo Azolyl, [Mode 30] a compound wherein, in [Mode 29], A is 6-chlorobenzo Azolyl, [Mode 31] A compound wherein, in [Mode 16], A is a quinine which may have one or more atoms or groups selected from Group B. A phenyl group, [Mode 32] a compound wherein, in [Mode 31], A is 6-chloroquine [Formula 33] A compound wherein, in any of [Mode 1] to [Mode 32], G ²¹ is hydrogen or a formula represented by the following formula:

Wherein R ⁶¹ represents a C _1-6 alkyl group, a C _3-8 cycloalkyl group, a C _1-6 alkoxy group, a C _3-6 alkenyloxy group, a C _3-6 alkynyloxy group, and may have a C group the selected one or more atom or group or a C _8-10 aryl group may have one or more C atoms or a group selected from the group of C _8-10 aryloxy group, W ²¹ is a C _1-3 alkoxy group Or a phenyl group having one or more atoms or groups selected from the group C, [Mode 34] a compound wherein, in [Mode 33], G ²¹ is hydrogen, [Mode 35] a compound in which [Mode 33] wherein G ²¹ is (C _1-6 alkyl)carbonyl, [Mode 36] a compound wherein, in [Mode 33], G ²¹ is an ethyl group, [Mode 37] a compound wherein In [Mode 33], G ²¹ is a propyl group, [Mode 38] a compound wherein, in [Mode 33], G ²¹ is an isobutyl group, [Mode 39] a compound in which [Mode 33 Wherein G ²¹ is a trimethylethenyl group, [Mode 40] a compound wherein, in [Mode 33], G ²¹ is a (C _1-6 alkoxy)carbonyl group, [Mode 41] a compound, wherein, in the [embodiment 33], G ²¹ is a methoxycarbonyl group, [embodiment 42] a compound, , The [embodiment 33] in, G ²¹ is a C _1-3 alkoxy-methyl group, [embodiment 43] A compound wherein, in the [embodiment 33], G ²¹ is methoxy methyl, [embodiment 44 ] a compound wherein, in the [embodiment 33], G ²¹ is benzyl group which has one or more atom or group selected from the group C, 45] of a compound [manner, wherein, in the [embodiment 33], G ²¹ is a benzyl group, [Mode 46] a compound wherein, in [Mode 33], G ²¹ is 2-nitrobenzyl, [Mode 47] a compound wherein [21], G ²¹ Is a cyclopropylcarbonyl group, [Mode 48] a compound wherein, in [Mode 33], G ²¹ is a cyclobutylcarbonyl group, [Mode 49] a compound wherein, in [Mode 33], G ²¹ is a ring A pentylcarbonyl group, [Mode 50] A compound wherein, in [Mode 33], G ²¹ is a cyclohexylcarbonyl group, [Mode 51] a compound wherein, in [Mode 33], G ²¹ is a benzyl fluorenyl group, [Mode 52] A compound wherein, in [Mode 33], G ²¹ is 2-methylbenzylidene, [Mode 53] a compound wherein, in [Mode 33], G ²¹ is 3-methyl Benzylidene group, [Mode 54] a kind A compound wherein, in [Mode 33], G ²¹ is a 4-methylbenzylidene group, [Formula 55] a hydrazine represented by the formula (Ib) Ketone compounds: Wherein [R ¹¹ represents C _1-3 alkyl, R ^21a represents C _1-6 alkyl or C _1-6 alkoxy, R ³¹ represents C _1-3 alkyl, and R ⁴¹ and R ⁵¹ represent hydrogen, A ²¹ represents an aryl group of a monocyclic or bicyclic condensed ring, or a monocyclic or bicyclic condensed ring containing 1 or 2 atoms selected from a group consisting of nitrogen, oxygen and sulfur as a hetero atom. The aryl group may have one or more atoms or groups selected from the group consisting of a halogen atom and a C _1-3 haloalkyl group, and G ²² is hydrogen or any one of the following formulas: ^Wherein R ^61b represents a C _1-6 alkyl group, a C _3-6 cycloalkyl group, a C _6-10 aryl group or a C _1-6 alkoxy group which may have one or more atoms or groups selected from the C group. a group, W ^21b represents a phenyl group which may have a C _1-6 alkoxy group or a nitro group]

[Mode 56] A kind of 嗒 A ketone compound, wherein, in [Mode 55], R ¹¹ represents a methyl group, R ²¹ represents hydrogen, a methyl group or a methoxy group, and A ²¹ represents a pyridyl group, a benzothiazolyl group, a benzo group. Azolyl or quinolyl, [Mode 57] A compound wherein, in the formula (I), R ¹ is a C _1-3 alkyl group, [Mode 58] a compound wherein, in [Mode 57], R ¹ is a methyl group, [Mode 59] a compound wherein, in [Mode 57] or [Mode 58], R ² is hydrogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-6 Alkoxy, C _1-6 haloalkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkoxy or (C _3-6 cycloalkyl) C _1-6 alkoxy, [method 60 A compound wherein, in [Mode 59], R ² is a C _1-3 alkyl group, [Mode 61] a compound wherein, in [Mode 60], R ² is a methyl group, [Mode 62] A compound wherein, in [Mode 59], R ² is a C _1-6 alkoxy group, [Mode 63] a compound wherein, in [Mode 62], R ² is a methoxy group, [Mode 64] A compound, wherein, in the formula (I), R ³ is a C _1-3 alkyl group, [method 65] a compound wherein, in any one of [Mode 57] to [Mode 63], R ³ is C _C1-3 alkyl, [embodiment 66] a compound wherein, in the [embodiment 65], R ³ is methyl, [embodiment 67] a compound wherein, in the [embodiment 65], R ³ is ethyl [Embodiment 68] A compound wherein, in formula (the I), R ⁴ is hydrogen, [embodiment 69] A compound wherein, in any of [embodiment 57] to [embodiment 67] The one embodiment, R ⁴ is hydrogen [Mode 70] A compound wherein, in the formula (I), R ⁵ is hydrogen, [Mode 71] a compound, wherein, in any one of [Mode 57] to [Mode 69], R ⁵ is Hydrogen, [Mode 72] a compound wherein, in the formula (I), A is phenyl, naphthyl, pyridyl, anthracene Base, pyrimidinyl, pyridyl Benzothiazolyl, benzo Azyl, quinolyl, porphyrin, quinazolinyl, quin Porphyrin or benzotrien Further, the group may have one or more atoms or groups selected from the group B, and [method 73] wherein, in any one of [Mode 57] to [Mode 71], A is a phenyl group. , naphthyl, pyridyl, anthracene Base, pyrimidinyl, pyridyl Benzothiazolyl, benzo Azyl, quinolyl, porphyrin, quinazolinyl, quin Porphyrin or benzotrien The group may have one or more atoms or groups selected from the group B, and [method 74], wherein in the method 73, A may have one or more selected from the group B. Atom or a phenyl group, [Mode 75] a compound wherein, in [Mode 74], A is 2-fluoro-4-cyanophenyl, [Mode 76] a compound wherein [Mode 74] Wherein A is 4-trifluoromethylphenyl, [Mode 77] a compound wherein, in [Mode 74], A is 2-chloro-4-trifluoromethylphenyl, [Mode 78] a compound In [Mode 73], A is a pyridyl group which may have one or more atoms or groups selected from the B group, [Mode 79] a compound in which, in [Mode 78], A is 5- Trifluoromethylpyridin-2-yl, [Mode 80] A compound wherein, in [Mode 78], A is 2-chloro-5-trifluoromethylpyridin-2-yl, [Mode 81] a compound Wherein, in [Mode 78], A is 2-fluoro-5-trifluoromethylpyridin-2-yl, [Mode 82] a compound wherein, in [Mode 78], A is 2-fluoro- 5-Chloromethylpyridin-2-yl, [Mode 83] a compound in which In 73], A is a benzothiazolyl group which may have one or more atoms or groups selected from the group B, [Mode 84] A compound in which, in [Mode 83], A is a benzothiazolyl group, [ Mode 85] A compound wherein, in [Mode 83], A is 6-chlorobenzothiazolyl, [Mode 86] a compound wherein, in [Mode 73], A is selected from Group B. More than one atom or group of benzo Azolyl, [Mode 87] a compound wherein, in [Mode 86], A is 6-chlorobenzo Azolyl, [Mode 88] A compound wherein, in [Mode 73], A is a quinine which may have one or more atoms or groups selected from the B group. A phenyl group, [Mode 89] a compound wherein, in [Mode 88], A is 6-chloroquine [Formula 90] A compound wherein, in the formula (I), G is hydrogen or a group represented by the following formula

(wherein R ^6a , R ^7a and W ^{a have the} same meanings as described above.)

[Aspect 91] A compound, wherein, in any one of [Mode 57] to [Mode 90], G is hydrogen or a group represented by the following formula:

(wherein R ^6a , R ^7a and W ^{a have the} same meanings as described above.)

[Mode 92] A compound wherein, in [Mode 91], G is a (C _1-12 alkyl)carbonyl group, [Mode 93] a compound wherein, in [Mode 91], G is a butyl group, [method] 94] A compound wherein, in [Mode 91], G is 2-methylbutanyl, [Mode 95] a compound wherein, in [Mode 91], G is 3-methylbutanyl, [Mode 96] A compound wherein, in [Form 91], G is a amyl group, [Mode 97] a compound wherein, in [Mode 91], G is 2-methylpentanyl, [Mode 98] a compound Wherein, in [Mode 91], G is 2-ethylpentanyl, [Mode 99] a compound wherein, in [Mode 91], G is 2-propylpentyl, [Mode 100] A compound wherein, in [Form 91], G is a hexyl group, [Mode 101] a compound wherein, in [Mode 91], G is 2-methylhexanyl, [Mode 102] a compound Wherein, in [Mode 91], G is 2-ethylhexyl, [Mode 103] a compound wherein, in [Mode 91], G is 3,5,5-trimethylhexyl , [Mode 104] a compound in which [Mode 9 In 1], G is {(a C _6-10 aryl group which may have one or more atoms selected from the D group), a C _1-12 alkyl}carbonyl group, [Mode 105] a compound in which [ In the formula 91], G is a phenethyl group, [Mode 106] a compound wherein, in [Mode 91], G is a 3-phenylpropanyl group [Mode 107], wherein [Mode 91] Wherein G is (C _6-10 aryloxy)carbonyl which may have one or more atoms or groups selected from the D group, [Mode 108] a compound in which [Form 91], G is phenoxy A carbonyl group, [Mode 109] a compound wherein, in [Form 91], G is {(C _1-6 alkoxy) C _1-6 alkyl}carbonyl, [Mode 110] a compound wherein [Form 91] wherein G is a methoxyethyl group, [Mode 111] a compound wherein, in [Mode 91], G is an ethoxyethyl hydrazide group, [Mode 112] a compound wherein [Form 91] wherein G is a propoxyethyl group, [Mode 113] a compound wherein, in [Form 91], G is 3-methoxypropenyl, [Mode 114] a compound wherein , in [Mode 91], G is 3-ethoxypropanyl [Mode 115] Compounds, wherein, in the [embodiment 91], G is 3-methoxy-2-methylpropan-acyl, [116 embodiment] A compound wherein, in the [embodiment 91], G is {(C _{1 -6} alkylthio)alkyl}carbonyl, [Mode 117] A compound wherein, in [Mode 91], G is ethylthioethyl, [Mode 118] a compound, wherein [Mode 91] Wherein G is a 3-(methylthio)propanyl group, [Mode 119] a compound wherein, in [Mode 91], G is {(may have one or more atoms or groups selected from the D group) C _6-10 aryloxy)C _1-12 alkyl}carbonyl, [Mode 120] A compound wherein, in [Mode 91], G is phenoxyethyl hydrazino, [Mode 121] a compound wherein In [Form 91], G is [{(C _6-10 aryl group which may have one or more atoms or groups selected from the D group) C _1-6 alkoxy} C _1-6 alkyl] Carbonyl, [Mode 122] A compound wherein, in [Mode 91], G is a benzyloxyethyl group, [Mode 123] a compound wherein, in [Mode 91], G is (may have a D a group of more than one atom or a C _6-10 aryl)carbonyl group, [Mode 124] a compound Wherein, in [Mode 91], G is 2-fluorobenzylidene, [Mode 125] a compound wherein, in [Mode 91], G is 3-fluorobenzylidene, [Mode 126] a compound Wherein, in [Mode 91], G is 4-fluorobenzylidene, [Mode 127] a compound wherein, in [Mode 91], G is 2-chlorobenzylidene, [Mode 128] a compound Wherein, in [Mode 91], G is 3-chlorobenzylidene, [Mode 129] a compound wherein, in [Mode 91], G is 4-chlorobenzylidene, [Mode 130] a compound Wherein, in [Mode 91], G is 2-bromobenzylidene, [Mode 131] a compound wherein, in [Mode 91], G is 4-bromobenzylidene, [Mode 132] a compound Wherein, in [Mode 91], G is 2-ethylbenzylidene, {Mode 133] a compound wherein, in [Mode 91], G is 2-methoxybenzylidene, [Mode 134] A compound wherein, in [Form 91], G is 3-methoxybenzylidene, [Mode 135] a compound wherein, in [Form 91], G is 4-methoxybenzylidene [Mode 136] a compound wherein, in [Mode 91], G is 2-ethoxy A compound according to [Mode 137], wherein, in [Mode 91], G is 2-methylthiobenzyl hydrazino, [Mode 138] a compound wherein [method 91], G is 4-Cyanobenzylidene, [Mode 139] A compound wherein, in [Form 91], G is 2-nitrobenzyl fluorenyl, [Mode 140] a compound, wherein, in [Mode 91], G is 4-nitrobenzyl fluorenyl, [Mode 141] a compound wherein, in [Mode 91], G is 2-(trifluoromethyl)benzyl fluorenyl, [Mode 142] a compound in which [Form 91] wherein G is 4-(trifluoromethyl)benzylhydrazine, [Mode 143] a compound wherein, in [Form 91], G is 4-(trifluoromethoxy)benzylhydrazine [Mode 144] A compound wherein, in [Mode 91], G is 2,6-difluorobenzylidene, [Mode 145] a compound wherein, in [Mode 91], G is 2, 3 - Benzylbenzyl, [Mode 146] A compound wherein, in [Form 91], G is 2,4-dichlorobenzylidene, [Mode 147] a compound wherein [Mode 91] , G is 2,5-dichlorobenzylidene, [Mode 148] a compound in which [Mode 91] G is 2,6-dichlorobenzylidene, [Mode 148] a compound wherein, in [Mode 91], G is 3,4-dichlorobenzylidene, [Mode 150] a compound in which [Form 91] wherein G is 3,5-dichlorobenzylidene, [Mode 151] a compound wherein, in [Mode 91], G is 2,6-dimethylbenzylidene, [Mode 152] A compound wherein, in [Mode 91], G is 2,6-dimethoxybenzylidene, [Mode 153] a compound wherein, in [Mode 91], G is a methanesulfonyl group, [Aspect 154] A compound wherein, in [Form 91], G is a phenylsulfonyl group, [Formula 155] a hydrazine represented by the formula (Ic) Ketone compounds: Wherein R ¹² represents C _1-3 alkyl, R ²² represents hydrogen, C _1-6 alkyl or C _1-6 alkoxy, R ³² represents C _1-3 alkyl, and R ⁴² and R ⁵² represent Hydrogen, A ²² represents an aryl group of a monocyclic or bicyclic condensed ring, or a monocyclic or bicyclic condensed ring containing 1 or 2 atoms selected from a group consisting of nitrogen, oxygen and sulfur as a hetero atom. The heteroaryl group may have one or more atoms or groups selected from the group consisting of a halogen atom and a C _1-3 haloalkyl group, and G ²² represents the same meaning as described above.

[Mode 156] A kind of 嗒 A ketone compound, wherein, in [Mode 155], R ¹ represents a methyl group, R ² represents hydrogen, a methyl group or a methoxy group, and A represents a pyridyl group, a benzothiazolyl group, a benzo group. Azyl or quinolyl.

The herbicides of the invention comprise a compound of the invention and an inert carrier. on Examples of the inert carrier include a solid carrier, a liquid carrier, and a gas carrier. The herbicide of the present invention is usually further added with a surfactant, a fixative, a dispersant, a stabilizer, and the like, and is prepared as a hydrating agent, a granule hydrating agent, a flowable agent, a granule, and a dry flowability. Agents, emulsions, aqueous liquids, oils, smokers, aerosols, microcapsules, and the like. The herbicide of the present invention usually contains 0.1 to 80% of the compound of the present invention in a weight ratio.

The inert carrier may, for example, be a solid carrier, a liquid carrier or a gas carrier.

Examples of the solid carrier include clays (for example, kaolin, diatomaceous earth, synthetic aqueous cerium oxide, fubasami clay, bentonite, acid white clay), talc, and other inorganic minerals (for example, strontium). A fine powder or a granule such as mica, quartz powder, sulfur powder, activated carbon, calcium carbonate or hydrated cerium oxide. Examples of the liquid carrier include water, alcohols (for example, methanol, ethanol), and ketones. (Examples include acetone, methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene, ethylbenzene, methylnaphthalene) and aliphatic hydrocarbons (for example, n-hexane, cyclohexane, and kerosene) ), esters (for example, ethyl acetate, butyl acetate), nitriles (such as acetonitrile, isobutyronitrile), ethers (for example, two Alkane, diisopropyl ether), decylamines (for example, N,N-dimethylformamide (hereinafter abbreviated as DMF), dimethylacetamide), halogenated hydrocarbons (for example, dichloroethane) Alkane, trichloroethylene, carbon tetrachloride, etc.

Examples of the surfactant include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers, and polyoxyethylenes thereof, and polyoxyethylene glycols. Ethers, polyol esters, sugar alcohol derivatives, and the like.

Examples of other preparation adjuvants include a fixing agent and a dispersing agent, and specific examples thereof include casein, gelatin, and polysaccharides (for example, starch, Acacia gum, cellulose derivative, alginic acid), lignin derivative, bentonite, sugar, synthetic water-soluble polymer (for example, polyvinyl alcohol, polyvinylpyrrolidone, polyacrylic acid), PAP (acidic phosphoric acid) Isopropyl ester), BHT (2,6-di-tert-butyl-4-methylphenol), BHA (2-tert-butyl-4-methoxyphenol and 3-tertiary butyl-4- a mixture of methoxyphenol), vegetable oil, mineral oil, fatty acid or its ester, and the like.

The weed control method of the present invention comprises the step of applying an effective amount of the compound of the present invention to a place where weeds or weeds grow or a place where it may grow. In the weed control method of the present invention, the herbicide of the present invention is usually used. With regard to the method of applying the herbicide of the present invention, for example, a method of treating the stems and leaves of the weeds with the herbicide of the present invention, a method of treating the surface of the soil in which the weeds grow or may grow with the herbicide of the present invention, A method of mixing a herbicide of the present invention in a soil in which weeds grow, and a method of treating surface water of a paddy field which is stored in a place where weeds grow or may grow with the herbicide of the present invention. In the weed control method of the present invention, the compound of the present invention is usually applied in an amount of from 1 to 5,000 g, preferably from 10 to 1,000 g, per 10,000 m ² relative to the area for controlling weeds.

The compound of the present invention can be used in the cultivation of agricultural fields such as "plants" listed below.

"Plants": Crops: corn, rice, wheat, barley, rye, oats, sorghum, cotton, soybeans, groundnuts, buckwheat, sugar beets, canola, sunflower, sugar cane, tobacco, hops, etc.

Vegetables: Solanaceae vegetables (egg, tomato, sweet pepper, pepper, potato, etc.), Cucurbitaceae vegetables (courgette, pumpkin, zucchini, watermelon, cantaloupe, oriental melon, etc.), cruciferous vegetables (radish, turnip, horseradish, Indigo, Chinese cabbage, kale, mustard, broccoli, broccoli, etc.), Asteraceae (burdock, artemisia, artichoke, lettuce) Etc.), Liliaceae vegetables (onions, onions, garlic, asparagus, etc.), Umbelliferous vegetables (carrots, parsley, celery, European windproof, etc.), Polygonaceae vegetables (spinach, leaf beet, etc.), Labiatae Vegetables (perilla, mint, nine-story tower, etc.), legumes (peas, kidney beans, red beans, broad beans, chickpeas, etc.), strawberries, sweet potatoes, Japanese yam, taro, medlar, ginger, okra, etc.

Fruit trees: pome fruits (apples, pears, pears, clams, clams, etc.), stone fruits (peach, plum, nectarine, plum, cherry, apricot, dried fruit, etc.), citrus (Wenzhou mandarin, orange, lemon) , lime, grapefruit, etc.), nuts (chestnuts, walnuts, alfalfa, almonds, pistachios, cashews, macadamia, etc.), berries (blueberries, cranberries, blackberries, raspberries, etc.), grapes, persimmons, Olives, alfalfa, bananas, coffee, dates, coconuts, oil palms, etc.

Trees other than fruit trees: tea, mulberry, flower and wood (皋月鹃, Camellia, Hydrangea, Chamo, Japanese yarrow, Sakura, Liriodendron, Lagerstroemia, Dangui, etc.), street trees (eucalyptus, birch , large flowers, four flowers, eucalyptus, ginkgo, lilac, maple, eucalyptus, poplar, bauhinia, sweet gum, sycamore, eucalyptus, Japanese cedar, Japanese fir, Japanese hemlock, juniper , pine, fish scale spruce, Japanese yew, eucalyptus, Japanese horse chestnut, etc.), coral tree, Podocarpus, Japanese cedar, Japanese cypress, Croton, holly euonymus, Photinia glabra.

Others: flowers (rose, carnation, chrysanthemum, eustoma, silk flower, gerbera, marigold, bunch of red, petunia, verbena, tulip, sable, gentian, lily, pansy, cyclamen, Orchid, lily of the valley, lavender, violet, leaf peony, primrose, poinsettia, gladioli, garland, daisy, cymbidium, begonia, etc.), biomass fuel plants (jatropha, safflower, flax, wind Grass (switchgrass), Miscanthus, Arundo, kenaf, cassava, willow, etc.), foliage plants, etc.

Genetically modified plants are also included in the above "plants".

The compound of the present invention can be used in combination or in combination with other herbicides, phytotoxicity reducing agents, plant growth regulators, insecticides, acaricides, nematicides, bactericides and/or synergists.

As the active ingredient of such a herbicide, the following compounds are mentioned, for example.

(1) phenoxy fatty acid herbicidal compounds 2,4-PA, MCP, MCPB, phenothiol, 2-(4-chloro-2-methylphenoxy)propionic acid (mecoprop), fluorine Fluoroxypyr, triclopyr, clomeprop, naproanilide, etc.; (2) benzylic acid herbicidal compound 2,3,6-TBA, rickett grass (dicamba), clopyralid, picloram, aminopyralid, quinclorac, quinmerac, etc.; (3) urea-based weeding The compounds are diuron, linuron, chlortoluron, isoproturon, fluometuron, isouron, and tebuthiuron. , methafenzthiazuron, cumyluron, daimuron, methyl-daimuron, etc.; (4) three Herbicidal compound atrazine, ametryn, cyanazine, simazine, propazine, simetryn, love to kill ( Dimethametryn), prometryn, metribuzin, three Triaziflam, indaziflam, etc.; (5) bipyridinium herbicidal compound paraquat, diquat, etc.; (6) hydroxybenzonitrile a herbicidal compound, bromoxynil, ioxynil, etc.; (7) a dinitroaniline herbicidal compound, pendimethalin, prodiamine, trifluralin, etc.; (8) organophosphorus herbicidal compounds amiprofos-methyl, butamifos, bensulide, piperophos, anilofos, jiaphos Glyphosate, glufosinate, glufosinate-P, bialaphos, etc.; (9) carbamate is a herbicidal compound oat enemy (di- Allate), tri-allate, EPTC, butarate, benthiocarb, esprocarb, molate, dimepiperate, extinction Swipe, chlorpropham, phenmedipham, phenisopham, pyributicarb, asulam, etc.; (10) guanamine herbicide Compounds such as propanil, propyzamide, bromobutide, etobenzanid, etc.; (11) chloroacetamide-containing herbicidal compound acetochlor, Alachlor, butachlor, dimethenamid, propachlor, metazachlor, metolachlor, pretilachlor, hin (thenylchlor), cetoxine, etc.; (12) diphenyl ether herbicidal compound acifluorfen-sodium, bifenox, oxyfluorfen, milk Lactofen, fomesafen, chlomethoxynil, aclifen, etc.; (13) cyclic quinone imine herbicidal compound oxadiazon ), cinidon-ethyl, carfentrazone-ethyl, sulfentrazone, flumiclorac-pentyl, flumioxazin ), pyraflufen-ethyl, propyne Oxadiargyl, cyclopentane Penoxoxazone, fluthiacet-methyl, butafenacil, benzfendizone, bencarbazone, saflufenacil, etc.; 14) pyrazole-based herbicidal compounds benzofenap, pyrazolate, pyrazoxyfen, topramezone, pyrosulfotole, etc.; (15) three Ketone herbicidal compound Isoxaflutole, benzobicyclon, sulcotrione, mesotrione, tembotrione, tefuryltrione, bicyclopyrene Bicyclopyrone, etc.; (16) aryloxyphenoxypropionic acid herbicidal compound clodinafop-propargyl, cyhalofop-butyl, diclofop-methyl, Fenoxaprop-ethyl, fluazifop-butyl, haloxyfop-methyl, quizalofop-ethyl, (13) Trione oxime is a herbicidal compound of alloxydim-sodium, sethoxydim, butroxydim, keto (clethodim), cloproxydim, cycloxydim, tepraloxydim, tralkoxydim, profoxydim, etc.; (18) sulfonium urea-based herbicide Compounds chlorsulfuron, sulfometuron-methyl, metsulfuron-methyl, chlorimuron-ethyl, methotrexate Tribenuron-methyl), triasulfuron, bensulfuron-methyl, thifensulfuron-methyl, pyrazosulfuron-ethyl, primisulfuron -methyl), nicosulfuron, amidosulfuron, cinosulfuron, imazosulfuron, rimsulfuron, halosulfuron-methyl , prosulfuron, ethametsulfuron-methyl, triflusulfuron-methyl ), flazasulfuron, cyclosulfamuron, flupyrsulfuron, sulfosulfuron, azimusulfuron, ethoxysulfuron, ring Oxalsulfuron, iodosulfuron-methyl-sodium, foramsulfuron, mesosulfuron-methyl, trifloxysulfuron , tritosulfuron, orthosulfamuron, flucetosulfuron, Propyrisulfuron, metazosulfuron, iofensulfuron-sodium, etc.; (19) imidazolinone is a herbicidal compound of methyl oxalate ( Imazamethabenz-methyl), imazamox, imazapic, imazapyr, imazaquin, imimathapyr, etc.; (20) sulfonate Acid amine herbicidal compound flumetsulam, metosulam, diclosulam, florasulam, chlorosulphos cloransulam -methyl), penoxsulam, pyroxulam, etc.; (21) pyrimidinyloxybenzyl acid herbicidal compound pyrithiobac-sodium, bispyribac -sodium), pyrimanobac-methyl, pyrimibenzoxim, pyrifalid, pyrimisulfan, triafamone, etc.; (22) other systems Herbicidal compounds bentazone, bromacil, terbacil, chlorthiamid, different Isoxaben, dinoseb, amitrol, cinmethylin, tridiphane, dalapon, diflufenzopyr- Sodium), dithiopyr, thiazopyr, flucarbazone-sodium, propoxycarbazone-sodium, mefenacet, flutica Flufenacet, fentrazamide, cafenstrole, indanofan, Oxaziclomefone, benfuresate, ACN, pyridate, chloridazon, norflurazon, flurtamone, diflufenican ), picolinafen, beflubutamid, clomazone, amicarbazone, pinoxaden, pyraclonil, Pyroxasulfone, thiencarbazone-methyl, aminocyclopyrachlor, ipfencarbazone, iso Methiozolin, fenoxasulfone.

As the active ingredient of such a drug reducing agent, for example, the following compounds can be mentioned.

Benoxacor, cloquintocet-mexyl, cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, chlorpyrifos (flurazole), furilazole, mefenpyr-diethyl, MG191, oxabetrinil, allidochlor, diphenyl Isoxadifen-ethyl, cyprosulfamide, fluxofenim, 1,8-naphthalic anhydride, AD-67.

Examples of the active ingredient of the plant growth regulator include the following compounds.

Hymexazol, paclobutrazol, uniconazole-P, inabenfide, prohexadione-calcium, aviglicine, 1-naphthyl Naphthalene acetamide, abscisic acid, indolebutyric acid, ethychlozate, ethephon, cloxyfonac, chlormequat , 2,4-dipropionic acid, gibberellins, prohydrojasmon, benzyladenine, forchlorfenuron, maleic hydrazide ), calcium peroxide, shrinkage Mepiquat-chloride, 4-chlorophenoxyacetic acid (4-CPA).

As the active ingredient of such an insecticide, the following compounds are mentioned, for example.

(1) Organic phosphorus compounds

Acephate, butathiofos, chlorethoxyfos, chlorfenvinphos, chlorpyrifos, chlorpyrifos-methyl, cyanosom : CYAP), diazinon, deichlofenthion (ECP), dichlorvos (DDVP), dimethoate, dimethylvinphos, disulfoton , EPN, ethion, ethoprophos, etrimfos, fenthion (MPP), fenitrothion (MEP), fosthiazate, buckwood Formothion, isofenphos, isoxathion, malathion, mesulfenfos, methidathion (DMTP), monocrotophos, nitsin (naled: BRP), oxydeprofos (ESP), parathion, phosalone, phosmet (PMP), pirimiphos-methyl, must Pyridafenthion, quinalphos, phenthoate (PAP), profenofos, Propaphos, prothiofos, pyraclofos, salithion, sulprofos, tebupirimfos, temephos, insecticide Tetrachlorvinphos, terbufos, thiometon, trichlorphon (DEP), vamidothion, phorate, and cadusafos.

(2) urethane compounds

Alanycarb, bendiocarb, benfuracarb, BPMC, carbaryl, carbofuran, carbosulfan, cloethocarb , ethiofencarb, fenobucarb, fenothiocarb, fenoxycarb, furathiocarb, isoprocarb (MIPC), sputum (metolcarb), methomyl, methiocarb, oxamyl, pirimicarb, propoxur (PHC), XMC, thiodicarb, annihilation Xylylcarb, aldicarb.

(3) Pyrethrin compounds

Acrinathrin, allethrin, beta-cyfluthrin, bifenthrin, cycloprothrin, cyfluthrin, cyhalothrin , cypermethrin, empenthrin, deltamethrin, esfenvalerate, ethofenprox, fenpropathrin, fenvalerate, care Flucythrinate, flufenoprox, flumethrin, fluvalinate, halfenprox, imiprothrin, permethrin , prallethrin, pyrethrins, resmethrin, sigma-cypermethrin, silafluofen, tefluthrin, thai Tralomethrin, transfluthrin, tetramethrin, phenothrin, cyphenothrin, alpha-cypermethrin, and statin Zeta-cypermethrin), lambda-cyhalothrin, gamma-cyhalothrin, normidine ester (furamethrin), tau-fluvalinate, metofluthrin, profluthrin, dimefluthrin, 2,2-dimethyl-3-(2 -cyano-1-propenyl)cyclopropanecarboxylate 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl, 2,2,3,3-tetramethylcyclopropanecarboxylic acid 2,3,5,6-tetrafluoro-4-(methoxymethyl)benzyl ester, protrifenbute.

(4) Nereis toxin compounds

Cartap, bensultap, thiocyclam, monosultap, bisultap.

(5) Neonicotinoid compounds

Imidacloprid, nitenpyram, acetamiprid, thiamethoxam, thiacloprid, dinotefuran, and clothianidin.

(6) benzyl hydrazine urea compound

Chlorfluazuron, bistrifluron, diflubenzuron, flulazuron, flucycloxuron, flufenoxuron, hexaflumuron , Lufenuron, novaluron, Noviflumuron, teflubenzuron, and triflumuron.

(7) Phenylpyrazole compound

Acetopyronitrile, ethiprole

Fipronil, vaniliprole, pyriprazole, pyridin Pyrafluprole.

(8) Bt toxin

Sprouts derived from Bacillus thuringiensis and producing crystal poison And the mixture of these.

(9) hydrazine compound

Chromofozide, halofenozide, methoxyfenozide, tebufenozide.

(10) organochlorine compounds

Aldrin, dieldrin, chlordane, DDT, dienochlor, endosulfan, methoxychlor

(11) Other insecticidal active ingredients

Machine oil, nicotine sulfate; avermectin-B, new bromopropylate, buprofezin, chlorphenapyr, race Cyromazine, dichlorodiisopropyl ether (DCIP), 1,3-dichloropropene (DD), emamectin-benzoate, fenazaquin , flupyrazofos, hydroprene, methoprene, indoxacarb, metoxadiazone, milbemycin-A, degenerate Pymetrozine, pyridalyl, pyriproxyfen, spinosad, sulfluramid, tolfenpyrad, triazamate, fluoride Flubendiamide, lepimectin, aluminium phosphide arsenous oxide, benclothiaz, calcium cyanamide, lime sulfur mixture ( Calcium polysulfide), DSP, flonicamid, flurimfen, formetanate, hydrogen (hydrogen) Phosphate), metam-ammonium, metam-sodium, methyl bromide, potassium oleate, spiromesifen, aphids Sulfoxaflor, sulfur, metaflumizone, spirotetramat, pyrifluquinazone, spinetoram, chlorantraniliprole , tralopyril, diafenthiuron.

a compound represented by the formula (A): (wherein, X ^a1 represents methyl, chlorine, bromine or fluorine, X ^a2 represents fluorine, chlorine, bromine, C ₁ to C ₄ haloalkyl or C ₁ to C ₄ haloalkoxy, and X ^a3 represents fluorine, chlorine Or bromine, X ^a4 represents a C ₁ to C ₄ alkyl group which may be substituted, a C ₃ to C ₄ alkenyl group which may be substituted, a C ₃ to C ₄ alkynyl group which may be substituted, a C ₃ to C which may be substituted ₅ cycloalkylalkyl or hydrogen, X ^a5 represents hydrogen or methyl, X ^a6 represents hydrogen, fluorine or chlorine, X ^a7 represents hydrogen, fluorine or chlorine)

a compound represented by the formula (B):

(wherein, X ^b1 represents X ^b2 -NH-C(=O) group, X ^b2 -C(=O)-NH-CH ₂ group, X ^b3 -S(O) group, substituted pyrrole-1 - group, may be substituted imidazol-1-yl, may be substituted pyrazol-1-yl or may be substituted triazol-1-yl, X ^b3 represents 2,2,2 a trifluoroethyl group or the like which may be substituted C ₁ to C ₄ haloalkyl or cyclopropyl, etc. may be substituted C ₃ to C ₈ cycloalkyl, and X ^b3 represents a methyl group or the like which may be substituted C ₁ to C ₄ Alkyl, X ^b4 represents hydrogen, chlorine, cyano or methyl)

a compound represented by the formula (C): (Wherein, X ^c1 represents a 3,3,3-trifluoropropyl group and the like can be substituted by C ₁ to C ₄ alkyl, 2,2,2-trichloroethoxycarbonyl and the like can be substituted by C ₁ to C _4-alkoxy, 4-cyanophenyl and the like may be substituted phenyl or 2-chloro-3-pyridyl and the like may be substituted pyridyl group, X ^c2 represents methyl or trifluoromethylthio, X ^c3 represents methyl Base or halogen)

As the active ingredient of such an acaricide, for example, the following compounds can be mentioned.

Acequinocyl, amitraz, benzoximate, bifenazate, bromopropylate, chinomethionat, chlorobenzilate, PCBS ( Chlorfenson), clofentezine, cyflumetofen, dicofol, etoxazole, fenbutatin oxide, fenothiocarb, fenproxil Fenpyroximate), fluacrypyrim, halfenprox, hexythiazox, propargite (BPPS), polynactins, pyripaben, Pyrimidifen, tebufenpyrad, tetradifon, spirodiclofen, spiromesifen, spirotetramat, amidoflumet, and Cyanopyrafen.

As the active ingredient of such a nematicide, for example, the following compounds can be mentioned.

DCIP, fosthiazate, levamisol hydrochloride, methylisothiocyanate, morantel tartarate, and imicyafos.

Examples of the active ingredient of such a bactericide include the following compounds.

(1) Polyhaloalkylthio compounds

Captan, folfet, etc.

(2) Organic phosphorus compounds

IBP, EDDP, tolclofos-methyl, and the like.

(3) benzimidazole compounds,

Benomyl, carbendazim, thiophanate-methyl, thiabendazole, and the like.

(4) Carboxamide compound

Carboxin, mepronil, fluolanil, thifluzamid, furametpyr, boscalid, penthiopyrad, and the like.

(5) Dicarboxy quinone imine compound

Procymidone, iprodione, vinclozolin, etc.

(6) mercaptoalanine compound

Metalaxyl and the like.

(7) azole compound

Triadimefon, triadimenol, propiconazole, tebuconazole, cyproconazole, epoxiconazole, prothioconazole, inocastazole Ipconazole), triflumizole, prochloraz, penconazole, flusilazole, diniconazole, bromuconazole, difenoconazole, extinction Metconazole, tetraconazole, myclobutanil, fenbuconazole, hexaconazole, fluquinconazole, triticonazole, bitertanol , Imazalil, flutriafol, etc.

(8) morpholine compound

Dodemorph, tridemorph, fenpropimorph, and the like.

(9) methoxy acrylate (strobilurin) compound

Azoxystrobin, kresoxim-methyl, metominostrobin, trifloxystrobin, picoxystrobin, pyraclostrobin, fluoxastrobin Fluoxastrobin), dimoxystrobin, and the like.

(10) Antibiotics

Validamycin A, blasticidin S, kasugamycin, polyoxin, and the like.

(11) Dithiocarbamate compound

Mancozeb, maneb, thiuram, etc.

(12) Other bactericidal active ingredients

Fthalide, probenazole, isoprothiolane, Tricyclazole, pyroquilon, ferimzone, acibenzolar S-methyl, carpropamid, chloramphenicol ( Diclocymet), fenoxanil, tiadinil, diclomezine, teclofthalam, pencycuron, oxolinic acid, TPN, race Triforine, fenpropidin, spiroxamine, fluazinam, iminoctadine, fenpiclonil, fludioxonil, sinuo Quinoxyfen, fenhexamid, silthiofam, proquinazid, cyflufenamid, basic copper sulphate (bordeaux mixture; bordeaux mixture) , dichlofluanid, cyprodinil, pyrimethanil, mepanipyrim, diethofencarb, pyribencarb, famoxadone , fenamidone, zoxamide, ethaboxam, amisulbrom, propyl (iprovalicarb), benthiavalicarb, cyazofamid, mandipropamid, metrafenone, fluopiram, bixafen )Wait.

As the active ingredient of such a synergist, the following compounds are mentioned, for example.

Piperonyl butoxide, sesamex, sulfoxide, N-(2-ethylhexyl)-8,9,10-tris-5-ene-2,3 - dimethyl quinone imine (MGK 264), N-declyimidazole, WARF-N, N-dibutyl-p-chlorobenzene sulfonamide (WARF-antiresistant), TBPT, TPP, IBP, PSCP , methane iodide (CH ₃ I), t-phenylbutenone (t-phenylbutenone), diethylmaleate, DMC, FDMC, ETP, and ETN.

For the object of controlling the herbicide of the present invention, for example, the following plants can be mentioned.

Digitaria ciliaris, Eleusine indica, Setaria viridis, Setaria faberi, Setaria glauca, Echinochloa crus-galli, Panicum dichotomiflorum ), Panicum texanum, Brachiaria platyphylla, Brachiaria plantaginea, Brachiaria decumbens, Sorghum halepense, Andropogon sorghum, Bermudagrass Cynodon dactylon), Avena fatua, Lolium multiflorum, Alopecurus myosuroides, Bromus tectorum, Bromus sterilis, Kidnapper (Phalaris minor), Apera spica-venti, Poa annua, Agropyron repens, Cyperus iria, Cyperus rotundus, Cyperus Esculentus), Portulaca oleracea, Amaranthus retroflexus, Amaranthus hybridus, Amaranthus palmeri, Amaranthus rudis, Castor Lon theophrasti), Sida spinosa, Fallopia convolvulus, Polygonum scabrum, Persicaria pennsylvanica, Persicaria vulgaris, Rumex crispus ), Rumex obtusifolius, Fallopia japonica, Chenopodium album, Kochia scoparia, Polygonum longisetum, Solanum nigrum, Datura stramonium, Ipomoea purpurea, Ipomoea hederacea, Ipomoea hederacea var.integriuscula, Ipomoea lacunosa, Convolvulus Arvensis), Lamium purpureum, Lamium amplexicaule, Xanthium pensylvanicum, Helianthus annuus, Matricaria perforata or inodora, Matricaria chamomilla , Chrysanthemum segetum, Matricaria matricarioides, Ambrosia artemisiifolia, Ambrosia trifida, Erigeron canadensis, Artemisia princeps, North America Yellow flower (Solidago altissima), Conyza bonariensis, Sesbania exaltata, Cassia obtusifolia, Desmodium tortuosum, Trifolium repens, Pueraria lobata, Vicia angustifolia, Commelina communis, Commelina benghalensis, Galium aparine, Stellaria media, Raphanus raphanistrum, wild mustard (Sinapis arvensis), amaranth (Capsella bursa-pastoris), Veronica persica, eyelashes (Ver) (onica hederifolia), wild leek (Viola arvensis), Viola tricolor, Papaver rhoeas, Myosotis scorpioides, Asclepias syriaca, Euphorbia helioscopia, Chamaesyce nutans, Geranium carolinianum, Erodium cicutarium, Equisetum arvense, Leersia japonica, Echinochloa oryzicola, Taiwan wild Echinochloa crus-galli var.formosensis, Leptochloa chinensis, Cyperus difformis, Fimbristylis miliacea, Eleocharis acicularis, Scirpus juncoides, pigs Scirpus wallichii, Cyperus serotinus, Eleocharis kuroguwai, Bolboschoenus koshevnikovii, Schoenoplectus nipponicus, Monochoria vaginalis, Lindernia procumbens, Dopatrium junceum, Rotala indica, Ammannia multiflora, Eladine triandra, Ludwigia epilobioides, Sagittaria pygmaea, Alisma canaliculatum, Sagittaria trifolia, eye Potamogeton distinctus, Oenanthe javanica, Callitriche palustris, Lindernia micrantha, Lindernia dubia, Eclipta prostrata, water bamboo leaves Weeds such as Murdannia keisak), Paspalum distichum, and Leersia oryzoides.

Alternanthera philoxeroides, Limnobium spongia, water fern (Salvinia genus), Pistia stratiotes, water pennywort (days) Hydrocotyle, filamentous algae (Pithophora, Cladophora), Ceratophyllum demersum, Zippin (Lemna), white flower (Cabomba caroliniana), Hydrilla verticillata, Najas guadalupensis, pondweed (Potamogeton crispus, Potamogeton illinoensis, dragon mustard) Grass (Potamogeton pectinatus), etc., water meal (Wolffia genus), watermilfoil (Myriophyllum spicatum), Myriophyllum heterophyllum Etc.), aquatic plants such as Eichhornia crassipes. Mosses, mosses, horns. Cyanobacteria. fern. Long-handed crops (such as pome fruits, stone fruits, berries, nuts, citrus, hops, grapes, etc.).

The compound of the present invention can be produced, for example, by the following production method.

Manufacturing Method 1

The compound represented by the formula (I-a) wherein G is hydrogen in the compound of the present invention is produced by a reaction of a compound represented by the formula (II), a compound represented by the formula (III) and a base.

Wherein X ¹ represents fluorine or chlorine, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A represent the same meaning as described above]

This reaction is usually carried out in a solvent. Examples of the solvent that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether and An ether such as an alkane, tetrahydrofuran (hereinafter abbreviated as THF) or dimethoxyethane; an amide such as dimethylformamide (hereinafter abbreviated as DMF); dimethyl hydrazine (hereinafter, abbreviated as DMSO) ) such as an anthraquinone; a nitrile such as acetonitrile; a ketone such as acetone or a mixed solvent thereof.

The base to be used in the reaction may, for example, be a metal alkoxide such as a tertiary potassium hydride or an inorganic base such as potassium carbonate, cesium carbonate or sodium hydride.

The compound represented by the formula (III) used in the present reaction is usually used in an amount of from 0.5 to 3 mol equivalents, preferably from 1 to 2 mol equivalents, based on the compound represented by the formula (II).

The amount of the base used in the reaction is usually from 1 to 1.0 mol equivalents, preferably from 1 to 3 mol equivalents, based on the compound represented by the formula (II).

The reaction temperature of the reaction is usually from 0 to 200 ° C, preferably from 20 to 100 ° C. The reaction time of the reaction is usually from 10 minutes to 30 hours.

After the completion of the reaction, it can be neutralized by, for example, adding an acid to the reaction mixture, mixed with water, extracted with an organic solvent, and the obtained organic layer is dried and concentrated to obtain a cerium oxide gel column chromatography. The compound represented by the formula (Ia) is isolated by an operation such as purification.

The compound represented by the formula (III) is a known compound or may be produced from a known compound.

Manufacturing method 2

In the compound of the present invention, a compound represented by the formula (I-b) wherein G is a group other than hydrogen can be produced by a reaction of a compound represented by the formula (I-a), a compound represented by the formula (IV) and a base.

Wherein G ¹ represents hydrogen other than the definition of G, X ² represents chlorine, bromine or iodine, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ and A represent the same meaning as described above]

This reaction is usually carried out in a solvent. Examples of the solvent that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether and An ether such as an alkane, THF or dimethoxyethane; a guanamine such as DMF; an anthracene such as DMSO; a nitrile such as acetonitrile; a ketone such as acetone or a mixed solvent thereof.

Examples of the base to be used in the reaction include inorganic bases such as potassium carbonate, cesium carbonate, and sodium hydride; triethylamine, pyridine, and 1,8-diazabicyclo[5.4.0]-7-undecene. Such as organic bases.

The compound represented by the formula (IV) used in the present reaction is usually used in an amount of from 0.5 to 10 mol equivalents, preferably from 1 to 3 mol equivalents, based on the compound represented by the formula (I-a). The amount of the base to be used in the reaction is usually from 0.5 to 10 mol equivalents, preferably from 1 to 5 mol equivalents, based on the compound represented by the formula (I-a).

The reaction temperature of the reaction is usually from -30 to 180 ° C, preferably from -10 to 80 ° C.

The reaction time of the reaction is usually from 10 minutes to 30 hours.

After the completion of the reaction, for example, the reaction mixture may be mixed with water, extracted with an organic solvent, and the obtained organic layer may be dried, concentrated, and purified by cerium oxide gel column chromatography, and separated. Compound represented by Ib). The compound represented by the formula (IV) is a known compound or may be produced from a known compound.

Manufacturing method 3

In the compound of the present invention, the compound represented by the formula (I-c) can be produced by reacting a compound represented by the formula (I-a) with a compound represented by the formula (V).

_Wherein R ¹⁰ represents a C _1-12 alkyl group, a C _3-8 cycloalkyl group, a C _2-12 alkenyl group, a C _2-12 alkynyl group, and may have one or more atoms selected from the D group or C _6-10 aryl group, (C _6-10 aryl group may have one or more atom or group selected from the group D) C _1-6 alkyl, (C _3-8 cycloalkyl) C _{1 -6} alkyl, (C _1-6 alkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, (C _1-6 alkylthio) C _{1- 6} alkyl, (C _1-6 alkylsulfinyl) C _1-6 alkyl, (C _1-6 alkylsulfonyl) C _1-6 alkyl, (may have 1 selected from group D one or more atoms or a C _6-10 aryloxy group) C _1-12 alkyl, (optionally having one or more atom or group selected from the group D C _6-10 arylthio) C _{1 -12} alkyl, {(C _6-10 aryl which may have 1 or more atoms selected from the D group) C _1-6 alkoxy} C _1-6 alkyl or 5 to 6 membered hetero The aryl group, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , A and D groups represent the same meaning as described above]

This reaction is usually carried out in a solvent. Examples of the solvent that can be used include aromatic hydrocarbons such as benzene, toluene, and xylene; diethyl ether and An ether such as an alkane, THF or dimethoxyethane; a guanamine such as DMF; an anthracene such as DMSO; a nitrile such as acetonitrile; a ketone such as acetone or a mixed solvent thereof.

A base can also be used in the reaction. Examples of the base which can be used include inorganic bases such as potassium carbonate, cesium carbonate and sodium hydride; and organic groups such as triethylamine, pyridine and 1,8-diazabicyclo[5.4.0]-7-undecene. Alkali. The amount of the base used in the reaction is usually from 0.5 to 10 mol equivalents based on the compound represented by the formula (I-a).

The compound represented by the formula (V) is usually used in an amount of from 1 to 20 mol equivalents based on the compound represented by the formula (I-a).

The reaction temperature of this reaction is usually from -30 to 180 °C. The reaction time of the reaction is usually from 10 minutes to 30 hours.

After completion of the reaction, for example, the reaction mixture may be mixed with water, extracted with an organic solvent, and the obtained organic layer may be dried, concentrated, and purified by cerium oxide gel column chromatography, and the separation method (Ic) ) the compound indicated. The compound represented by the formula (V) is a known compound or may be produced from a known compound.

Each of the compounds produced by the above Production Methods 1 to 3 may be isolated/purified by other known means such as a method such as dissolving, crystallization, recrystallization, or chromatography.

The method for producing the intermediate of the compound of the present invention is described below as a reference production method.

Reference manufacturing method 1

The compound represented by the formula (II) can be produced by, for example, reacting a compound represented by the formula (VI) with an acid.

Wherein R ¹⁵ represents a C _1-6 alkyl group or a benzyl group, R ¹⁶ represents hydrogen, a C _1-6 alkyl group or a benzyl group, and R ¹ , R ² , R ³ , R ⁴ and R ⁵ represent the same as defined above. Meaning]

As the acid to be used in the reaction, for example, hydrochloric acid or hydrogen bromide may be mentioned. The acid used in the present reaction is usually used in an amount of from 1 to 20 mol equivalents based on the compound represented by the formula (VI).

The reaction is carried out in the absence of a solvent or in a solvent. Examples of the usable solvent include organic acids such as acetic acid and propionic acid, and water or mixed solvents thereof.

The reaction temperature of the reaction is usually from 30 to 180 ° C, preferably from 50 to 130 ° C. The reaction time of the reaction is usually from 10 minutes to 30 hours.

After completion of the reaction, for example, the reaction mixture may be mixed with water, extracted with an organic solvent, and the obtained organic layer may be dried, concentrated, and purified by cerium oxide gel column chromatography, and separated (II). ) the compound indicated.

The compound represented by the formula (VI) is a known compound or may be produced from a known compound. It can also be produced, for example, in accordance with the method described in EP 2204366 A or WO 2009/035150.

Reference Manufacturing Method 2

The compound represented by the formula (VI-a) in the compound represented by the formula (VI) can be present in the presence of a catalyst and a base by, for example, a compound represented by the formula (VII) and a compound represented by the formula (VIII). Manufactured by the next reaction.

[wherein, X ² , R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ^{15 have the} same meanings as described above]

This reaction is usually carried out in a solvent. Examples of the solvent that can be used include aromatic hydrocarbons such as benzene and toluene; alcohols such as methanol, ethanol, and propanol; diethyl ether and An ether such as an alkane, THF or dimethoxyethane; a ketone such as acetone or methyl ethyl ketone: a guanamine such as DMF; an anthraquinone such as DMSO; water or a mixed solvent thereof.

The base to be used in the reaction may, for example, be an inorganic base such as sodium carbonate, potassium carbonate, sodium hydrogencarbonate, cesium carbonate or potassium phosphate. The base to be used is usually used in an amount of from 1 to 10 mol equivalents, preferably from 1 to 5 mol equivalents, based on the compound represented by the formula (VII).

The catalyst used in the reaction may, for example, be a palladium catalyst such as palladium (II) acetate, tetrakis(triphenylphosphine)palladium or tris(dibenzylideneacetone)dipalladium. The amount of the catalyst to be used is usually 0.001 to 0.5 mol equivalent, and preferably 0.01 to 0.2 mol equivalent, based on the compound represented by (VII).

A ligand can also be added in this reaction. Examples of the ligand to be used include 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl and the like. The amount of the ligand to be used is usually 0.002 to 1 mol equivalent, and preferably 0.02 to 0.4 mol equivalent, based on the compound represented by the formula (VII).

The compound represented by the formula (VIII) used in the present reaction is usually used in an amount of from 0.5 to 2 mol equivalents, preferably from 1 to 1.5 mols, based on the compound represented by the formula (VII). equivalent.

The reaction temperature of the reaction is usually from 0 to 180 ° C, preferably from 30 to 150 ° C. The reaction time of the reaction is usually from 10 minutes to 100 hours.

After completion of the reaction, for example, the reaction mixture may be mixed with water, extracted with an organic solvent, and the obtained organic layer may be dried, concentrated, and purified by cerium oxide gel column chromatography, and separated (VI). a compound represented by -a).

The compound represented by the formula (VIII) is a known compound or may be produced from a known compound.

The compound represented by the formula (VII) is a known compound or may be produced from a known compound. For example, it can be produced according to the method described in J. Heterocycl. Chem, 33, pages 1579 to 1582 (1996), or the like.

Reference Manufacturing Method 3

The compound represented by the formula (XV) wherein R ² is OR ¹⁷ and X ² is chlorine in the compound represented by the formula (VII) can be produced, for example, by the following reaction scheme.

In the formula, X ³ represents chlorine, bromine, iodine, or a C _1-3 alkylsulfonyloxy group which may have a halogen (for example, a methylsulfonyloxy group, a trifluoromethylsulfonyloxy group, etc.) , phenylsulfonyl or p-toluenesulfonyl, R ¹⁷ represents C _1-6 alkyl, C _1-6 haloalkyl, C _3-8 cycloalkyl, (C _3-8 cycloalkyl) C _{1 -6} alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (C _1-6 alkoxy) C _1-6 alkyl, C _3-6 alkenyl, C _3-6 alkynyl , cyano C _1-6 alkyl, (C _1-6 alkoxy)carbonyl C _1-6 alkyl, amine mercapto C _1-6 alkyl, [(C _1-6 alkyl)aminocarbonyl C _1-6 alkyl or (di(C _1-6 alkyl)aminocarbonyl) C _1-6 alkyl, and R ¹ and R ^{15 have the} same meanings as defined above. ]

Step 1 is a method of producing a compound represented by the formula (XI) by reacting a compound represented by the formula (IX) with a compound represented by the formula (X). This reaction is a dehydration condensation reaction of maleic anhydride with a hydrazine compound, and can be reacted under known conditions. For example, it can be manufactured in accordance with the method described in US7816357B.

Step 2 is a method of producing a compound represented by the formula (XIII) by reacting a compound represented by the formula (XI) with a compound represented by the formula (XII) in the presence of a base. This reaction can be carried out under known conditions. For example, it can be manufactured in accordance with the method described in WO2012/091156.

In the step 3, a compound represented by the formula (XV) can be produced by reacting a compound represented by the formula (XIII) and a compound represented by the formula (XIV) in the presence of a base.

This reaction is usually carried out in a solvent. Examples of the solvent that can be used include alcohols such as methanol, ethanol, and propanol; diethyl ether and An ether such as an alkane, THF or dimethoxyethane; a guanamine such as DMF; an anthraquinone such as DMSO or a mixed solvent thereof.

Examples of the base used in the reaction include sodium methoxide, tertiary potassium pentoxide, and sodium hydride. The amount of the base used in the reaction is usually from 0.5 to 10 mol equivalents, preferably from 1 to 1.5 mol equivalents, based on the compound represented by the formula (XIII).

The reaction temperature of the reaction is usually from -30 to 100 °C. The reaction time of the reaction is usually from 10 minutes to 50 hours.

After the completion of the reaction, for example, the reaction mixture is mixed with water, extracted with an organic solvent, and the obtained organic layer is dried, concentrated, and the like, and the separation formula (XV) is carried out. The compound represented.

Specific examples of the compound of the present invention are shown below.

1) A kind of 嗒 a ketone compound wherein, in the formulae (I ¹ ) to (I ⁵¹ ), G is hydrogen, and A is phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorobenzene Base, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2-methylphenyl, 3-methylphenyl, 4-methyl Phenyl, 2-trifluoromethylphenyl, 3-trifluoromethylphenyl, 4-trifluoromethylphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxy Phenylphenyl, 2-trifluoromethoxyphenyl, 3-trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, 2-nitrophenyl, 3-nitrophenyl, 4-nitrobenzene Base, 2-cyanophenyl, 3-cyanophenyl, 4-cyanophenyl, 2-fluoro-4-chlorophenyl, 2-fluoro-4-cyanophenyl, 2-fluoro-4-trifluoromethyl Phenyl, 2,4-dichlorophenyl, 2-chloro-4-cyanophenyl, 2-chloro-4-trifluoromethylphenyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 3-fluoropyridin-2-yl, 4-fluoropyridin-2-yl, 5-fluoropyridin-2-yl, 6-fluoropyridin-2-yl, 3-chloropyridin-2-yl, 4-chloropyridine- 2-yl, 5-chloropyridin-2-yl, 6-chloropyridin-2-yl, 3-trifluoromethylpyridin-2-yl, 4-trifluoromethylpyridin-2-yl, 5-trifluoro Methylpyridin-2-yl, 6-trifluoromethylpyridin-2-yl 3,5-difluoropyridine 2-yl, 3-fluoro-5-chloro-pyridin-2-yl, 3-fluoro-5-trifluoromethyl-pyridin-2-yl, 3-chloro-5-fluoropyridine -2-yl, 3,5-dichloropyridin-2-yl, 3-chloro-5-trifluoromethylpyridin-2-yl, 2-pyrimidinyl, 5-fluoropyrimidine, 5-chloropyrimidinyl, 6 -chlorine 3-yl, 2-quinolyl, 6-fluoroquinolin-2-yl, 7-fluoroquinolin-2-yl, 6-chloroquinolin-2-yl, 7-chloroquinolin-2-yl, 6 -trifluoromethylquinolin-2-yl, 7-trifluoromethylquinolin-2-yl, quin Porphyrin-2-yl, 6-fluoroquine Phenyl-2-yl, 6-chloroquine Oxa-2-yl, 6-trifluoromethylquin Benzin-2-yl, quinazolin-2-yl, 6-fluoroquinazolin-2-yl, 6-chloroquinazolin-2-yl, 6-trifluoromethylquinazolin-2-yl, benzene and Zin-2-yl, 5-fluorobenzo Zin-2-yl, 5-chlorobenzo Zyridin-2-yl, 5-trifluoromethylbenzo Zin-2-yl, 6-fluorobenzo Zin-2-yl, 6-chlorobenzo Zin-2-yl, 6-trifluoromethylbenzo Zin-2-yl, benzothiazol-2-yl, 5-fluorobenzothiazol-2-yl, 5-chlorobenzothiazol-2-yl, 5-trifluoromethylbenzothiazol-2-yl, 6-fluorobenzothiazol-2-yl, 6-chlorobenzothiazol-2-yl, 6-trifluoromethylbenzothiazol-2-yl, benzo[1,2,4]tri -3-yl, 6-fluorobenzo[1,2,4]3 3-yl, 6-chlorobenzo[1,2,4]3 -3-yl, 7-fluorobenzo[1,2,4] -3-yl or 7-chlorobenzo[1,2,4] -3- base.

2) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 4-trifluoromethylphenyl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, Isoamyl, trimethylethenyl, 2,2-dimethylbutyryl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, benzyl Mercapto, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethenyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, three Butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, phenylsulfonyl, p-Toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

3) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 2-fluoro-4-cyanophenyl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group. , isoamyl, trimethylethenyl, 2,2-dimethylbutanyl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, Benzylidene, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethenyl, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, Tertiary butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl , p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

4) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 2-chloro-4-trifluoromethylphenyl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, and a butyl fluorenyl group. , Isobutyl fluorenyl, isoamyl decyl, trimethylethenyl, 2,2-dimethylbutanyl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, ring Hexylcarbonyl, benzindenyl, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, isopropoxy Carbocarbonyl, tertiary butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzene Sulfonyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

5) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 5-trifluoromethylpyridin-2-yl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, Isobutyl fluorenyl, isoamyl decyl, trimethyl ethinyl, 2,2-dimethylbutanyl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexyl Carbonyl, benzamidine, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethenyl, methoxycarbonyl, ethoxycarbonyl, isopropoxy Carbonyl, tertiary butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonate Indenyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

6) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 2-fluoro-5-trifluoromethylpyridin-2-yl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propylene group Base, butyl sulfhydryl, isobutyl fluorenyl, isoamyl decyl, trimethyl ethinyl, 2,2-dimethylbutyryl, 3,3-dimethylbutyryl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentyl Carbonyl, cyclohexylcarbonyl, benzindenyl, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, Isopropoxycarbonyl, tert-butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonate Base, phenylsulfonyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

7) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 2-chloro-5-trifluoromethylpyridin-2-yl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, and a propyl hydrazine group. Base, butyl sulfhydryl, isobutyl fluorenyl, isoamyl sulfhydryl, trimethyl ethane fluorenyl, 2-methylbutyl fluorenyl, 3-methylbutyl fluorenyl, 2,2-dimethylbutyl fluorenyl, 3,3-dimethylbutyl fluorenyl, pentyl Sulfhydryl, 2-methylpentanyl, 2-ethylpentanyl, 2-propylpentyl, hexyl, 2-methylhexyl, 2-ethylhexyl, phenyl Sulfhydryl, 3-phenylpropenyl, methoxyethyl, ethoxyethyl, propoxyethyl, 3-methoxypropenyl, 3-ethoxypropyl, 3-methoxy-2-methylpropanyl, ethylthiomethyl, 3-(methylthio)propanyl, phenoxyethyl, benzyloxyethyl, cyclopropylcarbonyl , cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, benzindenyl, 2-fluorobenzylidene, 3-fluorobenzylidene, 4-fluorobenzylidene, 2-chlorobenzylidene, 3-chloro Benzyl hydrazino, 4-chlorobenzyl hydrazino, 2-bromobenzylhydrazine, 4-bromobenzylhydrazine, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, 2 -ethylbenzylidene, 2-methoxybenzidine , 3-methoxybenzylidene, 4-methoxybenzylidene, 2-ethoxybenzylidene, 2-methylthiobenzylhydrazone, 4-cyanobenzylidene, 2-nitrobenzyl Indenyl, 4-nitrobenzylhydrazino, 2-(trifluoromethyl)benzylidene, 4-(trifluoromethyl)benzylidene, 4-(trifluoromethoxy)benzylidene, 2, 6-difluorobenzylhydrazone, 2,3-dichlorobenzylidene, 2,4-dichlorobenzylhydrazine, 2,5-dichlorobenzylhydrazino, 2,6-dichlorobenzylidene, 3, 4-Dichlorobenzylhydrazone, 3,5-dichlorobenzylhydrazone, 2,6-dimethylbenzylhydrazino, 2,6-dimethoxybenzylidene, methoxycarbonyl, ethoxycarbonyl , isopropoxycarbonyl, tertiary butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonate Mercapto, phenylsulfonyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

8) A kind of 嗒 a ketone compound wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 6-chloroquine 啉-2-yl, and G is ethyl fluorenyl, trifluoroethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, isobutyl decyl, isoamyl decyl, trimethyl ethinyl, 2,2-dimethylbutenyl, 3 ,3-dimethylbutyryl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, benzindenyl, 2-methylbenzylidene, 3-methylbenzylidene, 4-methyl Benzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tert-butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylamino Carbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or - Nitrobenzyl.

9) A kind of 嗒 a ketone compound wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 6-chlorobenzone Carb-2-yl, and G is ethyl fluorenyl, trifluoroethyl fluorenyl, propyl fluorenyl, butyl fluorenyl, isobutyl decyl, isoamyl decyl, trimethyl ethinyl, 2,2-dimethylbutenyl, 3 ,3-dimethylbutyryl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, benzindenyl, 2-methylbenzylidene, 3-methylbenzylidene, 4-methyl Benzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tert-butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylamino Carbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonyl, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or - Nitrobenzyl.

10) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is a benzothiazol-2-yl group, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group, and an isobutyl group. Pentamidine, trimethylethenyl, 2,2-dimethylbutanyl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl, benzamidine Base, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, tertiary Butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, phenylsulfonyl, Toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

11) A kind of 嗒 a ketone compound, wherein, in the formulae (I ¹ ) to (I ⁵¹ ), A is 6-chlorobenzothiazol-2-yl, and G is an ethyl fluorenyl group, a trifluoroethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, and a different Butyl, isoamyl, trimethylethenyl, 2,2-dimethylbutanyl, 3,3-dimethylbutanyl, cyclopropylcarbonyl, cyclobutylcarbonyl, cyclopentylcarbonyl, cyclohexylcarbonyl , benzindenyl, 2-methylbenzylidene, 3-methylbenzylidene, 4-methylbenzylidene, phenylethylhydrazine, methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl , tertiary butoxycarbonyl, phenoxycarbonyl, allyloxycarbonyl, dimethylaminocarbonyl, dimethylaminothiocarbonyl, methanesulfonyl, trifluoromethanesulfonyl, benzenesulfonate Base, p-toluenesulfonyl, methoxymethyl, ethoxymethyl, benzyl or 2-nitrobenzyl.

(Example)

The production examples, the reference examples, the formulation examples, and the test examples are shown below to more specifically illustrate the present invention, but the present invention is not limited by the examples.

In the production examples and the reference examples, the room temperature usually means 10 to 30 °C. ¹ H NMR is a proton nuclear magnetic resonance spectrum. The internal standard is tetramethyl decane, and the chemical shift ( δ ) is expressed in ppm.

The code used in the manufacturing example and the reference example has the following meanings.

CDCl ₃ : deuterated chloroform; DMSO-d ₆ : deuterated dimethyl hydrazine; s: single peak; d: doublet; t: triplet; q: four peaks; brs: broad single peak; dd: both Peak: m: multiplet; J: coupling constant; MTBE: tertiary butyl methyl ether; DMF: N,N-dimethylformamide; THF: tetrahydrofuran; Me: methyl; Et: ethyl; i-Pr: isopropyl; c-Pr: cyclopropyl; Bu: butyl; c-Bu: cyclobutyl; n-: positive; t-: tertiary; t-Bu: tertiary butyl Pen: pentyl; c-Pen: cyclopentyl; Hex: hexyl; c-Hex: cyclohexyl; Ph: phenyl; Bn: benzyl.

Manufacturing example 1

4-(2-ethyl-4-(4-cyano-2-fluorophenoxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-indole Synthesis of ketone (compound (I-1))

4-(2-Ethyl-4-hydroxyphenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime A mixed solution of a ketone (500 mg of the compound (II-1), 294 mg of 3,4-difluorobenzonitrile, 751 mg of cesium carbonate and 3 ml of DMF was stirred at 70 ° C for 30 minutes. The reaction solution was cooled to room temperature, and 2N hydrochloric acid was added thereto. After acidification, it was extracted twice with MTBE, and the combined organic layers were washed successively with water and brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. 273 mg of the compound (I-1) was obtained.

¹ H NMR (CDCl ₃ ) δ ppm: 1.10 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.38-2.58 (2H, m), 3.75 (3H, s), 5.77 (1H, br s), 6.95 (1H, dd, J = 8.3, 2.4 Hz), 7.08-7.18 (3H, m), 7.40-7.44 (1H, m), 7.50 (1H, dd, J = 9.9, 1.7 Hz).

Manufacturing Example 2

Substituting 4-fluorobenzotrifluoride for 3,4-difluorobenzonitrile, according to Production Example 1, 4-(2-ethyl-4-(4-trifluoromethylphenoxy) group was obtained. Phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-2)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.11 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.39-2.58 (2H, m), 3.76 (3H, s), 5.46 (1H, br s), 6.96 (1H, dd, J = 8.3, 2.7 Hz), 7.08-7.17 (4H, m), 7.61 (2H, d, J = 8.5 Hz).

Manufacturing Example 3

3-(3-ethyl-4-(2-chloro-4-trifluoromethyl) 4-(4-ethyl-4-(2-chloro-4-trifluoromethyl) was obtained by the procedure of Preparation 1 using 3-chloro-4-fluorobenzotrifluoride. Phenoxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-3)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.11 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.39-2.59 (2H, m), 3.77 (3H, s), 5.47 (1H, br s), 6.93 (1H, dd, J = 8.5, 2.6 Hz), 7.10 (1H, d, J = 2.6 Hz), 7.12 (1H, d, J = 8.5 Hz), 7.15 (1H, d, J = 8.5) Hz), 7.49 (1H, d, J = 8.5 Hz), 7.76 (1H, s).

Manufacturing Example 4

Substituting 2-chloro-5-trifluoromethylpyridine for 3,4-difluorobenzonitrile, according to Production Example 1, 4-(2-ethyl-4-(5-trifluoromethylpyridine-2) was obtained. -yloxy)fluoro)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-4)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.12 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.40-2.60 (2H, m), 3.76 (3H, s), 6.42 (1H, br s), 7.05-7.11 (2H, m), 7.17 (1H, d, J = 2.2 Hz), 7.19 (1H, d, J = 8.3 Hz), 7.94 (1H, dd, J = 8.7, 2.6 Hz), 8.38-8.40 (1H, m).

Manufacturing Example 5

Substituting 2,5-dichloro-3-fluoropyridine for 3,4-difluorobenzonitrile, and operating according to the production example to obtain 4-(2-ethyl-4-(3-fluoro-5-chloropyridine-2) -yloxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-5)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.12 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.40-2.60 (2H, m), 3.76 (3H, s), 5.52 (1H, s ), 6.94 (1H, dd, J = 8.3, 2.5 Hz), 7.10 (1H, d, J = 2.5 Hz), 7.18 (1H, d, J = 8.3 Hz), 7.36 (1H, d, J = 2.2 Hz) ), 8.16 (1H, d, J = 2.2Hz).

Manufacturing Example 6

Substituting 2,3-difluoro-5-trifluoromethylpyridine for 3,4-difluorobenzonitrile, and operating according to Production Example 1, 4-(2-ethyl-4-(3-fluoro-5-) was obtained. Trifluoromethylpyridin-2-yloxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-6)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (3H, t, J = 7.5 Hz), 2.34 (3H, s), 2.40-2.65 (2H, m), 3.76 (3H, s), 6.38 (1H, br s), 7.12 (1H, dd, J = 8.2, 2.4 Hz), 7.19-7.24 (2H, m), 7.72 (1H, dd, J = 9.3, 1.8 Hz), 8.14 (1H, d, J = 1.8 Hz) ).

Manufacturing Example 7

Substitution of 2,3-dichloro-5-trifluoromethylpyridine for 3,4-difluorobenzonitrile was carried out in accordance with Preparation Example 1 to give 4-(2-ethyl-4-(3-chloro-5-). Trifluoromethylpyridin-2-yloxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-7)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.42 - 2.62 (2H, m), 3.77 (3H, s), 6.43 (1H, br s), 7.11 (1H, dd, J = 8.2, 2.5 Hz), 7.20 (1H, d, J = 2.5 Hz), 7.23 (1H, d, J = 8.2 Hz), 8.02 (1H, d, J = 2.1) Hz), 8.22-8.24 (1H, m).

Manufacturing Example 8

Use 2,6-dichloroquine The phenyl group was substituted with 3,4-difluorobenzonitrile, and the procedure of Production Example 1 was carried out to obtain 4-(2-ethyl-4-(6-chloroquine). Oxalin-2-yloxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-8)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (3H, t, J = 7.6 Hz), 2.36 (3H, s), 2.43-2.64 (2H, m), 3.78 (3H, s), 7.00 (1H, br s), 7.19 (1H, dd, J = 8.3, 2.3 Hz), 7.23 - 7.27 (2H, m), 7.61 (1H, dd, J = 8.9, 2.3 Hz), 7.66 (1H, d, J = 8.9 Hz) ), 8.07 (1H, d, J = 2.3 Hz), 8.73 (1H, s).

Manufacturing Example 9

Use 2,6-dichlorobenzo The azole was substituted for 3,4-difluorobenzonitrile, and the procedure of Production Example 1 was carried out to obtain 4-(2-ethyl-4-(6-chlorobenzo). Zin-2-yloxy)phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-9)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.5 Hz), 2.34 (3H, s), 2.44-2.63 (2H, m), 3.76 (3H, s), 6.27 (1H, br s), 7.24-7.29 (2H, m), 7.35-7.39 (2H, m), 7.41 (1H, d, J = 2.4 Hz), 7.48 (1H, d, J = 1.9 Hz).

Manufacturing Example 10

4-(2-ethyl-4-(benzothiazol-2-yloxy)phenyl)- was obtained by the operation of Production Example 1 using 2-chlorobenzothiazole in place of 3,4-difluorobenzonitrile. 2,6-dimethyl-5-hydroxy-3(2H)-嗒 Ketone (compound (I-10)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.5 Hz), 2.35 (3H, s), 2.43-2.63 (2H, m), 3.77 (3H, s), 6.15 (1H, br s), 7.23 (1H, d, J = 8.5 Hz), 7.28-7.34 (2H, m), 7.37-7.43 (2H, m), 7.68 (1H, d, J = 8.0 Hz), 7.71 (1H, d , J=8.0Hz).

Manufacturing Example 11

Using 2,6-dichlorobenzothiazole in place of 3,4-difluorobenzonitrile, the procedure of Production Example 1 was carried out to obtain 4-(2-ethyl-4-(6-chlorobenzothiazol-2-yloxy). Phenyl)-2,6-dimethyl-5-hydroxy-3(2H)嗒 Ketone (compound (I-11)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.42 - 2.62 (2H, m), 3.76 (3H, s), 6.04 (1H, br s), 7.23 (1H, d, J = 8.5 Hz), 7.32 (1H, dd, J = 8.5, 2.4 Hz), 7.34 - 7.38 (2H, m), 7.59 (1H, d, J = 8.7 Hz), 7.68 (1H, d, J = 1.9 Hz).

Manufacturing Example 12

Using 4-(2-methyl-4-hydroxyphenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime The ketone (Compound II-2) was replaced by the compound II-1, and the product was obtained according to Preparation 7 to give 4-(2-methyl-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy). Phenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime Ketone (compound (I-12)).

¹ H NMR (CDCl ₃ ) δ ppm: 2.22 (3H, s), 2.34 (3H, s), 3.77 (3H, s), 6.11 (1H, s), 7.11 (1H, dd, J = 8.5, 2.4 Hz ), 7.17 (1H, d, J = 2.4 Hz), 7.25 (1H, d, J = 8.5 Hz), 8.01 (1H, d, J = 2.2 Hz), 8.23 - 8.27 (1H, m).

Manufacturing Example 13

4-(2-Ethyl-4-hydroxyphenyl)-2-methyl-6-methoxy-5-hydroxy-3(2H)-oxime The ketone (Compound II-3) was substituted for the compound II-1, and the procedure of Production Example 7 was carried out to obtain 4-(2-ethyl-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy). Phenyl)-2-methyl-6-methoxy-5-hydroxy-3(2H)-oxime Ketone (compound (I-13)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (3H, t, J = 7.5 Hz), 2.44-2.62 (2H, m), 3.69 (3H, s), 3.99 (3H, s), 6.36 (1H, br s), 7.07 (1H, dd, J = 8.5, 2.4 Hz), 7.16 (1H, d, J = 2.4 Hz), 7.21 (1H, d, J = 8.5 Hz), 7.98 (1H, d, J = 2.1) Hz), 8.24 - 8.27 (1H, m).

Manufacturing Example 14

4-(2-Ethyl-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-2,6-dimethyl-5-ethyloxy-3 2H)-嗒 Synthesis of ketone (compound (I-14-1))

In a solution obtained by dissolving 300 mg of the compound (I-7) and 0.28 ml of triethylamine in 3 ml of THF, 0.97 ml of acetamidine chloride was added dropwise at room temperature, followed by stirring for 30 minutes. The reaction mixture was filtered over EtOAc (EtOAc)EtOAc. The residue was purified by yttrium gel column chromatography (hexane: ethyl acetate = 3:1) to afford 295 mg of Compound (I-14-1).

¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.03 (3H, s), 2.27 (3H, s), 2.38-2.65 (2H, m), 3.82 (3H, s ), 7.02 (1H, dd, J = 8.5, 2.3 Hz), 7.09 (1H, d, J = 8.5 Hz), 7.14 (1H, d, J = 2.3 Hz), 7.99 (1H, d, J = 2.3 Hz) ), 8.25-8.28 (1H, m).

The physical property value of the compound of the present invention produced in accordance with Production Example 14 using a compound represented by the formula X ² -G ¹ in place of ethyl chloroform, is shown in Table 1 together with the compound (I-14-1).

(I-14-1); ¹ H NMR (CDCl ₃ ) is described in Production Example 14.

(I-14-2); ¹ H NMR (CDCl ₃ ) δ ppm: 0.99 (3H, t, J = 7.7 Hz), 1.16 (3H, t, J = 7.6 Hz), 2.26 (3H, s), 2.29 (2H,q,J=7.7Hz), 2.38-2.62(2H,m),3.83(3H,s),7.01(1H,dd,J=8.3,2.4Hz),7.08(1H,d,J=8.3 Hz), 7.13 (1H, d, J = 2.4 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.22 - 8.24 (1H, m).

(I-14-3); ¹ H NMR (CDCl ₃ ) δ ppm: 0.97-1.03 (6H, m), 1.16 (3H, t, J = 7.6 Hz), 2.25 (3H, s), 2.38-2.61 ( 3H, m), 3.83 (3H, s), 7.00 (1H, dd, J = 8.2, 2.3 Hz), 7.08 (1H, d, J = 8.2 Hz), 7.12 (1H, d, J = 2.3 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.18-8.21 (1H, m).

(I-14-4); ¹ H NMR (CDCl ₃ ) δ ppm: 1.05 (9H, s), 1.15 (3H, t, J = 7.6 Hz), 2.24 (3H, s), 2.38-2.61 (2H, m), 3.83 (3H, s), 6.99 (1H, dd, J = 8.4, 2.3 Hz), 7.07 (1H, d, J = 8.4 Hz), 7.10 (1H, d, J = 2.3 Hz), 7.97 ( 1H, d, J = 2.1 Hz), 8.16-8.19 (1H, m).

(I-14-5); ¹ H NMR (CDCl ₃ ) δ ppm: 0.80 (3H, t, J = 7.4 Hz), 1.16 (3H, t, J = 7.6 Hz), 1.43-1.53 (2H, m) , 2.23-2.30(5H,m), 2.38-2.62(2H,m),3.83(3H,s),7.01(1H,dd,J=8.4,2.4Hz),7.09(1H,d,J=8.4Hz ), 7.13 (1H, d, J = 2.4 Hz), 7.98 (1H, d, J = 2.0 Hz), 8.22 - 8.25 (1H, m).

(I-14-6); ¹ H NMR (CDCl ₃ ) δ ppm: 0.72-0.78 (3H, m), 0.94-0.99 (3H, m), 1.15 (3H, t, J = 7.6 Hz), 1.27- 1.39 (1H, m), 1.45-1.59 (1H, m), 2.26 (3H, s), 2.31-2.62 (3H, m), 3.83 (3H, s), 7.00 (1H, dd, J = 8.4, 2.4 Hz), 7.06-7.10 (1H, m), 7.11 (1H, d, J = 2.4 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.19-8.21 (1H, m).

(I-14-7); ¹ H NMR (CDCl ₃ ) δ ppm: 0.80 (6H, d, J = 6.9 Hz), 1.16 (3H, t, J = 7.6 Hz), 1.85-1.97 (1H, m) , 2.17 (2H, d, J = 6.9 Hz), 2.26 (3H, s), 2.38 - 2.63 (2H, m), 3.82 (3H, s), 7.01 (1H, dd, J = 8.2, 2.1 Hz), 7.09 (1H, d, J = 8.2 Hz), 7.12 (1H, d, J = 2.1 Hz), 7.98 (1H, d, J = 1.6 Hz), 8.20-8.26 (1H, m).

(I-14-8); ¹ H NMR (CDCl ₃ ) δ ppm: 0.83 (3H, t, J = 7.4 Hz), 1.10-1.21 (5H, m), 1.37-1.46 (2H, m), 2.25 ( 3H, s), 2.28 (2H, t, J = 7.4 Hz), 2.38-2.62 (2H, m), 3.82 (3H, s), 7.01 (1H, dd, J = 8.3, 2.4 Hz), 7.08 (1H) , d, J = 8.4 Hz), 7.13 (1H, d, J = 2.5 Hz), 7.98 (1H, d, J = 2.0 Hz), 8.23 - 8.26 (1H, m).

(I-14-9); ¹ H NMR (CDCl ₃ ) δ ppm: 0.77-0.86 (3H, m), 0.96 (3H, d, J = 6.9 Hz), 1.04-1.29 (6H, m), 1.40- 1.53 (1H, m), 2.25 (3H, s), 2.38-2.61 (3H, m), 3.83 (3H, s), 7.00 (1H, dd, J = 8.2, 2.2 Hz), 7.06-7.10 (1H, m), 7.12 (1H, d, J = 2.2 Hz), 7.97 (1H, d, J = 2.1 Hz), 8.19-8.23 (1H, m).

(I-14-10); ¹ H NMR (CDCl ₃ ) δ ppm: 0.73 (3H, t, J = 7.4 Hz), 0.81 (3H, t, J = 6.9 Hz), 1.01-1.11 (2H, m) , 1.15 (3H, t, J = 7.5 Hz), 1.25-1.51 (4H, m), 2.23-2.33 (4H, m), 2.39-2.61 (2H, m), 3.82 (3H, s), 7.01 (1H) , dd, J = 8.4, 2.3 Hz), 7.09 (1H, d, J = 8.4 Hz), 7.12 (1H, d, J = 2.3 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.21-8.24 (1H,m).

(I-14-11); ¹ H NMR (CDCl ₃ ) δ ppm: 0.80 (6H, t, J = 7.2 Hz), 1.01-1.11 (4H, m), 1.15 (3H, t, J = 7.6 Hz) , 1.23-1.45 (4H, m), 2.26 (3H, s), 2.31-2.61 (3H, m), 3.82 (3H, s), 7.01 (1H, dd, J = 8.4, 2.4 Hz), 7.09 (1H , d, J = 8.4 Hz), 7.12 (1H, d, J = 2.4 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.22 - 8.25 (1H, m).

(I-14-12); ¹ H NMR (CDCl ₃ ) δ ppm: 0.84 (3H, t, J = 7.1 Hz), 1.07-1.28 (7H, m), 1.37-1.48 (2H, m), 2.23 2.30 (5H, m), 2.38-2.62 (2H, m), 3.83 (3H, s), 7.01 (1H, dd, J = 8.3, 2.4 Hz), 7.08 (1H, d, J = 8.2 Hz), 7.13 (1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 1.8 Hz), 8.23 - 8.27 (1H, m).

(I-14-13); ¹ H NMR (CDCl ₃ ) δ ppm: 0.80-0.88 (3H, m), 0.96 (3H, d, J = 7.0 Hz), 1.01-1.30 (8H, m), 1.41- 1.53 (1H, m), 2.25 (3H, s), 2.36-2.61 (3H, m), 3.83 (3H, s), 7.00 (1H, dd, J = 8.3, 2.4 Hz), 7.06-7.14 (2H, m), 7.97 (1H, d, J = 2.0 Hz), 8.19-8.23 (1H, m).

(I-14-14); ¹ H NMR (CDCl ₃ ) δ ppm: 0.72 (3H, t, J = 7.4 Hz), 0.80-0.89 (3H, m), 0.98-1.51 (11H, m), 2.22 2.32 (4H, m), 2.39-2.62 (2H, m), 3.82 (3H, s), 7.01 (1H, dd, J = 8.3, 2.2 Hz), 7.07-7.14 (2H, m), 7.97 (1H, d, J = 1.8 Hz), 8.21-8.25 (1H, m).

(I-14-15); ¹ H NMR (CDCl ₃ ) δ ppm: 0.85 (3H, t, J = 7.1 Hz), 1.09-1.30 (9H, m), 1.37-1.47 (2H, m), 2.23 2.31 (5H, m), 2.38-2.63 (2H, m), 3.82 (3H, s), 7.01 (1H, dd, J = 8.4, 2.3 Hz), 7.08 (1H, d, J = 8.4 Hz), 7.13 (1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 2.0 Hz), 8.23 - 8.27 (1H, m).

(I-14-16); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.28 (3H, s), 2.39-2.63 (2H, m), 3.24 (3H, s), 3.84 (3H, s), 3.97 (2H, s), 7.02 (1H, dd, J = 8.4, 2.4 Hz), 7.10 (1H, d, J = 8.4 Hz), 7.14 (1H, d, J) =2.4 Hz), 7.98 (1H, d, J = 2.0 Hz), 8.21-8.24 (1H, m).

(I-14-17); ¹ H NMR (CDCl ₃ ) δ ppm: 1.10 - 1.22 (6H, m), 2.27 (3H, s), 2.38 - 2.63 (2H, m), 3.26 - 3.41 (2H, m ), 3.83 (3H, s), 4.01 (2H, s), 7.02 (1H, dd, J = 8.3, 2.2 Hz), 7.09 (1H, d, J = 8.3 Hz), 7.14 (1H, d, J = 2.2Hz), 7.99 (1H, d, J = 1.8Hz), 8.21-8.26 (1H, m).

(I-14-18); ¹ H NMR (CDCl ₃ ) δ ppm: 0.88 (3H, t, J = 7.4 Hz), 1.16 (3H, t, J = 7.6 Hz), 1.49-1.59 (2H, m) , 2.27 (3H, s), 2.39-2.62 (2H, m), 3.17-3.28 (2H, m), 3.83 (3H, s), 4.00 (2H, s), 7.02 (1H, dd, J = 8.4, 2.3 Hz), 7.09 (1H, d, J = 8.4 Hz), 7.14 (1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.23 - 8.25 (1H, m).

(I-14-19); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (6H, t, J = 7.5 Hz), 2.26-2.63 (7H, m), 3.17 (2H, s), 3.83 (3H, s), 7.02 (1H, dd, J = 8.4, 2.3 Hz), 7.10 (1H, d, J = 8.4 Hz), 7.14 (1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 2.0) Hz), 8.23-8.28 (1H, m).

(I-14-20); ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (3H, t, J = 7.5 Hz), 2.16 (3H, s), 2.27-2.38 (1H, m), 2.42-2.54 ( 1H, m), 3.58 (2H, s), 3.81 (3H, s), 6.94 (1H, dd, J = 8.4, 2.3 Hz), 6.99-7.04 (3H, m), 7.07 (1H, d, J = 2.3Hz), 7.24-7.30(3H,m), 8.00(1H,d,J=2.3Hz), 8.20-8.24(1H,m).

(I-14-21); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.27 (3H, s), 2.40-2.63 (2H, m), 3.84 (3H, s), 4.04 (2H, s), 4.33 (2H, s), 7.02 (1H, dd, J = 8.4, 2.3 Hz), 7.11 (1H, d, J = 8.4 Hz), 7.15 (1H, d, J) =2.3 Hz), 7.20-7.25 (2H, m), 7.28-7.36 (3H, m), 7.96 (1H, d, J = 1.8 Hz), 8.01-8.04 (1H, m).

(I-14-22); ¹ H NMR (CDCl ₃ ) δ ppm: 1.12 (3H, t, J = 7.6 Hz), 2.26 (3H, s), 2.35-2.61 (2H, m), 3.83 (3H, s), 4.57 (2H, s), 6.62 (2H, d, J = 8.7 Hz), 6.99 (1H, t, J = 7.4 Hz), 7.04 (1H, dd, J = 8.3, 2.2 Hz), 7.11 ( 1H, d, J = 8.3 Hz), 7.16 (1H, d, J = 2.2 Hz), 7.25 (2H, dd, J = 8.7, 7.4 Hz), 7.99 (1H, d, J = 2.3 Hz), 8.12 8.15 (1H, m).

(I-14-23); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.27 (3H, s), 2.38-2.62 (4H, m), 3.27 (3H, s), 3.49 (2H, t, J = 6.3 Hz), 3.83 (3H, s), 7.01 (1H, dd, J = 8.4, 2.3 Hz), 7.08 (1H, d, J = 8.4 Hz), 7.13 ( 1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 2.3 Hz), 8.24 - 8.27 (1H, m).

(I-14-24); ¹ H NMR (CDCl ₃ ) δ ppm: 1.11-1.20 (6H, m), 2.27 (3H, s), 2.38-2.62 (4H, m), 3.43 (2H, q, J =7.0Hz), 3.51-3.57(2H,m), 3.83(3H,s).7.01(1H,dd,J=8.4,2.3Hz),7.08(1H,d,J=8.4Hz),7.13(1H , d, J = 2.3 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.24 - 8.28 (1H, m).

(I-14-25); ¹ H NMR (CDCl ₃ ) δ ppm: 0.85-0.93 (3H, m), 1.16 (3H, t, J = 7.6 Hz), 2.26 (3H, s), 2.38-2.61 ( 2H, m), 2.68-2.78 (1H, m), 3.25-3.33 (4H, m), 3.37-3.46 (1H, m), 3.83 (3H, s), 6.98-7.03 (1H, m), 7.06- 7.14(2H,m), 7.97(1H,d,J=2.3Hz), 8.18-8.22(1H,m).

(I-14-26); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.05 (3H, s), 2.28 (3H, s), 2.38-2.62 (6H, m), 3.83 (3H, s), 7.01 (1H, dd, J = 8.4, 2.3 Hz), 7.08 (1H, d, J = 8.4 Hz), 7.13 (1H, d, J = 2.3 Hz), 7.98 ( 1H, d, J = 2.0 Hz), 8.28-8.31 (1H, m).

(I-14-27); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.15 (3H, s), 2.37-2.62 (4H, m), 2.67-2.74 ( 2H,m), 3.82 (3H, s), 6.99 (1H, dd, J=8.4, 2.5 Hz), 7.06-7.14 (4H, m), 7.18-7.30 (3H, m), 7.91-7.93 (1H, m), 7.95 (1H, d, J = 2.0 Hz).

(I-14-28); ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.6 Hz), 2.28 (3H, s), 2.38-2.62 (2H, m), 2.75 (2H, t, J = 6.3 Hz), 3.83 (3H, s), 4.03-4.10 (2H, m), 6.81 (2H, d, J = 7.7 Hz), 6.95 (1H, t, J = 7.7 Hz), 7.00 ( 1H, dd, J = 8.4, 2.3 Hz), 7.09 (1H, d, J = 8.4 Hz), 7.13 (1H, d, J = 2.3 Hz), 7.26 (2H, t, J = 7.7 Hz), 7.97 ( 1H, d, J = 2.3 Hz), 8.15-8.19 (1H, m).

(I-14-29); ¹ H NMR (CDCl ₃ ) δ ppm: 0.79-0.93 (4H, m), 1.15 (3H, t, J = 7.6 Hz), 1.55-1.65 (1H, m), 2.26 ( 3H, s), 2.37-2.48 (1H, m), 2.50-2.61 (1H, m), 3.82 (3H, s), 7.02 (1H, dd, J = 8.2, 2.3 Hz), 7.07 (1H, d, J = 8.2 Hz), 7.14 (1H, d, J = 2.3 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.24 - 8.26 (1H, m).

(I-14-30); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 1.74-2.16 (6H, m), 2.25 (3H, s), 2.39-2.62 ( 2H,m), 3.08-3.18(1H,m),3.83(3H,s),7.01(1H,dd,J=8.5,2.3Hz), 7.10(1H,d,J=8.5Hz),7.12(1H , d, J = 2.3 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.17-8.19 (1H, m).

(I-14-31); ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.6 Hz), 1.42-1.61 (6H, m), 1.68-1.81 (2H, m), 2.25 ( 3H, s), 2.38-2.61 (2H, m), 2.67-2.78 (1H, m), 3.83 (3H, s), 7.00 (1H, dd, J = 8.3, 2.4 Hz), 7.07 (1H, d, J = 8.3 Hz), 7.12 (1H, d, J = 2.4 Hz), 7.98 (1H, d, J = 2.3 Hz), 8.20-8.22 (1H, m).

(I-14-32); ¹ H NMR (CDCl ₃ ) δ ppm: 1.10-1.31 (8H, m), 1.56-1.72 (5H, m), 2.24 (3H, s), 2.25-2.34 (1H, m ), 2.38-2.48 (1H, m), 2.50-2.61 (1H, m), 3.82 (3H, s), 7.00 (1H, dd, J = 8.3, 2.4 Hz), 7.07 (1H, d, J = 8.3) Hz), 7.12 (1H, d, J = 2.4 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.19-8.22 (1H, m).

(I-14-33); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.46-2.56 (1H, m), 2.58-2.68 ( 1H, m), 3.86 (3H, s), 6.93 (1H, dd, J = 8.5, 2.4 Hz), 7.07 (1H, d, J = 2.4 Hz), 7.16 (1H, d, J = 8.5 Hz), 7.44 (2H, t, J = 7.8 Hz), 7.62 (1H, t, J = 7.8 Hz), 7.90 (2H, d, J = 7.8 Hz), 7.93 (1H, d, J = 2.2 Hz), 8.11 8.13 (1H, m).

(I-14-34); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.44-2.68 (2H, m), 3.86 (3H, s), 6.96 (1H, dd, J = 8.3, 2.4 Hz), 7.07-7.22 (4H, m), 7.54-7.63 (1H, m), 7.67-7.75 (1H, m), 7.95 (1H, d, J=2.0Hz), 8.12-8.18(1H,m).

(I-14-35); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.30 (3H, s), 2.44-2.69 (2H, m), 3.87 (3H, s), 6.94 (1H, dd, J = 8.4, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.14 (1H, d, J = 8.4 Hz), 7.29-7.36 (1H, m), 7.39-7.46 (1H, m), 7.53-7.59 (1H, m), 7.68-7.73 (1H, m), 7.94 (1H, d, J = 1.8 Hz), 8.12-8.17 (1H, m).

(I-14-36); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.5 Hz), 2.29 (3H, s), 2.44-2.68 (2H, m), 3.86 (3H, s), 6.93 (1H, dd, J = 8.4, 2.5 Hz), 7.06-7.16 (4H, m), 7.89-7.96 (3H, m), 8.13-8.17 (1H, m).

(I-14-37); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.37 (3H, s), 2.43-2.67 (2H, m), 3.87 (3H, s), 7.00 (1H, dd, J = 8.3, 2.5 Hz), 7.13 (1H, d, J = 2.5 Hz), 7.17 (1H, d, J = 8.3 Hz), 7.22 - 7.28 (1H, m), 7.34 (1H, d, J = 7.7 Hz), 7.44 - 7.48 (2H, m), 7.97 (1H, d, J = 2.3 Hz), 8.17-8.20 (1H, m).

(I-14-38); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.45-2.68 (2H, m), 3.87 (3H, s), 6.94 (1H, dd, J = 8.3, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.14 (1H, d, J = 8.3 Hz), 7.39 (1H, t, J = 8.1) Hz), 7.57-7.61 (1H, m), 7.76-7.80 (1H, m), 7.87 (1H, t, J = 1.7 Hz), 7.94 (1H, t, J = 1.0 Hz), 8.14 - 8.16 (1H , m).

(I-14-39); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.43-2.68 (2H, m), 3.86 (3H, s), 6.93 (1H, dd, J = 8.4, 2.4 Hz), 7.07 (1H, d, J = 2.4 Hz), 7.13 (1H, d, J = 8.4 Hz), 7.41 (2H, d, J = 8.5) Hz), 7.82 (2H, d, J = 8.5 Hz), 7.94 (1H, d, J = 2.0 Hz), 8.12-8.16 (1H, m).

(I-14-40); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.38 (3H, s), 2.44-2.66 (2H, m), 3.87 (3H, s), 7.01 (1H, dd, J = 8.3, 2.4 Hz), 7.14 (1H, d, J = 2.4 Hz), 7.17 (1H, d, J = 8.3 Hz), 7.24 - 7.32 (2H, m), 7.34-7.39 (1H, m), 7.66 (1H, d, J = 8.0 Hz), 7.97 (1H, d, J = 2.3 Hz), 8.17-8.21 (1H, m).

(I-14-41); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.43-2.68 (2H, m), 3.86 (3H, s), 6.92 (1H, dd, J = 8.4, 2.5 Hz), 7.07 (1H, d, J = 2.5 Hz), 7.12 (1H, d, J = 8.4 Hz), 7.58 (2H, d, J = 8.7) Hz), 7.74 (2H, d, J = 8.7 Hz), 7.94 (1H, d, J = 2.0 Hz), 8.13-8.16 (1H, m).

(I-14-42); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.42 (3H, s), 2.46-2.68 (2H, m), 3.86 (3H, s), 6.96 (1H, dd, J = 8.5, 2.4 Hz), 7.10 (1H, d, J = 2.4 Hz), 7.16 (1H, d, J = 8.5 Hz), 7.19- 7.29 (2H, m), 7.44 (1H, t, J = 7.4 Hz), 7.66 (1H, d, J = 7.6 Hz), 7.95 (1H, d, J = 2.1 Hz), 8.13-8.17 (1H, m ).

(I-14-43); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.38 (3H, s), 2.46-2.69 (2H, m), 3.86 (3H, s), 6.94 (1H, dd, J = 8.4, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.16 (1H, d, J = 8.4 Hz), 7.32 ( 1H, t, J = 7.8 Hz), 7.42 (1H, d, J = 7.7 Hz), 7.67-7.72 (2H, m), 7.93 (1H, d, J = 2.0 Hz), 8.11-8.14 (1H, m ).

(I-14-44); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.41 (3H, s), 2.47-2.69 (2H, m), 3.86 (3H, s), 6.92 (1H, dd, J = 8.5, 2.3 Hz), 7.06 (1H, d, J = 2.3 Hz), 7.15 (1H, d, J = 8.5 Hz), 7.23 ( 2H, d, J = 8.1 Hz), 7.79 (2H, d, J = 8.1 Hz), 7.93 (1H, d, J = 2.1 Hz), 8.08-8.12 (1H, m).

(I-14-45); ¹ H NMR (CDCl ₃ ) δ ppm: 1.11 (3H, t, J = 7.5 Hz), 1.17 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.45 -2.68 (3H, m), 2.74-2.85 (2H, m), 3.86 (3H, s), 6.97 (1H, dd, J = 8.3, 2.4 Hz), 7.11 (1H, d, J = 2.4 Hz), 7.15-7.23(2H,m), 7.27(1H,d,J=7.6Hz), 7.48(1H,t,J=7.6Hz), 7.60(1H,d,J=7.6Hz),7.95(1H,d , J = 1.8 Hz), 8.13-8.17 (1H, m).

(I-14-46); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.33 (3H, s), 2.45-2.67 (2H, m), 3.84 (3H, s), 3.86 (3H, s), 6.91 (1H, t, J = 7.5 Hz), 6.94-6.99 (2H, m), 7.11 (1H, d, J = 2.3 Hz), 7.18 (1H, d, J) = 8.4 Hz), 7.43 - 7.47 (1H, m), 7.48 - 7.54 (1H, m), 7.95 (1H, d, J = 2.0 Hz), 8.15-8.19 (1H, m).

(I-14-47); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.30 (3H, s), 2.45-2.68 (2H, m), 3.81 (3H, s), 3.86 (3H, s), 6.94 (1H, dd, J = 8.4, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.12 - 7.17 (2H, m), 7.31 - 7.38 (2H , m), 7.47-7.51 (1H, m), 7.93 (1H, d, J = 2.3 Hz), 8.12-8.16 (1H, m).

(I-14-48); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.44-2.69 (2H, m), 3.86 (6H, s), 6.88-6.95 (3H, m), 7.07 (1H, d, J = 2.5 Hz), 7.15 (1H, d, J = 8.2 Hz), 7.86 (2H, d, J = 8.9 Hz), 7.93 ( 1H, d, J = 1.8 Hz), 8.12 - 8.15 (1H, m).

(I-14-49); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 1.40 (3H, t, J = 7.0 Hz), 2.35 (3H, s), 2.44 -2.68 (2H, m), 3.85 (3H, s), 4.08 (2H, q, J = 7.0 Hz), 6.85-6.99 (3H, m), 7.11 (1H, d, J = 2.3 Hz), 7.18 ( 1H, d, J = 8.2 Hz), 7.38 (1H, dd, J = 7.9, 1.8 Hz), 7.44 - 7.50 (1H, m), 7.95 (1H, d, J = 2.1 Hz), 8.17-8.19 (1H , m).

(I-14-50); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.5 Hz), 2.32 (3H, s), 2.44 (3H, s), 2.46-2.68 (2H, m), 3.86 (3H, s), 6.95 (1H, dd, J = 8.4, 2.4 Hz), 7.08-7.13 (2H, m), 7.17 (1H, d, J = 8.4 Hz), 7.27 (1H, d , J = 7.9 Hz), 7.51 (1H, t, J = 7.9 Hz), 7.69 (1H, d, J = 7.9 Hz), 7.94 (1H, d, J = 2.3 Hz), 8.14 - 8.17 (1H, m ).

(I-14-51); ¹ H NMR (CDCl ₃ ) δ ppm: 1.17 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.43-2.68 (2H, m), 3.87 (3H, s), 6.93 (1H, dd, J = 8.4, 2.4 Hz), 7.09 (1H, d, J = 2.4 Hz), 7.12 (1H, d, J = 8.4 Hz), 7.75 (2H, d, J = 8.8) Hz), 7.95 (1H, d, J = 2.0 Hz), 7.99 (2H, d, J = 8.8 Hz), 8.15-8.17 (1H, m).

(I-14-52); ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.5 Hz), 2.41-2.66 (5H, m), 3.87 (3H, s), 6.69 (1H, d, J = 7.6 Hz), 7.05 (1H, dd, J = 8.3, 2.4 Hz), 7.14 - 7.21 (2H, m), 7.54 (1H, t, J = 7.6 Hz), 7.65 (1H, t, J) =7.6 Hz), 8.00-8.07 (2H, m), 8.20-8.24 (1H, m).

(I-14-53); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.31 (3H, s), 2.44-2.69 (2H, m), 3.88 (3H, s), 6.94 (1H, dd, J = 8.4, 2.4 Hz), 7.09 (1H, d, J = 2.4 Hz), 7.13 (1H, d, J = 8.4 Hz), 7.95 (1H, d, J = 2.0) Hz), 8.06 (2H, d, J = 8.6 Hz), 8.15-8.17 (1H, m), 8.29 (2H, d, J = 8.6 Hz).

(I-14-54); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.5 Hz), 2.36 (3H, s), 2.43-2.66 (2H, m), 3.87 (3H, s), 7.00-7.07 (2H, m), 7.15-7.19 (2H, m), 7.49 (1H, t, J = 7.8 Hz), 7.64 (1H, t, J = 7.8 Hz), 7.77 (1H, d , J = 7.8 Hz), 7.99 (1H, d, J = 2.0 Hz), 8.17 - 8.21 (1H, m).

(I-14-55); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.30 (3H, s), 2.44-2.69 (2H, m), 3.87 (3H, s), 6.93 (1H, dd, J = 8.4, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.14 (1H, d, J = 8.4 Hz), 7.71 (2H, d, J = 8.3) Hz), 7.94 (1H, d, J = 2.0 Hz), 8.00 (2H, d, J = 8.3 Hz), 8.08-8.12 (1H, m).

(I-14-56); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.4 Hz), 2.29 (3H, s), 2.44-2.68 (2H, m), 3.87 (3H, s), 6.94 (1H, dd, J = 8.5, 2.5 Hz), 7.08 (1H, d, J = 2.5 Hz), 7.13 (1H, d, J = 8.5 Hz), 7.26 (2H, d, J = 8.0) Hz), 7.92-7.97 (3H, m), 8.12-8.14 (1H, m).

(I-14-57); ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.5 Hz), 2.37 (3H, s), 2.42-2.66 (2H, m), 3.86 (3H, s), 6.95 (2H, t, J = 8.3 Hz), 7.00 (1H, dd, J = 8.4, 2.4 Hz), 7.12 (1H, d, J = 2.4 Hz), 7.15 (1H, d, J = 8.4) Hz), 7.44 - 7.53 (1H, m), 7.97 (1H, d, J = 2.3 Hz), 8.19-8.22 (1H, m).

(I-14-58); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.5 Hz), 2.37 (3H, s), 2.43-2.66 (2H, m), 3.87 (3H, s), 7.01 (1H, dd, J=8.4, 2.5 Hz), 7.10-7.22 (4H, m), 7.62 (1H, dd, J=7.9, 1.8 Hz), 7.98 (1H, d, J = 2.3 Hz) ), 8.20-8.24 (1H, m).

(I-14-59); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.35 (3H, s), 2.42-2.66 (2H, m), 3.87 (3H, s), 6.99 (1H, dd, J = 8.3, 2.4 Hz), 7.11-7.16 (2H, m), 7.23 (1H, dd, J = 8.6, 1.9 Hz), 7.31 (1H, d, J = 8.6 Hz) ), 7.48 (1H, d, J = 1.9 Hz), 7.97 (1H, d, J = 1.8 Hz), 8.16 - 8.21 (1H, m).

(I-14-60); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.36 (3H, s), 2.43-2.67 (2H, m), 3.87 (3H, s), 7.02 (1H, dd, J = 8.5, 2.3 Hz), 7.13-7.18 (2H, m), 7.31 (1H, d, J = 2.3 Hz), 7.36-7.45 (2H, m), 7.96 (1H) , d, J = 2.1 Hz), 8.16-8.20 (1H, m).

(I-14-61); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.5 Hz), 2.45-2.63 (5H, m), 3.85 (3H, s), 7.02 (1H, Dd, J = 8.4, 2.4 Hz), 7.12 (1H, d, J = 2.4 Hz), 7.19 (1H, d, J = 8.4 Hz), 7.29-7.32 (3H, m), 7.98 (1H, d, J) =2.0Hz), 8.26-8.29 (1H, m).

(I-14-62); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.43-2.67 (2H, m), 3.87 (3H, s), 6.94 (1H, dd, J = 8.3, 2.4 Hz), 7.08 (1H, d, J = 2.4 Hz), 7.12 (1H, d, J = 8.3 Hz), 7.52 (1H, d, J = 8.5) Hz), 7.70 (1H, dd, J = 8.5, 2.2 Hz), 7.94 (1H, d, J = 2.2 Hz), 7.96 (1H, d, J = 1.8 Hz), 8.13-8.16 (1H, m).

(I-14-63); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.29 (3H, s), 2.43-2.68 (2H, m), 3.87 (3H, s), 6.96 (1H, dd, J = 8.5, 2.4 Hz), 7.10 (1H, d, J = 2.4 Hz), 7.12 (1H, d, J = 8.5 Hz), 7.60 (1H, t, J = 2.0) Hz), 7.75 (2H, d, J = 2.0 Hz), 7.95 (1H, d, J = 2.3 Hz), 8.15-8.19 (1H, m).

(I-14-64); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.08 (6H, s), 2.40 (3H, s), 2.44-2.65 (2H, m), 3.85 (3H, s), 6.98-7.04 (3H, m), 7.13 (1H, d, J = 2.5 Hz), 7.18 (1H, d, J = 8.4 Hz), 7.23 (1H, t, J =7.6 Hz), 7.98 (1H, d, J = 2.3 Hz), 8.21-8.24 (1H, m).

(I-14-65); ¹ H NMR (CDCl ₃ ) δ ppm: 1.15 (3H, t, J = 7.6 Hz), 2.44 (3H, s), 2.45-2.65 (2H, m), 3.69 (6H, s), 3.84 (3H, s), 6.50 (2H, d, J = 8.4 Hz), 7.02 (1H, dd, J = 8.4, 2.4 Hz), 7.15 (1H, d, J = 2.4 Hz), 7.18 ( 1H, d, J = 8.4 Hz), 7.30 (1H, t, J = 8.4 Hz), 7.98 (1H, d, J = 2.0 Hz), 8.22 - 8.25 (1H, m).

(I-14-66); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.37 (3H, s), 2.44-2.66 (2H, m), 3.29 (3H, s), 3.77 (3H, s), 4.61 (1H, d, J = 5.9 Hz), 4.64 (1H, d, J = 5.9 Hz), 7.05 (1H, dd, J = 8.5, 2.4 Hz), 7.15 ( 1H, d, J = 2.4 Hz), 7.23 (1H, d, J = 8.5 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.25-8.28 (1H, m).

(I-14-67); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.37-2.65 (5H, m), 3.85 (3H, s), 6.93 (2H, d, J = 7.8 Hz), 7.09 (1H, dd, J = 8.4, 2.3 Hz), 7.18-7.28 (3H, m), 7.33 (2H, t, J = 7.8 Hz), 8.00 (1H, d, J) =2.3Hz), 8.17-8.21 (1H, m).

(I-14-68); ¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.37 (3H, s), 2.44-2.66 (2H, m), 3.29 (3H, s), 3.77 (3H, s), 4.61 (1H, d, J = 5.9 Hz), 4.64 (1H, d, J = 5.9 Hz), 7.05 (1H, dd, J = 8.5, 2.4 Hz), 7.15 ( 1H, d, J = 2.4 Hz), 7.23 (1H, d, J = 8.5 Hz), 7.98 (1H, d, J = 2.1 Hz), 8.24 - 8.27 (1H, m).

(I-14-69); ¹ H NMR (CDCl ₃ ) δ ppm: 1.21 (3H, t, J = 7.6 Hz), 2.43-2.67 (8H, m), 3.84 (3H, s), 7.10 (1H, Dd, J = 8.4, 2.4 Hz), 7.19 (1H, d, J = 2.4 Hz), 7.28 (1H, d, J = 8.4 Hz), 7.99 (1H, d, J = 2.0 Hz), 8.15-8.18 ( 1H, m).

(I-14-70); ¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (3H, t, J = 7.6 Hz), 2.25-2.52 (2H, m), 2.55 (3H, s), 3.82 (3H, s), 6.82 (1H, dd, J = 8.4, 2.5 Hz), 6.92 (1H, d, J = 2.5 Hz), 7.02 (1H, d, J = 8.4 Hz), 7.40 (4H, d, J = 4.5) Hz), 7.56-7.62 (1H, m), 8.02 (1H, d, J = 2.0 Hz), 8.28-8.32 (1H, m).

(I-14-71); ¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.10 (3H, s), 2.41-2.51 (1H, m), 2.53-2.64 ( 1H, m), 3.74 (3H, s), 3.91 (3H, s), 7.02 (1H, dd, J = 8.4, 2.3 Hz), 7.09 (1H, d, J = 8.4 Hz), 7.15 (1H, d , J = 2.3 Hz), 7.99 (1H, d, J = 2.2 Hz), 8.27-8.29 (1H, m).

Manufacturing Example 15

4-(2-Ethyl-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl)-2,6-dimethyl-5-benzyloxy-3 (2H )-despair Synthesis of ketone (compound (I-15-1))

A mixed solution of 300 mg of the compound (I-7), 128 mg of benzyl bromide, 267 mg of cesium carbonate and 10 ml of acetone was stirred under reflux with heating for 3 hours. After cooling the reaction mixture to room temperature, it was filtered with purified celite, and the filtrate was concentrated under reduced pressure. The residue was purified by yttrium gel column chromatography (hexane: ethyl acetate = 2:1) to afford 324 mg of Compound (I-15-1) as an oil.

¹ H NMR (CDCl ₃ ) δ ppm: 1.18 (3H, t, J = 7.6 Hz), 2.31 (3H, s), 2.44-2.68 (2H, m), 3.77 (3H, s), 4.49 (1H, d , J = 11.2 Hz), 4.53 (1H, d, J = 11.2 Hz), 7.06 - 7.14 (3H, m), 7.18 (1H, d, J = 2.3 Hz), 7.27-7.34 (4H, m), 7.99 (1H, d, J = 2.3 Hz), 8.24 - 8.26 (1H, m).

4-(2-ethyl-4-(3-chloro-5-trifluoromethylpyridin-2-yloxy)phenyl was obtained according to Preparation 15 using 2-nitrobenzyl chloride in place of benzyl bromide. -2,6-Dimethyl-5-(2-nitrobenzyloxy)-3(2H)-oxime Ketone (compound (I-15-2)).

¹ H NMR (CDCl ₃ ) δ ppm: 1.19 (3H, t, J = 7.6 Hz), 2.34 (3H, s), 2.45-2.69 (2H, m), 3.78 (3H, s), 4.98 (2H, s ), 6.99 (1H, dd, J = 8.4, 2.4 Hz), 7.14 (1H, d, J = 2.4 Hz), 7.19 (1H, d, J = 8.4 Hz), 7.48 (1H, t, J = 7.8 Hz) ), 7.52 (1H, d, J = 7.8 Hz), 7.60-7.66 (1H, m), 7.97 (1H, d, J = 1.8 Hz), 8.08 (1H, dd, J = 7.8, 1.1 Hz), 8.24 -8.26(1H,m).

Next, the production examples of the compound represented by the formula (II) are shown in Reference Example 1 to Reference Example 3.

Reference example 1

Synthesis of Compound (II-1)

Reference example 1-1

Synthesis of 4-bromo-3-ethylphenol

To a solution obtained by dissolving 25.2 g of 3-ethylphenol in 300 ml of chloroform, 69.27 g of pyridinium bromide perbromide was added, and the mixture was stirred at room temperature for 30 minutes. The reaction mixture was washed with water (2×), brine, evaporated The residue was purified by silica gel column chromatography (hexane: ethyl acetate=95:5) to yield 39.1 g of 4-bromo-3-ethylphenol as an oil.

¹ H NMR (CDCl ₃ ) δ ppm: 1.21 (3H, t, J = 7.6 Hz), 2.69 (2H, q, J = 7.6 Hz), 4.80 (1H, s), 6.55 (1H, dd, J = 8.7 , 3.1 Hz), 6.73 (1H, d, J = 3.1 Hz), 7.35 (1H, d, J = 8.7 Hz).

Reference example 1-2

Synthesis of 4-benzyloxy-2-ethylbromobenzene

A mixed solution of 39.1 g (194 mmol) of 4-bromo-3-ethylphenol, 33.2 g (194 mmol) of benzyl bromide, 29.6 g (214 mmol) of potassium carbonate and 120 ml of acetonitrile was stirred under reflux for 4 hours. The reaction solution was cooled to room temperature and then filtered, and the filtrate was concentrated under reduced pressure. The residue was purified by silica gel column chromatography (hexane: ethyl acetate = 95:5) to afford 46.2 g of 4-benzyloxy-2-ethylbromobenzene as an oil.

¹ H NMR (CDCl ₃ ) δ ppm: 1.21 (3H, t, J = 7.6 Hz), 2.71 (2H, q, J = 7.6 Hz), 5.03 (2H, s), 6.68 (1H, dd, J = 8.7 , 3.1Hz), 6.87 (1H, d, J = 3.1Hz), 7.30-7.45 (6H, m).

Reference example 1-3

Synthesis of 4-benzyloxy-2-ethylphenylboronic acid

A solution of 46.2 g of 4-benzyloxy-2-ethylbromobenzene dissolved in 180 ml of anhydrous THF was cooled to -70 ° C, and slowly dropped into n-butyllithium (1.64 mol/L, hexane solution) 106 ml. . After the completion of the dropwise addition, the mixture was stirred at -50 to -60 ° C for 3 hours, and then 35 ml of trimethyl borate was gradually added dropwise. After the reaction mixture was stirred at -78 ° C for 3 hours, it was stirred at room temperature overnight. To the reaction liquid, 136 ml of 4N hydrochloric acid was added, and the mixture was stirred for 2 hours. The reaction mixture was extracted twice with EtOAc (EtOAc)EtOAc. The residue was purified by cerium oxide gel column chromatography to give 3.83 g of 4-benzyloxy-2-ethylphenylboronic acid as a solid.

¹ H NMR (CDCl ₃ ) δ ppm: 1.34 (3H, t, J = 7.5 Hz), 3.20 (3H, q, J = 7.5 Hz), 5.14 (2H, s), 6.89-6.96 (2H, m), 7.31-7.50 (5H, m), 8.18 (1H, d, J = 8.2 Hz).

Reference example 1-4

4-(2-ethyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-indole Ketone synthesis

4-bromo-5-methoxy-2,6-dimethyl-3(2H)-oxime 4.81 g of ketone, 5.82 g of 4-benzyloxy-2-ethylphenylboronic acid, 955 mg of tetrakis(triphenylphosphine)palladium, 4.81 g of sodium carbonate, 1.66 g of tetrabutylammonium bromide, 1,4-two A mixture of 170 ml of alkane and 50 ml of water was stirred under a nitrogen atmosphere for 5 hours under reflux. The reaction mixture was cooled to room temperature. The residue was purified by yttrium gel column chromatography (hexane: ethyl acetate = 2:1) to afford 4-(2-ethyl-4-benzyloxyphenyl)-2. -Dimethyl-5-methoxy-3(2H)-oxime Ketone 6.91 g.

¹ H NMR (CDCl ₃ ) δ ppm: 1.16 (3H, t, J = 7.6 Hz), 2.27 (3H, s), 2.37-2.59 (2H, m), 3.37 (3H, s), 3.73 (3H, s ), 5.08 (2H, s), 6.85 (1H, dd, J = 8.5, 2.6 Hz), 6.96 (1H, d, J = 2.6 Hz), 7.08 (1H, d, J = 8.5 Hz), 7.33 (1H) , t, J = 7.3 Hz), 7.40 (2H, t, J = 7.3 Hz), 7.45 (2H, d, J = 7.3 Hz).

Reference example 1-5

Synthesis of Compound (II-1)

In the 4-(2-ethyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-oxime 7.45 g of a ketone was dissolved in 40 ml of acetic acid, and 23 ml of 47% hydrogen bromide was added thereto, followed by stirring at 100 ° C for 3 hours. The reaction mixture was poured into ice water, and the mixture was evaporated to ethylamine. The obtained solid was washed with hexane to obtain 5.03 g of Compound (II-1).

¹ H NMR (DMSO-d ₆ ) δ ppm: 0.99 (3H, t, J = 7.6 Hz), 2.20 (3H, s), 2.26 (2H, q, J = 7.6 Hz), 3.55 (3H, s), 6.61 (1H, dd, J = 8.3, 2.5 Hz), 6.70 (1H, d, J = 2.5 Hz), 6.79 (1H, d, J = 8.3 Hz), 9.36 (1H, br s), 9.82 (1H, s).

Reference example 2

Synthesis of Compound (II-2)

Reference example 2-1

4-(2-Methyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-indole Ketone synthesis

Substituting 4-benzyloxy-2-methylphenylboronic acid for 4-benzyloxy-2-ethylphenylboronic acid gave 4-(2-methyl-4-benzyloxy) according to Reference Example 1-4. Phenyl)-2,6-dimethyl-5-methoxy-3(2H)-oxime ketone.

¹ H NMR (CDCl ₃ ) δ ppm: 2.18 (3H, s), 2.27 (3H, s), 3.36 (3H, s), 3.73 (3H, s), 5.07 (2H, s), 6.85 (1H, dd , J = 8.5, 2.7 Hz), 6.90 (1H, d, J = 2.7 Hz), 7.10 (1H, d, J = 8.5 Hz), 7.30-7.46 (5H, m).

Reference example 2-2

Synthesis of Compound (II-2)

4-(2-Methyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-oxime Ketone-substituted 4-(2-ethyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-oxime Ketone, Compound II-2 was obtained according to Reference Example 1-5.

¹ H NMR (DMSO-d ₆ ) δ ppm: 1.96 (3H, s), 2.20 (3H, s), 3.55 (3H, s), 6.60 (1H, dd, J = 8.4, 2.3 Hz), 6.67 (1H) , d, J = 2.3 Hz), 6.84 (1H, d, J = 8.4 Hz), 9.35 (1H, s), 9.84 (1H, s).

Reference example 3

Synthesis of Compound (II-3)

Reference example 3-1

4,5-Dichloro-6-hydroxy-2-methyl-3(2H)-嗒 Ketone synthesis

In a solution obtained by dissolving 107 g of dichloromalonic anhydride in 200 ml of THF, 29.5 g of methylamine was slowly added dropwise under ice cooling. The reaction solution was stirred under heating and reflux for 2 hr. The obtained solid was washed with MTBE and acetone to obtain 4,5-dichloro-6-hydroxy-2-methyl-3(2H)-indole. Ketone 100g.

¹ H NMR (DMSO-d ₆ ) δ ppm: 3.54 (3H, s), 12.37 (1H, br s).

Reference example 3-2

4,5-Dichloro-6-methoxy-2-methyl-3(2H)-oxime Ketone synthesis

In a mixture of 22.4 g of dimethyl sulfate, 36.8 g of cesium carbonate and 100 ml of DMF, 4,5-dichloro-6-hydroxy-2-methyl-3(2H)-oxime was slowly added at 70 °C. The ketone was 20 g and stirred for 30 minutes. The reaction solution was poured into ice water, and the obtained solid was filtered, and the solid was washed successively with water and MTBE, and dried to obtain 4,5-dichloro-6-methoxy-2-methyl-3 (2H). -despair Ketone 15.1 g.

¹ H NMR (CDCl ₃ ) δ ppm: 3.72 (3H, s), 3.92 (3H, s).

Reference example 3-3

4-chloro-5,6-dimethoxy-2-methyl-3(2H)-oxime Ketone synthesis

In 4,5-dichloro-6-methoxy-2-methyl-3(2H)-oxime To a mixture of 2.0 g (9.56 mmol) of ketone and 20 ml of methanol, 1.93 g of a 28% sodium methoxide methanol solution was added at room temperature, followed by stirring for 3 hours. The reaction solution was concentrated under reduced pressure. The obtained solid was washed with water, washed with a mixed solvent of hexane:MTBE=3:1, and dried to give 4-chloro-5,6-dimethoxy-2-methyl-3(2H)-indole. Ketone 1.22 g.

¹ H NMR (CDCl ₃ ) δ ppm: 3.68 (3H, s), 3.90 (3H, s), 4.06 (3H, s).

Reference example 3-4

4-(2-ethyl-4-benzyloxyphenyl)-2-methyl-5,6-dimethoxy-3(2H)-indole Ketone synthesis

4-Chloro-5,6-dimethoxy-2-methyl-3(2H)-oxime Ketone 1.03g, 4-benzyloxy-2-ethylphenylboronic acid 1.42g, 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl 830mg, tris(dibenzylideneacetone) II A mixture of 457 mg of palladium, 4.31 g of potassium phosphate and 50 ml of ethylene glycol dimethyl ether was stirred under heating under reflux for 11 hours under a nitrogen atmosphere. After cooling the reaction mixture at room temperature, it was concentrated under reduced pressure. Water was added to the residue, and the mixture was evaporated. The residue was purified by cerium oxide gel column chromatography (hexane: ethyl acetate = 2:1) to give 4-(2-ethyl-4-benzyloxyphenyl)-2- Radyl-5,6-dimethoxy-3(2H)-oxime Ketone 1.75 g.

¹ H NMR (CDCl ₃ ) δ ppm: 1.14 (3H, t, J = 7.5 Hz), 2.37-2.58 (2H, m), 3.56 (3H, s), 3.66 (3H, s), 3.92 (3H, s ), 5.08 (2H, s), 6.85 (1H, dd, J = 8.5, 2.7 Hz), 6.96 (1H, d, J = 2.7 Hz), 7.05 (1H, d, J = 8.5 Hz), 7.33 (1H) , t, J = 7.2 Hz), 7.39 (2H, t, J = 7.2 Hz), 7.45 (2H, d, J = 7.0 Hz).

Reference example 3-5

Synthesis of Compound (II-3)

4-(2-Ethyl-4-benzyloxyphenyl)-2-methyl-5,6-dimethoxy-3(2H)-oxime Ketone-substituted 4-(2-ethyl-4-benzyloxyphenyl)-2,6-dimethyl-5-methoxy-3(2H)-oxime The ketone was obtained according to Reference Example 1-5 to give the compound (II-3).

¹ H NMR (CDCl ₃ ) δ ppm: 1.08 (3H, t, J = 7.5 Hz), 2.32-2.49 (2H, m), 3.68 (3H, s), 3.95 (3H, s), 6.65 (1H, dd , J = 8.3, 2.6 Hz), 6.74 (1H, d, J = 2.6 Hz), 6.90 (1H, d, J = 8.3 Hz), 8.31 (1H, br s).

Reference example 4

Synthesis of Compound (II-1)

Reference example 4-1

Synthesis of 2-ethyl-4-methoxybromobenzene

To a solution obtained by dissolving 3.02 g of 4-bromo-3-ethylphenol in 14 ml of acetonitrile, 1.22 ml of methyl iodide and 3.12 g of potassium carbonate were added, and the mixture was stirred at 60 ° C for 4 hours. The reaction solution was cooled to room temperature, filtered, and the filtrate was concentrated. The residue was purified by yttrium gel column chromatography (hexane: ethyl acetate = 95:5) to yield 2.79 g of the object.

¹ H NMR (CDCl ₃ ) δ ppm: 1.22 (3H, t, J = 7.6 Hz), 2.71 (2H, q, J = 7.6 Hz), 3.78 (3H, s), 6.62 (1H, dd, J = 8.7 , 3.0Hz), 6.79 (1H, d, J = 3.0Hz), 7.40 (1H, d, J = 8.7Hz).

Reference example 4-2

Synthesis of 2-ethyl-4-methoxybenzylaldehyde

A solution of 2.79 g of 2-ethyl-4-methoxybromobenzene dissolved in 13 ml of anhydrous THF was cooled to -70 ° C, and slowly dropped into n-butyllithium (1.64 mol/L, hexane solution) 9 ml. . After stirring at -50 to -78 ° C for 1 hour after the completion of the dropwise addition, 2 ml of DMF was slowly added dropwise. After the reaction mixture was stirred at -78 ° C for 15 minutes, 20 ml of 2N hydrochloric acid was added at room temperature and stirred for 30 minutes. The reaction mixture was extracted twice with EtOAc (EtOAc) EtOAc.

¹ H NMR (CDCl ₃ ) δ ppm: 1.27 (3H, t, J = 7.6 Hz), 3.05 (2H, q, J = 7.6 Hz), 3.88 (3H, s), 6.78 (1H, d, J = 2.6 Hz), 6.85 (1H, dd, J = 8.6, 2.6 Hz), 7.80 (1H, d, J = 8.6 Hz), 10.13 (1H, s).

Reference example 4-3

Synthesis of 2-ethyl-4-methoxybenzyl alcohol

In a solution obtained by dissolving 40 g of 2-ethyl-4-methoxybenzyl aldehyde in 200 ml of ethanol, 4.38 g of sodium borohydride was added in small portions several times. The reaction solution was stirred at room temperature for 1 hour. After completion of the reaction, acetone was added thereto, followed by quenching, followed by concentration under reduced pressure. Water was added to the residue, and the mixture was extracted twice with ethyl acetate.

¹ H NMR (CDCl ₃ ) δ ppm: 1.25 (3H, t, J = 7.6 Hz), 2.72 (2H, q, J = 7.6 Hz), 3.81 (3H, s), 4.66 (2H, s), 6.73 ( 1H, dd, J = 8.2, 2.7 Hz), 6.79 (1H, d, J = 2.7 Hz), 7.26 (2H, d, J = 8.2 Hz).

Reference example 4-4

Synthesis of 2-ethyl-4-methoxybenzyl chloride

In a solution obtained by dissolving 37 g of 2-ethyl-4-methoxybenzyl alcohol in 100 ml of toluene, 15.4 ml of sulfite chloride was added dropwise under ice cooling. After the completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours. The reaction mixture was washed with water, washed with brine, dried over anhydrous magnesium sulfate, and evaporated.

¹ H NMR (CDCl ₃ ) δ ppm: 1.28 (3H, t, J = 7.6 Hz), 2.76 (2H, q, J = 7.6 Hz), 3.81 (3H, s), 4.62 (2H, s), 6.72 ( 1H, dd, J = 8.2, 2.7 Hz), 6.78 (1H, d, J = 2.7 Hz), 7.25 (1H, d, J = 8.2 Hz).

Reference example 4-5

Synthesis of 2-ethyl-4-methoxybenzeneacetonitrile

2.2 g of 2-ethyl-4-methoxybenzyl chloride was dissolved in 5 ml of anhydrous DMF. To the solution was added 0.62 g of sodium cyanide, and the mixture was stirred at room temperature overnight. MTBE was added to the reaction mixture, and water was added thereto, and the mixture was extracted twice with EtOAc (EtOAc).

¹ H NMR (CDCl ₃ ) δ ppm: 1.26 (3H, t, J = 7.6 Hz), 2.63 (2H, q, J = 7.6 Hz), 3.64 (2H, s), 3.81 (3H, s), 6.75 ( 1H, dd, J = 8.3, 2.8 Hz), 6.79 (1H, d, J = 2.8 Hz), 7.27 (3H, d, J = 8.3 Hz).

Reference example 4-6

Synthesis of 2-ethyl-4-methoxyphenylacetic acid

To a solution obtained by dissolving 1.0 g of 2-ethyl-4-methoxyphenylacetonitrile in 2 ml of acetic acid, 4 ml of a 50% aqueous sulfuric acid solution was added, and the mixture was stirred at 105 ° C for 3 hours. The reaction mixture was poured into ice water, and the mixture was extracted twice with EtOAc.

¹ H NMR (CDCl ₃ ) δ ppm: 1.21 (3H, t, J = 7.6 Hz), 2.62 (2H, q, J = 7.6 Hz), 3.62 (2H, s), 3.79 (3H, s), 6.71 ( 1H, dd, J = 8.4, 2.8 Hz), 6.78 (1H, d, J = 2.8 Hz), 7.12 (1H, d, J = 8.4 Hz).

Reference example 4-7

4-(2-ethyl-4-methoxyphenyl)-2,6-dimethyl-5-hydroxy-3(2H)-indole Ketone synthesis

A mixed solution of 3.06 g of 2-ethyl-4-methoxyphenylacetic acid, 2.3 ml of sulfinium chloride and 15 ml of toluene was stirred at 100 ° C for 1 hour, and then concentrated under reduced pressure. Will The mixed solution was added to a mixed solution of 2.1 g of ethyl 2-(2-methylimino)propanoate, 1.72 ml of pyridine and 20 ml of THF under ice cooling. After the reaction mixture was stirred at room temperature overnight, water was added, and the mixture was evaporated. A solution obtained by dissolving the residue in 15 ml of anhydrous THF was added to a solution of 5.83 g of potassium tributoxide and 20 ml of anhydrous THF at 35 to 40 °C. After the reaction mixture was stirred at room temperature for 1 hour, 50 ml of 2N hydrochloric acid was added, and the mixture was extracted twice with MTBE, washed with brine, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. Purification by column chromatography gave 1.41 g of the object.

¹ H NMR (CDCl ₃ ) δ ppm: 1.11 (3H, t, J = 7.6 Hz), 2.32 (3H, s), 2.35-2.55 (2H, m), 3.74 (3H, s), 3.84 (3H, s ), 5.54 (1H, s), 6.84 (1H, dd, J = 8.5, 2.6 Hz), 6.94 (1H, d, J = 2.6 Hz), 7.05 (1H, d, J = 8.5 Hz).

Reference example 4-8

Synthesis of Compound (II-1)

In the 4-(2-ethyl-4-methoxyphenyl)-2,6-dimethyl-5-hydroxy-3(2H)-oxime A solution of 1.22 g of ketone dissolved in 5 ml of acetic acid was added to 5 ml of 47% hydrogen bromide, and the mixture was stirred at 110 ° C for 12 hours. The reaction mixture was poured into ice water, and the mixture was evaporated to ethylamine. The obtained solid was washed with hexane to obtain 1.07 g of Compound (II-1).

Next, the formulation examples are shown.

Formulation Example 1

Hydrating agent

The above components are mixed and pulverized to obtain a hydrating agent.

Substituting the compound (I-1), the compound (I-2) to the compound (I-13), the compound (I-14-1) to the compound (I-14-71), and the compound (I-15) are obtained in the same manner. -1) to the respective hydrating agents of the compound (I-15-2).

Formulation Example 2

Granule

The above ingredients are mixed, water is added and kneaded and granulated/dried to obtain granules.

Substituting the compound (I-1), the compound (I-2) to the compound (I-13), the compound (I-14-1) to the compound (I-14-71), and the compound (I-15) are obtained in the same manner. -1) to the respective granules of the compound (I-15-2).

Formulation Example 3

Flowability agent

The above components are mixed and finely pulverized by a wet pulverization method to obtain a flowable agent. Substituting the compound (I-1), the compound (I-2) to the compound (I-13), the compound (I-14-1) to the compound (I-14-71), and the compound (I-15) are obtained in the same manner. -1) to respective flowable agents of the compound (I-15-2).

Test Example 1 Post-emergence treatment test in dry land

In a plastic cup having a diameter of 8 cm and a depth of 6.5 cm, a commercially available seedling soil was filled, and the seed of the pot was seeded in the cup, and the soil was covered for about 0.5 cm, and then cultivated in a greenhouse for a certain period of time. When the plant is grown to the 1st to 2nd leaf stage, the drug diluent containing the compound of the present invention is evenly spread over the entire plant with a certain amount of treatment. Further, the drug diluent is a dimethylformamide which is dissolved in a Tween emulsifier 20 (tween 20, polyoxyethylene sorbitan fatty acid ester, MP Biomedicals) by a certain amount of the compound of the present invention. The solution (2%) was prepared by diluting with deionized water. The treated plants were cultivated in a greenhouse, and after 20 days of treatment, the efficacy of the control against cockroaches was evaluated and evaluated in 11 stages of 0 to 10 (0 no effect, 10 completely dead, and the middle was divided into 1 to 9 stages to be evaluated. ).

In the same manner, other compounds of the invention are also provided for testing.

As a result, the compounds (I-1), (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8) ), (I-9), (I-11), (I-12), (I-13), (I-14-1), (I-14-2), (I-14-3), (I-14-5), (I-14-6), (I-14-7), (I-14-8), (I-14-9), (I-14-10), (I -14-11), (I-14-12), (I-14-13), (I-14-14), (I-14-15), (I-14-16), (I-14 -17), (I-14-18), (I-14-19), (I-14-20), (I-14-21), (I-14-22), (I-14-23 ), (I-14-24), (I-14-25), (I-14-26), (I-14-27), (I-14-28), (I-14-29), (I-14-30), (I-14-31), (I-14-32), (I-14-33), (I-14-34), (I-14-35), (I -14-36), (I-14-37), (I-14-38), (I-14-39), (I-14-40), (I-14-41), (I-14 -42), (I-14-43), (I-14-44), (I-14-45), (I-14-46), (I-14-47), (I-14-48 ), (I-14-49), (I-14-50), (I-14-51), (I-14-52), (I-14-53), (I-14-55), (I-14-56), (I-14-57), (I-14-58), (I-14-59), (I-14-60), (I-14-62), (I -14-63), (I-14-65), (I-14-66), (I-14-67), (I-14-68), (I-14-69), (I-14 -70), (I-14-71), (I-15-1), and (I-15-2) exhibit an efficacy of 9 or more at a treatment amount of 1,000 g/10000 m ² .

Test Example 2 Pre-emergence treatment test in dry land

In a plastic cup having a diameter of 8 cm and a depth of 6.5 cm, steam-sterilized dry soil was filled, and seeds of Italian ryegrass were planted in the cup, covering about 0.5 cm. Subsequently, the drug diluent containing the compound of the present invention is evenly spread on the surface of the soil with a certain amount of treatment. Further, the drug diluent was prepared in the same manner as in Test Example 1. The plants treated with the drug were cultivated in a greenhouse, and the efficacy of the control against Italian ryegrass was evaluated after 3 weeks of treatment, and was shown in 11 stages divided into 0 to 10 in the same manner as in Test Example 1.

In the same manner, other compounds of the invention are also provided for testing.

As a result, the compounds (I-2), (I-3), (I-4), (I-5), (I-6), (I-7), (I-8), (I-11) ), (I-12), (I-13), (I-14-1), (I-14-2), (I-14-3), (I-14-5), (I-14 -6), (I-14-7), (I-14-8), (I-14-9), (I-14-12), (I-14-15), (I-14-16 ), (I-14-17), (I-14-19), (I-14-20), (I-14-22), (I-14-23), (I-14-24), (I-14-25), (I-14-26), (I-14-27), (I-14-29), (I-14-30), (I-14-31), (I -14-32), (I-14-33), (I-14-34), (I-14-35), (I-14-36), (I-14-38), (I-14 -39), (I-14-40), (I-14-41), (I-14-43), (I-14-44), (I-14-47), (I-14-51 ), (I-14-52), (I-14-53), (I-14-55), (I-14-56), (I-14-58), (I-14-59), (I-14-62), (I-14-63), (I-14-66), (I-14-67), (I-14-68), (I-14-70), (I -14-71) and (I-15-2) exhibit an efficacy of 9 or more at a treatment amount of 1,000 g/10000 m ² .

Test Example 3 Test for weeding effect on weeds in paddy fields

The steam-sterilized soil was filled in a plastic cup having a diameter of 9 cm and a depth of 10 cm, and the rice bran was sown and cultivated in a greenhouse to a certain growth stage (1 leaf stage). After adjusting the water storage depth to 3 cm, the drug dilution containing the compound of the present invention was treated with a certain treatment amount to treat the water storage soil. Further, the drug diluent is obtained by dissolving a predetermined amount of the compound of the present invention in an acetone solution (2%) of Tween emulsifier 20 (polyoxyethylene sorbitan fatty acid ester, MP Biomedicals). Dilute with deionized water to prepare. The plants treated with the medicament were cultivated in a greenhouse, and the efficacy of weed control was evaluated after 20 days of treatment, and was represented by 11 stages of 0 to 10 (0 no effect, 10 complete death, and 1 to 9 at equal intervals therebetween) Stage evaluation).

As a result, the compounds (I-3), (I-4), (I-5), (I-9), (I-11), and (I-14-66) are treated with 1,000 g/10000 m ² of the drug. The amount shows an effect of 9 or more. Compounds (I-2), (I-6), (I-7), (I-8), (I-12), (I-13), (I-14-1), (I-14- 2), (I-14-3), (I-14-29), (I-14-32), (I-14-33), (I-14-66), (I-14-68) (I-14-71), (I-15-1), and (I-15-2) exhibited an efficacy of 9 or more at a treatment amount of 250 g/10000 m ² .

Test Example 4 Test for weeding effect on weeds in paddy fields

The steam-sterilized soil was filled in a plastic cup having a diameter of 9 cm and a depth of 10 cm, and the rice bran was sown and cultivated in a greenhouse to a certain growth stage (1 leaf stage). After adjusting the water storage depth to 0 cm, the drug dilution containing the compound of the present invention was subjected to stem and leaf treatment at a predetermined treatment amount. Further, the drug diluent is obtained by dissolving a predetermined amount of the compound of the present invention in a dimethylformamide solution of Tween emulsifier 20 (polyoxyethylene sorbitan fatty acid ester, MP Biomedicals). 2%), prepared by dilution with deionized water. After 24 hours of treatment, water was refilled to make the water storage depth 3 cm. Dispensing the agent The plants were cultivated in a greenhouse, and the efficacy of weed control was evaluated after 20 days of treatment, and was expressed in 11 stages of 0 to 10 (0 no effect, 10 complete death, and a stage evaluation of 1 to 9 at equal intervals) ).

As a result, (I-14-5), (I-14-6), (I-14-7), (I-14-8), (I-14-12), (I-14-13) , (I-14-15), (I-14-16), (I-14-17), (I-14-18), (I-14-19), (I-14-20), ( I-14-21), (I-14-22), (I-14-23), (I-14-24), (I-14-25), (I-14-26), (I- 14-27), (I-14-28), (I-14-30), (I-14-31), (I-14-34), (I-14-35), (I-14- 36), (I-14-37), (I-14-38), (I-14-39), (I-14-40), (I-14-41), (I-14-43) , (I-14-44), (I-14-46), (I-14-47), (I-14-48), (I-14-51), (I-14-52), ( I-14-53), (I-14-55), (I-14-56), (I-14-58), (I-14-59), (I-14-60), (I- 14-62), (I-14-63), (I-14-67), (I-14-69), and (I-14-70) compounds exhibit 9 or more at a treatment dose of 1,000 g/10000 m ² Effectiveness.

Comparative test example 1 herbicidal effect test on weeds in paddy fields

The herbicidal effect test on the weeds in the paddy field was carried out according to the method described in Test Example 3 using the compound (I-2) and the comparative compound 1. The result is shown in the second table.

Comparative Compound 1 is a compound which is described as herbicidal activity in Table 5CA (pp. 67 to 68) of WO2009086041A1.

The compounds of the invention have weed control efficacy.

Claims (11)

嗒 expressed by formula (I) Ketone compounds: Wherein R ¹ represents hydrogen, C _1-6 alkyl, C _3-8 cycloalkyl, (C _3-8 cycloalkyl) C _1-6 alkyl, C _3-4 alkenyl or C _{3- 4} alkynyl, R ² represents hydrogen, halogen, cyano, nitro, C _1-6 alkyl, C _1-6 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _1-6 alkylthio, C _1-6 alkylsulfinyl, C _1-6 alkylsulfonyl, C _1-6 haloalkylthio, C _1-6 haloalkylsulfinyl, C _1-6 haloalkylsulfonyl, C _3-8 cycloalkyl, (C _3-8 cycloalkyl) C _1-6 alkyl, C _3-8 cycloalkoxy, (C _3-8 naphthenic) yl) C _1-6 alkoxy, (C _1-6 alkylthio) C _1-6 alkoxy, (C _1-6 alkoxy) C _1-6 alkoxy, C _3-6 alkenyloxy a group, a C _3-6 alkynyloxy group, a cyano C _1-6 alkoxy group, a (C _1-6 alkoxy)carbonyl C _1-6 alkoxy group, an amine carbaryl C _1-6 alkoxy group, {(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy, {di(C _1-6 alkyl)aminocarbonyl}C _1-6 alkoxy, amine, C _1-6 An alkylamino group, a di(C _1-6 alkyl)amino group, a decylamino group, a (C _1-6 alkyl)carbonylamino group, a hydroxy C _1-6 alkyl group, a (C _1-6 alkoxy group) C _1-6 alkyl, (C _1-6 haloalkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, {(C _3-8 naphthenic) Base) C _1-6 alkoxy} C _1-6 alkane , (C _1-6 alkylthio) C _1-6 alkyl, (C _1-6 haloalkylthio) C _1-6 alkyl, cyano C _1-6 alkyl, hydroxyimino C _{1 a -6} alkyl group, a (C _1-6 alkoxy) imido C _1-6 alkyl group, a decyl group or a (C _1-6 alkyl) carbonyl group, and R ³ represents a halogen, a C _1-3 alkyl group, C _1-3 haloalkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-3 alkoxy, C _1-3 haloalkoxy or C _3-8 cycloalkyl, R ⁴ and R ⁵ may be the same or different and represents hydrogen, halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _2-4 alkenyl, C _2-4 alkynyl, C _1-3 alkoxy, C _1-3 haloalkoxy or C _3-8 cycloalkyl, A represents an aryl group of a monocyclic or bicyclic condensed ring, or one or more selected from the group consisting of nitrogen, oxygen and sulfur. a heteroaryl group having a monocyclic or bicyclic condensed ring of a hetero atom, wherein the group may have one or more atoms or groups selected from the group B, and G represents hydrogen or any one of the following formulas: Wherein L represents oxygen or sulfur, and R ⁶ represents C _1-12 alkyl, C _3-8 cycloalkyl, C _2-12 alkenyl, C _2-12 alkynyl, and may have 1 selected from group D. one or more atoms or C _6-10 aryl group, (D may have selected a group of one or more atoms or groups C _6-10 aryl) C _1-12 alkyl, C _1-12 alkoxy a C _3-8 cycloalkoxy group, a C _3-12 alkenyloxy group, a C _3-12 alkynyloxy group, a C _6-10 aryloxy group which may have one or more atoms or groups selected from the D group, (C _6-10 aryl group having 1 or more atoms or groups selected from the D group) C _1-12 alkoxy group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _{1 -6} alkoxy) C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (C _{1- 6} alkylsulfinyl acyl) C _1-6 alkyl, (C _C1-6 alkylsulfonyl group) C _1-6 alkyl, (C may have a group selected from D or more atoms or groups _6-10 aryloxy) C _1-12 alkyl, (D may have selected a group of one or more atom or group of C _6-10 arylthio) C _1-12 alkyl, {(may have One or more atoms selected from group D or a C _6-10 aryl)C _1-6 alkoxy}C _1-6 alkyl group, (C _3-8 cycloalkyl) C _1-6 alkoxy group base Di (C _1-6 alkyl) amino, di (C _3-6 alkenyl) amino, (C _1-6 alkyl) (C _6-10 aryl) amino group or 5-6 heteroaryl And R ⁷ represents a C _1-6 alkyl group, a C _1-3 haloalkyl group, a C _6-10 aryl group or a di(C _1-6 alkyl group) which may have one or more atoms or groups selected from the D group. Amino, R ⁸ and R ⁹ may be the same or different and represent C _1-6 alkyl, C _3-8 cycloalkyl, C _6-10 aryl, C _1-6 alkoxy, C _3-8 Cycloalkoxy, C _6-10 aryloxy, (C _6-10 aryl) C _1-6 alkoxy, C _1-6 alkylthio or di(C _1-6 alkyl)amine, R ¹⁰ represents hydrogen or C _1-6 alkyl, W represents a one or more atom or group selected from the group D is phenyl, C _1-6 alkoxy, C _1-6 alkylthio, C _{1- a 6} -alkylsulfinyl group or a C _1-6 alkylsulfonyl group; here, any of R ⁶ , R ⁷ , R ⁸ , R ⁹ and W each independently may have a halogen, R ⁶ C _3-8 cycloalkyl, R ⁶ , R ⁸ and R ⁹ C _3-8 cycloalkoxy, R ⁸ and R ⁹ (C _1-6 alkyl)(C _6-10 aryl)amino Any of the aromatic moiety and the heteroaryl group of 5 to 6 members may have a C _1-6 alkyl group, and the group B: halogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-3 alkane Oxyl, C _{1- 3} -haloalkoxy, C _3-8 cycloalkyl, C _2-4 alkenyl, C _2-4 haloalkenyl, C _2-4 alkynyl, C _1-3 alkylthio, C _1-3 halo Sulfhydryl, C _1-3 alkylsulfinyl, C _1-3 haloalkylsulfinyl, C _1-3 alkylsulfonyl, C _1-3 haloalkylsulfonyl, nitro, Cyano, (C _1-6 alkyl)carbonyl, (C _1-6 alkoxy)carbonyl, aminecarbamyl, (C _1-3 alkyl)aminocarbonyl, di(C _1-3 alkyl) Aminocarbonyl, (C _1-6 alkyl)carbonylamino, (C _3-8 cycloalkyl)carbonylamino, (C _3-8 alkoxy)carbonylamino, and (C _1-3 alkoxy a group of C _1-3 alkyl groups, group D: from halogen, C _1-6 alkyl, C _1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy a group of C _1-3 alkylthio, cyano and nitro groups]. As described in the first paragraph of the patent application scope a ketone compound, wherein A represents a phenyl group, a naphthyl group, a pyridyl group, an anthracene Base, pyrimidinyl, pyridyl Benzothiazolyl, benzo Azyl, quinolyl, porphyrin, quinazolinyl, quin Porphyrin or benzotrien The group may have one or more atoms or groups selected from the group B, and G represents hydrogen or any of the groups represented by the following formula: ^Wherein R ^6a represents a C _1-12 alkyl group, a C _1-12 haloalkyl group, a C _3-8 cycloalkyl group, or a C _6-10 aryl group which may have one or more atoms or groups selected from the D group. a group, a C _6-10 aryl group (which may have one or more atoms or groups selected from the D group), a C _1-12 alkyl group, a C _1-12 alkoxy group, a C _3-12 alkenyloxy group, a C ₃ group _{a -12} alkynyloxy group, a C _6-10 aryloxy group having 1 or more atoms or groups selected from the D group, (C _3-8 cycloalkyl) C _1-6 alkyl group, (C _1-6 Alkoxy)C _1-6 alkyl, (C _3-8 cycloalkoxy) C _1-6 alkyl, (C _1-6 alkylthio) C _1-6 alkyl, (may have a group D C _6-10 aryl group selected one or more atom or group) C _1-12 alkyl, (which may have one or more atom or group selected from the group D C _6-10 arylthio) C _1-12 alkyl, {(C _6-10 aryl which may have 1 or more atoms selected from the D group) C _1-6 alkoxy} C _1-6 alkyl or (C _{3- 8} -cycloalkyl)C _1-6 alkoxy, R ^7a represents a C _1-6 alkyl group or a C _6-10 aryl group which may have one or more atoms or groups selected from the D group, and W ^a represents C _{1 a -3} alkoxy group or a phenyl group B which may have one or more atoms or groups selected from the D group is a halogen, a C _1-3 alkyl group , C _1-3 haloalkyl, C _1-3 alkoxy, C _1-3 haloalkoxy, nitro or cyano. As described in the second paragraph of the patent application scope a ketone compound, wherein R ² is hydrogen, C _1-3 alkyl, C _1-3 haloalkyl, C _1-6 alkoxy, C _1-6 haloalkoxy, C _3-8 cycloalkyl, C _3-8 cycloalkoxy or (C _3-8 cycloalkyl) C _1-6 alkoxy. As described in item 3 of the patent application scope A ketone compound wherein R ¹ is a methyl group. As described in item 3 of the patent application scope A ketone compound wherein R ² is hydrogen, methyl or methoxy. As described in the second paragraph of the patent application scope A ketone compound wherein R ¹ is methyl, R ² is hydrogen, methyl or methoxy, and R ³ is methyl, ethyl, propyl, cyclopropyl, halogen or halomethyl. As described in the first paragraph of the patent application scope a ketone compound wherein A is pyridyl, benzothiazolyl, benzo The azole group or the quinolyl group may have one or more atoms or groups selected from the group B. As described in item 6 of the patent application scope a ketone compound wherein R ³ is methyl, ethyl, propyl or cyclopropyl, R ⁴ and R ⁵ are hydrogen, and A is pyridyl, benzothiazolyl, benzo The azole group or the quinolyl group may have one or more atoms or groups selected from the group B. A herbicide containing the hydrazine as described in any one of claims 1 to 8. A ketone compound is used as an active ingredient. A method for controlling weeds according to any one of claims 1 to 8 An effective amount of a ketone compound is applied to the control of weeds in weeds or weed-growing soils. A patent application according to any one of claims 1 to 8 The use of ketone compounds is used for the control of weeds.