JP2016117714A - Heterocyclic amide compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel agrochemical, particularly a herbicide, which has effects on a wide range of weeds at a low dosage, and reduces problems such as contamination of the soil and influence on crops.SOLUTION: The present invention provides a heterocyclic amide compound represented by formula (1) and a herbicide comprising the same (Q is a 5 membered aromatic heterocycle comprising N and/or O; W is a benzotriazol derivative; X is S or S; Ris H, alkyl, haloalkyl, cycloalkyl or the like).SELECTED DRAWING: None

Description

  The present invention relates to a novel heterocyclic amide compound and a salt thereof, and an agrochemical, particularly a herbicide, containing the heterocyclic amide compound and a salt thereof as an active ingredient. The agrochemical in the present invention means an insecticide / acaricide, nematicide, herbicide, fungicide, etc. in the field of agriculture and horticulture.

  For example, Patent Documents 1 to 10 disclose certain types of heterocyclic amide compounds, but do not disclose any heterocyclic amide compounds according to the present invention.

International Publication No. 2013/092834 International Publication No. 2013/139760 International Publication No. 2013/144231 International Publication No. 2013/164333 International Publication No. 2014/053473 International Publication No. 2014/086737 International Publication No. 2014/126070 International Publication No. 2014/135654 International Publication No. 2014/192936 International Publication No. 2015/007633

  The object of the present invention is a highly safe and effective herbicide active ingredient that reliably shows effects on various weeds at a lower dose, and has reduced problems such as soil contamination and effects on subsequent crops. It is to provide useful chemical substances.

  As a result of intensive studies aimed at solving the above-mentioned problems, the present inventors have found that the novel heterocyclic amide compound represented by the following formula (1) according to the present invention has excellent herbicidal activity and target as a herbicide. The present invention has been completed by discovering that it is a highly useful compound that has a high safety against certain crops and has almost no adverse effect on non-target organisms such as mammals, fish and beneficial insects.

  That is, the present invention relates to the following [1] to [4].

[1]
Formula (1):

[Wherein Q represents an aromatic heterocycle represented by any one of Q-1 to Q-7,

  W represents an aromatic heterocyclic ring represented by W-1,

X represents an oxygen atom or a sulfur atom,
R ^1a is (C ₁ -C ₆ ) alkyl optionally substituted by R ⁶ , —N (R ³⁶ ) R ³⁷ , —OR ⁴⁰ , —S (O) _m1 R ⁷ , U-1, U-2 , U-3, U-4, U-5, U-6, U-7, U-21 or U-22,
R ^2a represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, —C (O) R ²⁵ , cyano, nitro, —OR ²⁶ or —S (O) _m5 R ²⁷ . , N represents an integer of 2 or more, each R ^2a may be the same as or different from each other,
Further, when two R ^2a are adjacent, the two adjacent R ^2a are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ^2a is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ³ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or -C (O ) Represents R ²⁹
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g and R ^4h are each independently optionally substituted with a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, or R ³¹ . _(C 1 _{~C 6)} represents _alkyl, C 3 -C ₆ cycloalkyl, phenyl substituted by phenyl or ^(R _{32) q2,}
R ^5a , R ^5b and R ^5c are each independently substituted with a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl, phenyl or (R ³² ) _q2 optionally substituted with R ³¹ Represented phenyl,
R ^{6 _{is, -OR 11, -S (O)}} m2 R 12, U-3, U-4, U-8, U-9, U-10, U-11, U-12, U-13, U -23, U-24, U-25, U-26, U-27, U-28 or U-29,
R ⁷ is optionally substituted by ^{R 9} _(C 1 ^~C ₆₎ alkyl, ^phenyl, phenyl substituted by _{^{(R 10) q1, U-}} 11, U-12, U-13, U'-11 , U′-12, U′-13, U-14, U-15, U-16, U-23, U-24, U-25, U-30, U-31, U-32, U-33 , U-34, U-35, U-36, U-37 or U-38,
R ⁸ is a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -C (O ) R ¹³ , cyano, —OR ¹⁴ , —N (R ¹⁵ ) R ¹⁶ or —S (O) _m3 R ^17, and when p4, p5, p7 or p9 represents an integer of 2 or more, each R ⁸ May be the same or different from each other,
Furthermore, when two R ⁸ are adjacent, the two adjacent R ⁸ are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ⁸ is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally is substituted by ₁ -C ₆₎ alkyl Even if well,
R ^8a represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ⁹ represents -OR ¹⁸ , U-17, U-18 or U-19,
U-1 to U-38 and U′-11 to U′-13 each represent a heterocyclic ring represented by the following structure,

R ¹⁰ is a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -C (O ) R ¹³ , cyano, —OR ²⁰ , —N (R ²¹ ) R ²² or —S (O) _m4 R ^23, and when q1 represents an integer of 2 or more, each R ¹⁰ is the same as each other Or different from each other,
Further, when two R ¹⁰ are adjacent, the two adjacent R ¹⁰ are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ¹⁰ is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ¹¹ and R ¹² each independently represent phenyl substituted by (R ¹⁰ ) _q1 ;
R ¹³ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ²⁴ ,
R ¹⁴ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl, or R ¹⁵ together with R ¹⁶ is C ₂ -C ₆ represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to which R ¹⁵ and R ¹⁶ are bonded by forming an alkylene chain, in which case the alkylene chain has an oxygen atom, a sulfur atom or a nitrogen atom. may 1 comprise, and a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 -C _{6) alkyl,} C 1 -C ₆ alkoxy, _formyl, C 1 -C _{6 alkylcarbonyl,} C 1 -C ₆ alkoxy Optionally substituted by carbonyl, oxo or thioxo,
R ¹⁷ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ¹⁸ represents -C (O) R ¹⁹ ;
R ¹⁹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²¹ and R ²² each independently represent a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl, or R ²¹ together with R ²² represents C ₂ -C ₆ represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to which R ²¹ and R ²² are bonded by forming an alkylene chain, and this alkylene chain has an oxygen atom, a sulfur atom or a nitrogen atom. may 1 comprise, and a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 -C _{6) alkyl,} C 1 -C ₆ alkoxy, _formyl, C 1 -C _{6 alkylcarbonyl,} C 1 -C ₆ alkoxy Optionally substituted by carbonyl, oxo or thioxo,
R ²³ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁴ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁵ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ²⁸ ;
R ²⁶ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or phenyl;
R ²⁷ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁸ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁹ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ³⁰ ;
R ³⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³¹ represents a halogen atom, phenyl, —OR ³³ or —S (O) _m6 R ³⁴ ,
R ³² represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ^35, and when q 2 represents an integer of 2 or more, each R ³² is the same as each other Or different from each other,
Furthermore, when two R ³² are adjacent, two adjacent R ³² are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 _{O -, - OCH 2 CH 2} O -, - CH 2 CH 2 CH 2 S -, - OCH by 2 _CH 2 S- or forming a -CH = CH-CH = CH-, each of the two ^{R 32} May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ³³ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁴ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁵ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁶ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halo (C ₂ -C ₆ ) alkenyl, C Represents _2- C ₆ alkynyl, halo (C ₂ -C ₆ ) alkynyl, phenyl or phenyl substituted by (R ¹⁰ ) _{q 1} ;
R ³⁷ is (C ₃ -C ₆ ) cycloalkyl, —OH, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, U-16, U-23, optionally substituted by R ³⁸ . Represents U-24 or U-25,
R ³⁸ represents a halogen atom, cyano or —C (O) OR ³⁹ ;
R ³⁹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ⁴⁰ represents C ₁ -C ₆ alkyl optionally substituted with R ⁴¹ or phenyl substituted with (R ¹⁰ ) _q1 ,
R ⁴¹ represents a halogen atom, C ₁ -C ₆ alkoxy or halo (C ₁ -C ₆ ) alkoxy,
G ¹ and G ² each independently represent —S (O) _m —,
m, m1, m2, m3, m4, m5 and m6 each independently represents an integer of 0, 1 or 2;
n independently represents an integer of 0, 1, 2, or 3,
p2 represents an integer of 0, 1 or 2;
p3 represents an integer of 0, 1, 2, or 3,
p4 represents an integer of 0, 1, 2, 3 or 4;
p5 represents an integer of 0, 1, 2, 3, 4 or 5;
p7 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
p9 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9,
q1 and q2 each independently represent an integer of 1, 2, 3, 4 or 5;
r6 represents an integer of 1, 2, 3, 4, 5 or 6;
r8 represents an integer of 1, 2, 3, 4, 5, 6, 7 or 8;
r10 represents an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Or a salt thereof.

[2]
Q represents Q-1 or Q-3,
X represents an oxygen atom,
R ^1a is (C ₁ -C ₆ ) alkyl optionally substituted with R ⁶ , —N (R ³⁶ ) R ³⁷ , —OR ⁴⁰ , —S (O) _m1 R ⁷ , U-1, U-3 , U-7, U-21 or U-22,
R ^2a represents halo (C ₁ -C ₆ ) alkyl;
R ³ represents a hydrogen atom,
R ^4a represents a hydrogen atom or C ₁ -C ₆ alkyl;
R ^5a represents C ₁ -C ₆ alkyl;
R ^{6 represents _{-OR 11, -S (O) m2}} R 12, U-3, U-8, U-11, U-12, U-13, U-25, U-26 or U-27 ,
R ⁷ is optionally substituted by ^{R 9} _(C 1 ^~C ₆₎ alkyl, ^phenyl, phenyl substituted by _{^{(R 10) q1, U-}} 11, U-12, U'-12, U-13 , U-15, U-16, U-23, U-24, U-25, U-31, U-32, U-33 or U-38,
R ⁸ represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, —C (O) R ¹³ or —OR ¹⁴ ;
R ^8a represents C ₁ -C ₆ alkyl;
R ⁹ represents -OR ¹⁸ or U-17,
R ¹⁰ represents cyano or —OR ²⁰ ,
R ¹³ represents —OR ²⁴ ;
R ¹⁴ , R ¹⁹ , R ²⁰ and R ²⁴ each independently represent C ₁ -C ₆ alkyl;
R ³⁶ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ³⁷ represents (C ₃ -C ₆ ) cycloalkyl, C ₁ -C ₆ alkoxy, U-16 or U-23, optionally substituted by R ³⁸ ,
R ³⁸ represents cyano,
R ⁴¹ represents a halogen atom or C ₁ -C ₆ alkoxy;
m1 represents an integer of 0 or 1,
n represents an integer of 1;
p2 represents an integer of 0 or 1,
p3 represents an integer of 0;
p4 represents an integer of 0 or 1,
p5, p7 and p9 represent an integer of 0;
q1 represents an integer of 1 or 2,
r8 and r10 represent an integer of 1; ] The heterocyclic amide compound or its salt as described in said [1] represented by these.

[3]
An agrochemical containing one or more selected from the heterocyclic amide compounds according to the above [1] to [2] and salts thereof as active ingredients.

[4]
A herbicide containing, as an active ingredient, one or more selected from the heterocyclic amide compounds according to the above [1] to [2] and salts thereof.

  The compound of the present invention has excellent herbicidal activity against various weeds and has high safety against the target crop. Furthermore, it has little adverse effect on non-target organisms such as mammals, fish and beneficial insects, has low persistence, and has a light impact on the environment.

  Therefore, the present invention can provide a herbicide useful in the field of agriculture and horticulture such as paddy fields, upland fields, and orchards.

  The compounds included in the present invention may have geometrical isomers of E-form and Z-form depending on the type of substituent, and the present invention is not limited to these E-form, Z-form or E-form. And a mixture containing the Z-form in an arbitrary ratio. In addition, the compounds included in the present invention include optically active substances resulting from the presence of one or more asymmetric carbon atoms, but the present invention includes all optically active substances or racemates.

  Among the compounds included in the present invention, those that can be converted into acid addition salts according to a conventional method include, for example, hydrohalic acids such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, and the like. Salt of inorganic acid such as salt, nitric acid, sulfuric acid, phosphoric acid, chloric acid, perchloric acid, salt of sulfonic acid such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, Salts of carboxylic acids such as formic acid, acetic acid, propionic acid, trifluoroacetic acid, fumaric acid, tartaric acid, succinic acid, maleic acid, malic acid, succinic acid, benzoic acid, mandelic acid, ascorbic acid, lactic acid, gluconic acid, citric acid, etc. A salt of an amino acid such as glutamic acid or aspartic acid can be used.

  Alternatively, among the compounds included in the present invention, those that can be converted into a metal salt according to a conventional method include, for example, alkali metal salts such as lithium, sodium, and potassium, and alkaline earth metals such as calcium, barium, and magnesium. It can be a salt or a salt of aluminum.

  Next, specific examples of each substituent shown in the present specification are shown below. Here, n- represents normal, i- represents iso, s- represents secondary, and tert- or t- represents tertiary, and Ph represents phenyl.

  Examples of the halogen atom in the present specification include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. In the present specification, the notation “halo” also represents these halogen atoms.

The notation of C _a -C _b alkyl in the present specification represents a linear or branched hydrocarbon group having a carbon number of _a to _b , for example, methyl group, ethyl group, n-propyl group, Specific examples include i-propyl group, n-butyl group, i-butyl group, s-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, n-hexyl group, and the like. Each selected range of carbon atoms is selected.

In the present specification, C _a -C _b cycloalkyl represents a cyclic hydrocarbon group having a carbon number of _a to _b , and forms a monocyclic or complex ring structure having 3 to 6 members. I can do it. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. Specific examples include, for example, cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group and the like. Selected in a range of numbers.

In the present specification, C _a -C _b alkenyl is a linear or branched chain composed of _a to _b carbon atoms and has one or more double bonds in the molecule. Represents a saturated hydrocarbon group, for example, vinyl group, 1-propenyl group, 2-propenyl group, 1-methylethenyl group, 2-butenyl group, 2-methyl-2-propenyl group, 3-methyl-2-butenyl group, 1 , 1-dimethyl-2-propenyl group and the like are listed as specific examples, and each is selected within the range of the designated number of carbon atoms.

In the present specification, C _a -C _b alkynyl is a linear or branched chain composed of _a to _b carbon atoms and has one or more triple bonds in the molecule. Represents a hydrocarbon group, for example, ethynyl group, 1-propynyl group, 2-propynyl group, 1-butynyl group, 2-butynyl group, 3-butynyl group, 1,1-dimethyl-2-propynyl group, etc. Each of which is selected for each specified number of carbon atoms.

In the present specification, the notation of halo (C _a -C _b ) alkyl is a straight or branched chain consisting of _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom A chain-like hydrocarbon group is represented, and when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, fluoromethyl group, chloromethyl group, bromomethyl group, iodomethyl group, difluoromethyl group, dichloromethyl group, trifluoromethyl group, chlorodifluoromethyl group, trichloromethyl group, bromodifluoromethyl group, 2-fluoroethyl group, 2- Chloroethyl group, 2-bromoethyl group, 2,2-difluoroethyl group, 2,2,2-trifluoroethyl group, 2-chloro-2,2-difluoroethyl group, 2,2,2-trichloroethyl group, 1 , 1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, pentafluoroethyl group, 3,3,3-trifluoropropyl group, 2,2,3,3 , 3-pentafluoropropyl group, 1,1,2,3,3,3-hexafluoropropyl group, heptafluoropropyl group 2,2,2-trifluoro-1- (trifluoromethyl) ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,3,4, Specific examples include 4,4-heptafluorobutyl group, nonafluorobutyl group and the like, and each is selected within the range of the number of carbon atoms designated.

The notation of halo (C _a -C _b ) alkenyl in the present specification is linear or branched having _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom An unsaturated hydrocarbon group which is chain-like and has one or more double bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. For example, 2,2-dichlorovinyl group, 2-fluoro-2-propenyl group, 2-chloro-2-propenyl group, 3-chloro-2-propenyl group, 2-bromo-2-propenyl group, 3,3-difluoro -2-propenyl group, 2,3-dichloro-2-propenyl group, 3,3-dichloro-2-propenyl group, 2,3,3-trifluoro-2-propenyl group, 2,3,3-trichloro- 2-propenyl group, 1- (trifluoromethyl) ethenyl group, 4,4-difluoro-3-butenyl group, 3,4,4-trifluoro-3-butenyl group, 3-chloro-4,4,4- Specific examples include a trifluoro-2-butenyl group and the like, and each is selected within the range of the designated number of carbon atoms.

In the present specification, the notation of halo (C _a -C _b ) alkynyl is linear or branched having _a to _b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom An unsaturated hydrocarbon group which is chain-like and has one or more triple bonds in the molecule. At this time, when substituted by two or more halogen atoms, these halogen atoms may be the same as or different from each other. Specific examples include 2-chloroethynyl group, 2-bromoethynyl group, 2-iodoethynyl group, 3-chloro-2-propynyl group, 3-bromo-2-propynyl group, 3-iodo-2-propynyl group and the like. Each of which is selected for each specified number of carbon atoms.

The notation of C _a -C _b alkoxy in the present specification represents an alkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxy group, ethoxy group, n-propyloxy group, Specific examples include an i-propyloxy group, an n-butyloxy group, an i-butyloxy group, an s-butyloxy group, a tert-butyloxy group, and the like, and each is selected within the range of the designated number of carbon atoms.

The notation of halo (C _a -C _b ) alkoxy in this specification represents a halo (C _a -C _b ) alkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example chloro Specific examples include methoxy group, 2-chloroethoxy group, 2,2-difluoroethoxy group, 2,2,2-trifluoroethoxy group, 2,2,2-trichloroethoxy group, and the like. It is selected in the range of the number of atoms.

The notation of C _a -C _b alkylcarbonyl in the present specification represents an alkyl-C (O) -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, acetyl group, propionyl group, butyryl group. , Isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group, and the like, and specific examples thereof are selected within the range of the number of carbon atoms designated.

The notation of C _a -C _b alkoxycarbonyl in the present specification represents an alkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl Group, n-propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, tert-butoxycarbonyl group and the like, and specific ranges of the number of carbon atoms are designated. Selected.

"Optionally substituted by ^{R 6} _(C a ^~C _b) alkyl" as used herein, "optionally substituted by ^{R 9} _(C a ^~C _b) alkyl" optionally substituted with ^{"R 31} and _(C a _{~C b)} alkyl "or notation" optionally substituted by ^{R 41} _(C a _{~C b)} alkyl ", respectively, by any ^{R 6, R 9, R 31} or ^{R 41,} It represents an alkyl group having the above-mentioned meaning, wherein the number of carbon atoms in which hydrogen atoms bonded to carbon atoms are optionally substituted is a to b, and is selected in the range of each designated number of carbon atoms. At this time, when two or more substituents R ⁶ on each (C _a -C _b ) alkyl group are present, each R ⁶ may be the same as or different from each other.

In the present specification, “R ¹⁵ may form a C ₂ -C ₆ alkylene chain together with R ¹⁶ to form a 3- to 7-membered ring together with the nitrogen atom to which R ¹⁵ and R ¹⁶ are bonded. It indicates that, at this time the alkylene chain an oxygen atom, may contain one sulfur atom or a nitrogen atom, and a halogen _atom, C 1 -C ₆ alkyl group, halo _(C 1 -C ₆₎ alkyl group, _{C 1} -C ₆ alkoxy group, a formyl _group, C 1 -C ₆ alkylcarbonyl _group, C 1 -C ₆ alkoxycarbonyl group, may be optionally substituted by an oxo group or thioxo group "or" ^{R 21} and ^{R 22} by forming a C ₂ -C ₆ alkylene chain together, it indicates that may form a 3- to 7-membered ring together with the nitrogen atom to which R ²¹ and R ²² are bonded, the Al this time Ren chain oxygen atom may contain one sulfur atom or a nitrogen atom, and a halogen _atom, C 1 -C ₆ alkyl group, halo _(C 1 -C ₆₎ alkyl _group, C 1 -C ₆ alkoxy group, a formyl Specific examples of the expression “optionally substituted by a group, a C ₁ -C ₆ alkylcarbonyl group, a C ₁ -C ₆ alkoxycarbonyl group, an oxo group or a thioxo group” include, for example, aziridine, azetidine, azetidine- 2-one, pyrrolidine, pyrrolidin-2-one, oxazolidine, oxazolidine-2-one, oxazolidine-2-thione, thiazolidine, thiazolidine-2-one, thiazolidine-2-thione, imidazolidine, imidazolidin-2-one, Imidazolidine-2-thione, piperidine, piperidin-2-one, piperidin-2-thione 2H-3,4,5,6-tetrahydro-1,3-oxazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-oxazin-2-thione, morpholine, 2H- 3,4,5,6-tetrahydro-1,3-thiazin-2-one, 2H-3,4,5,6-tetrahydro-1,3-thiazin-2-thione, thiomorpholine, thiomorpholine-1- Oxide, thiomorpholine-1,1-dioxide, perhydropyrimidin-2-one, piperazine, homopiperidine, homopiperidin-2-one, heptamethyleneimine, etc., and selected within the range of each designated number of atoms. The

Next, the manufacturing method of this invention compound is demonstrated below.
Manufacturing method A
The heterocyclic amide compound represented by the formula (1) can be produced, for example, by reacting the compound represented by the formula (2) with the compound represented by the formula (3a).

Formula (2) [wherein Q and R ³ represent the same meaning as described above. Or a salt thereof and the formula (3a) [wherein W and X represent the same meaning as described above. Or a salt thereof in a solvent or in the absence of a solvent, using a base, a condensing agent, and a catalyst if necessary, and adding and reacting if necessary, to add a compound represented by the formula (1) [ In the formula, Q, R ³ , W and X represent the same meaning as described above. This invention compound represented by this can be manufactured.

  In this reaction, the compound represented by the formula (3a) can be used in the range of 0.1 to 100 equivalents with respect to 1 equivalent of the compound represented by the formula (2).

  When a solvent is used, the solvent used may be inert to the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazo Polar solvents such as linone, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, tetrachloride Examples thereof include halogenated hydrocarbons such as carbon and 1,2-dichloroethane, and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  When using a base, the base used can be an organic base such as triethylamine, pyridine, 4- (dimethylamino) pyridine, or an inorganic base such as potassium carbonate or sodium carbonate, and is represented by the formula (2). The compound can be used in the range of 0.1 to 50 equivalents per equivalent of the compound.

  When a condensing agent is used, the condensing agent used is 1H-benzotriazol-1-yloxytris (dimethylamino) phosphonium hexafluorophosphate, N, N′-dicyclohexylcarbodiimide, 1- (3-dimethylaminopropyl) -3-Ethylcarbodiimide hydrochloride, 2-chloro-1-methylpyridinium iodide, etc. are mentioned, and it is used in the range of 0.1 to 50 equivalents with respect to 1 equivalent of the compound represented by formula (2). it can.

  When an additive is used, examples of the additive used include 3H- [1,2,3] triazolo [4,5-b] pyridin-3-ol, 1-hydroxybenzotriazole, and the like. Can be used in the range of 0.1 to 50 equivalents relative to 1 equivalent of the compound represented by formula (1).

  The reaction temperature can be set to any temperature from −78 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually in the range of 5 minutes to 100 hours. Can be set.

  Some of the compounds represented by formula (2) are known compounds, and some of them are commercially available.

Some of the compounds represented by the formula (3a) are known compounds and can be synthesized by a method according to a known method described in the literature. Examples of known methods known in the literature include the method described in International Publication No. 2008/006540.
Manufacturing method B
The heterocyclic amide compound represented by the formula (1) can be produced, for example, by reacting the compound represented by the formula (2) with the compound represented by the formula (3b).

Formula (2) [wherein Q and R ³ represent the same meaning as described above. Or a salt thereof and formula (3b) [wherein W and X represent the same meaning as described above, and Xa represents a leaving group such as ^a halogen atom. ] Or a salt thereof in a solvent or in the absence of a solvent, and if necessary, using a base, the compound of formula (1) [wherein Q, R ³ , W and X are the same as defined above. Represents meaning. This invention compound represented by this can be manufactured.

  In this reaction, the compound represented by the formula (3b) can be used in the range of 0.1 to 100 equivalents with respect to 1 equivalent of the compound represented by the formula (2).

  When a solvent is used, the solvent used may be inert to the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazo Polar solvents such as linone, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, tetrachloride Examples thereof include halogenated hydrocarbons such as carbon and 1,2-dichloroethane, and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  When using a base, the base used is an organic base such as triethylamine, pyridine or 4- (dimethylamino) pyridine, or an inorganic base such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or sodium hydride. And can be used in the range of 0.1 to 50 equivalents with respect to 1 equivalent of the compound represented by Formula (2). These bases may be used alone, or two or more of these may be mixed and used.

The reaction temperature can be set to any temperature from −78 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually arbitrary in the range of 5 minutes to 100 hours. Can be set.
Reaction formula 1
The compound represented by the formula (3b) can be produced, for example, by reacting the compound represented by the formula (3a) with a halogenating agent.

Formula (3a) [wherein W and X represent the same meaning as described above. And a salt thereof and a halogenating agent in a solvent or without a solvent, and if necessary, using a base, the compound of formula (3b) [wherein W, X and X ^a are Represents the same meaning as above. The compound represented by this can be manufactured.

  Examples of the halogenating agent include thionyl chloride, oxalyl chloride, phosphoryl chloride and the like. As an equivalent of a halogenating agent, it can use in 0.1-100 equivalent with respect to 1 equivalent of compounds represented by Formula (3a).

  When a solvent is used, the solvent used may be inert to the reaction. For example, N, N-dimethylformamide, N, N-dimethylacetamide, acetonitrile, dimethyl sulfoxide, 1,3-dimethyl-2-imidazo Polar solvents such as linone, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane, diphenyl ether, aromatic hydrocarbons such as benzene, toluene, xylene, methylene chloride, chloroform, tetrachloride Examples thereof include halogenated hydrocarbons such as carbon and 1,2-dichloroethane, and aliphatic hydrocarbons such as n-pentane and n-hexane. These solvents may be used alone or as a mixture of two or more thereof.

  When using a base, the base used is an organic base such as triethylamine, pyridine or 4- (dimethylamino) pyridine, or an inorganic base such as potassium carbonate, sodium carbonate, potassium hydrogen carbonate, sodium hydrogen carbonate or sodium hydride. And can be used in the range of 0.1 to 50 equivalents with respect to 1 equivalent of the compound represented by the formula (3a). These bases may be used alone, or two or more of these may be mixed and used.

  The reaction temperature can be set to any temperature from −78 ° C. to the reflux temperature of the reaction mixture, and the reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but is usually in the range of 5 minutes to 100 hours. Can be set.

  After the completion of the reaction, a production intermediate (3b) that is a raw material compound of production method B can be obtained by carrying out usual post-treatment.

  In addition, the production intermediate (3b) produced by this method can be used as it is in the next step without isolation and purification.

Specific examples of the active compound included in the present invention include compounds shown in Table 1. However, the compounds in Table 1 are for illustrative purposes, and the present invention is not limited thereto. In the table, the substituent described as Me represents a methyl group, hereinafter, Et represents an ethyl group, n-Pr and Pr-n represent normal propyl groups, i-Pr and Pr-i. Is an isopropyl group, c-Pr and Pr-c are cyclopropyl groups, n-Bu and Bu-n are normal butyl groups, s-Bu and Bu-s are secondary butyl groups, i-Bu and Bu- i is an isobutyl group, t-Bu and Bu-t are tertiary butyl groups, c-Bu and Bu-c are cyclobutyl groups, n-Pen and Pen-n are normal pentyl groups, i-Pen and Pen -I is an isopentyl group, s-Pen and Pen-s are secondary pentyl groups, t-Pen and Pen-t are tertiary pentyl groups, c-Pen and Pen-c are cyclopentyl groups, -Pen is a -CH _{(Et) 2} group, a n-Hex and Hex-n is n-hexyl group, c-Hex and Hex-c is a cyclohexyl group, Ph represents respectively a phenyl group.

  In the tables, the substituents represented by J-1 to J-243 each represent the following structure.

[Table 1]

  The compound of the present invention can be used as a herbicide for paddy fields in any treatment method of soil treatment and foliage treatment under flooded water. As paddy field weeds, for example, weeping family (Potamogetonaceatiaceae) represented by Potamogeton distinctus, etc. ) Weeds, Azegaya (Leptochloa chinensis), Echinochloa crus-galli, Echinochloa oryzicola, Hashilochurus japonosum and H. Gramineae weed, Kurowai (Eleocharis kuroguwai), Firefly (Sirpus juncoides), Shizui (Sirpus nipponicus), Cyrus sera (Cyprus seritinus) (Cyperaceae) weeds, duckweeds (Spirodella polyrhiza), duckweeds (Lemna paucicostata) and other species of duckweed (Lemnaceae) weeds, duckweeds (Murdania coenaceae) Weeds (Pontederiaceae) represented by the blue mallow (Monochoria korsakowii) and the white oak (Monochoria vaginalis), and the juveniles of the moss (Elatine triadra) ) And other species such as Lythraceaae, Lydwigia epiobioides, and other species such as Oenotheraceae weeds, Dopatrium junceum, and Grap. sessilifolia), Azena (Lindernia pyxidaria), American Azena (Lindernia dubia) Examples thereof include Compositae weeds represented by Bidens tripartita.

  In addition, the compound of the present invention can be used as a herbicide for upland fields and orchards in any treatment method of soil treatment, soil admixture treatment, and foliage treatment. Examples of upland field weeds include Solanumae weeds represented by Solanum nigrum and Datura stramonium, Solanasae weeds represented by Grunum carolinianum, and Aceaeaceae cereals (Gae) cereals (Gaeumaceae) (Abutilon theophrasti) and malvaaceae weeds represented by Sida spinosa, etc., Ipomoea purpurea, etc. and Ipomoea spps. Convolvulaceae weed, Amaran (Amaran) hus lividus) and slender amaranth (Amaranthus retroflexus) Amaranthaceae represented by such (Amaranthaceae) weeds, cocklebur (xanthium pensylvanicum), ragweed (Ambrosia artemisiaefolia), sunflower (Helianthus annuus), galinsoga quadriradiata (Galinsoga ciliata), western thorns thistle (Cirsium arvense, Sorgio vulgaris, Erigeron annus, and other species of Compositae weeds, Roppa indica, Shirapis arvensis Ca a bursaceae weed, represented by a Bursapastoris, etc. Weeds represented by, for example, Polygonaceae weeds represented by, for example, Polygonum bulvoluis, Polygonum convolvulus, olulaceae, etc. (Portulacaceae) weeds, white-spotted (Chenopodium album), red-breasted (Chenopodium falifolium), weeds (Chenopodiacee) weeds represented by weeds (Cenopodiaceae) The Weeds such as Sphaphulariaceae represented by Veronica persica, Ceminaurae weeds represented by Commelina communis, etc., and Lamium urumiles. Euphorbiaceae (Euphorbiaceae) and other species such as Euphorbiaceae (Galium spurium), representatives of Euphorbiaceula (Euporbiaacea) Rubyaceae Weeds such as Violaceae weeds represented by weeds and violets (Viola mandhurica) and leguminous weeds represented by Sesbania exaltata and Cassia obtusifolia, etc. Broad-leaved weeds such as the representative Oxsaldasee. Wild sorghum (Sorgham dichotomiflorum), Johnson grass (Sorghum halo chilli), Echinochloa cru-galli var. Crus-galli , Barnyard grass (Digitaria ciliaris), oats (Avena fatua), blackgrass (Alopecurus myosuroides), barnyard grass (Eleusine indica), Enocologia (Sateria viridis), Akinosae faberi) and water foxtail (Alopecurus aegualis) gramineous weeds (Graminaceous weeds typified etc.) and Cyperus (Cyperus rotundus, Cyperus esculentus) Cyperaceae weeds (Cyperaceous weeds typified like).

  Further, the compound of the present invention can be used for soil treatment, soil admixture treatment, and foliage treatment in non-agricultural lands such as turf, playground, open space, roadside, and track end in addition to the fields of agriculture and horticulture such as paddy fields, upland fields and orchards It can also be used in the processing method. The weeds include those mentioned in upland and orchard weeds, Poa annua, Taraxacum officinale, Conyzaol samsensis, Cardamine minx, (Hydrocotyl sibthorpioides), Plantago asiatica, Cyperus brevifolia, Kyllinga brevifolia, Equisetum arvense and the like.

  The compound of the present invention may be mixed and applied with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists, and the like, as necessary, during formulation or spraying.

  In particular, when mixed with other herbicides, cost reduction due to a decrease in the amount of applied medicine, expansion of the herbicidal spectrum due to the synergistic action of the mixed drugs, and higher herbicidal effects can be expected. At this time, a combination with a plurality of known herbicides is also possible.

Preferred herbicides to be used in combination with the compound of the present invention include, for example, acetochlor (acetochlor / generic name), acifluorfen (acifluorfen / generic name), aclonifen (aclonifen / generic name), alachlor (alachlor / (Generic name), alloxidim (alloxydim / generic name), sodium alloxidim-sodium / generic name, ametrine (generic name), amicarbazone (generic name), amidosulfuron (common name), Aminocyclopyrachlor (generic name), salts and esters of aminocyclopyracryl (aminocyclopirachlo) r-salts and esters, aminopyralides (generic names), salts and esters of aminopyralides (aminopyridid-salts and esters), amiprophos-methyl (common names), amitrol (common names) (Anifofos / generic name), ashram (asulam / generic name), atrazine (atrazine / generic name), azaphenidin (azafenidin / generic name), azimusulfuron (generic name), beflubutamid (generic name), beazoline Benazolin-ethyl / generic name), bencarbazone / generic name , Benfluralin (benfulin / generic name), benfrate (benfurateate / generic name), bensulfuron methyl (bensulfuron-methyl / generic name), bensulide (bensulide / generic name), bentazone (sodium name), bentazone (sodium) bentazone-sodium / generic name), bentazone salt (bentazone-salts), benziocarb (general name), benzfendizone (generic name), benzobicyclon (generic name), benzophenap (generic name) benzofenap / generic name), bialaphos (generic name), bialaphos sodium ( bialaphos-sodium / generic name), bicyclopyrone (bicyclopyrone / generic name), bifenox (bifenox / generic name), bispyribac (bispyribac / generic name), bispilibac sodium (bispyribac-sodium / generic name), bromacil (birocil) (Generic name), bromobutide (generic name), bromophenoxime (generic name), bromoxynil (generic name), salts and esters of bromoxynil (general name) and butachlor (general name) , Butafenacil (generic name), butamifos (butamifos) (Generic name), butenachlor (butenachlor / generic name), butralin (butralin / generic name), butroxydim (butoxydim / generic name), butyrate (butylate / generic name), fenfentrol (calfenstrole / generic name), carbetamid (carbetamide / common name) ), Carfentrazone-ethyl, chloromethoxyphene (generic name), chloromethoxynyl (generic name), chloramben (general name), chloramben salts and esters (chloramben-salts and esters) ), Chloransrammethyl l / generic name), chlorflurenol-methyl / generic name, chloridazon / generic name, chlorimuron-ethyl / generic name, chlorobromuron / generic name, Chlorotoluron (generic name), chloroxuron (generic name), chlorphthalim (general name), chloroprofam (general name), chloro IPC (chloroprophlon / generic name), chlorosulfuron (chlorsulfuron) Name), chlorthal dimethyl (general name), chlorthiamid ( hlorthiamid / generic name), sinidone ethyl (cinidon-ethyl / generic name), cinmesulin (generic name), sinosulfuron (cynosulfuron / generic name), cletodim (generic name), clodina hop (generic name) Hoppropargyl (clodinafop-propargyl / generic name), clomazone (clomazone / generic name), clomeprop (cloproprop / generic name), clopyralid (clopyralid / generic name), clopyralid salts and esters (clopyralid-Nsalts, clospandid-salts) (Generic name), cumylron (generic name), cyanazine (cyanazi) / Generic name), cycloate (cycloate / generic name), cyclopyrimoleate (cyclopyrimorate / generic name, SW-065 / study name), cyclosulfamuron (cyclosulfamuron / generic name), cycloxydim (cycloxydim / generic name), Cyhalofop butyl (cyhalofop-butyl / generic name), DAH-500 (test name), darapon (dalapon / generic name), dazomet (dazomet / generic name), desmedifam (desmedifam / generic name), desmethrin (desmetrin) / Common name), dicamba (generic name), dicamba-salts and esters, diclobenil / ), Diclohop (generic name), diclohop methyl (generic name), dichloroprop (generic name), dichlorprop salts and esters, dichlorprop-salts and esters Chlorprop- (P / generic name), salts and esters of P-dichloroprop-P-salts and esters, dicroslam (diclosulam / generic name), difenzoquat (common name), diflufenic (difluenic) Name), diflufenzopyr (diflufenzopyr / generic name), diflufenzopyr sodium (difluf) nzopyr-sodium / generic name), dimethylpiperate (dimipeperate / generic name), dimetamethrin (dimtammetry / generic name), dimetachlor (dimethachlor / generic name), dimethenamide (dimethenamide / generic name), P-dimethenamide (generic name) , Dimesipine (dimethipine / generic name), dinitroamine (dinitramine / generic name), dinoseb (dinoseb / generic name), dinoteb (dinotarb / generic name), DNOC / generic name, diphenamide (generic name), diquat / Generic name), dithiopyr (dithiopyl / generic name), diuron (diuron / generic name), DSMA / generic name, Daimlon (genom / generic name), Endothal (endothal / generic name), EPTC / generic name, esprocarb (generic name), ethalfluralin (ethalfluralin / generic name), ethamesulfuron-methyl (general name) Name), etofumesate (ethofumesate / generic name), ettobenzanide (etobenzanid / generic name), ethoxysulfuron (ethoxysulfuron / generic name), flazasulfuron (general name), fenoxaprop / generic name, Sapropethyl (fenoxaprop-ethyl / generic name), phenoxasulfone (fenoxasulfone) (Generic name), fenquinotrione (generic name), fentolazamide (general name), flamprop (generic name), flazasulfuron (common name), florasulfuron (generic name), fluazihop (Fluazifop / generic name), fluazifop butyl (fluazifop-butyl / generic name), fluazolate (fluazolate / generic name), flucarbazone sodium (flucarbazone-sodium / generic name), flucetsulfuron / generic name , Fluchloralin (generic name), flufenacet (generic name), Rufenpyrethyl (flufenpyl-ethyl / generic name), flumeturum (flumetsulam / generic name), fluromicrolac-pentyl (generic name), flumioxazin (generic name), fluometuron (generic name) , Fluoroglycofen-ethyl (fluoroglycofen-ethyl / generic name), flupylsulfuron (flupyrsulfuron / generic name), flupoxam (fluoxam / generic name), flulenol (generic name), fluridone (generic name), flurodone / generic name Lydon (flurochloridone / generic name), fluroxypyr (fluroxypyr / generic name), fluro Cypil esters (fluroxypyr-esters), fluprimidol (flurprimidol / generic name), flutamon (flurtamone / generic name), fluthiaset-methyl (generic name), fomesafen (fomesafen / generic name), foramsulfen (Foramsulfuron / generic name), fosamine (fosamine / generic name), glufosinate (glufosinate / generic name), glufosinate-ammonium (generic name), glyphosate (generic name), glyphosate-ammonium Name), glyphosate isopropylamine (glyphos) te-iso-propylamonium / generic name), glyphosate potassium (glyphosate-potassium / generic name), glyphosate sodium (glyphosate-sodium / generic name), glyphosate-trimesium (generic name), axium (Generic name), salts and esters of haloxifene-salts and esters, halosafene (halosafen / generic name), halosulfuron (halosulfuron / generic name), halosulfuron methyl (halosulfuron-methyl / generic name), haloxyhop ( haloxyfop / generic name), haloxyhop methyl (haloxy) op-methyl / generic name), hexazinone (hexazinone / generic name), timer The meta benz methyl (imazamethabenz-methyl / generic name), imazamox (imazamox / generic name), Imazapiku (i
mazapic / common name), imazapyr (common name), imazetapyr (common name), imazaquin (generic name), imazosulfuron (common name), indanophan Common name), iodosulfuron-methyl-sodium / generic name, ioxynyl octanoate / general name, salts and esters of ioxynil-salts and esters, ipfencarbazone / ipfencarbazone Name), isoproturon (common name), iso Ron (isouron / generic name), isoxaben (isoxaben / generic name), isoxaflutol (isoxafulle / generic name), carbutylate (common name), lactofen (generic name), renacil (lenacil / generic name) Linulin (linuron / generic name), maleic hydrazide (generic name), MCPA (generic name), MCPA salts and esters (MCPA-salts and esters), MCPB (generic name), MCPB salts and esters (MCPB-salts and esters), mecoprop (MCPP / generic name), mecoprop salts and esters (mecoprop-salts and e ters), P mecoprop (P, MCPP-P / generic name), salts and esters of P mecoprop (mecoprop-P-salts and esters), mefenacet (generic name), mefluide (mefluidide / generic name), Mesosulfuron-methyl (generic name), mesotrione (metrition / generic name), metam (metam / generic name), metamihop (metamihop / generic name), metamitron (metamitron / generic name), metazachlor (metazalch / general) Name), metabenzthiazuron (general name), metazosulfuron (general name) Name), Methiozoline (generic name), Methyl azide (common name), Methyl bromide (generic name), Methyl dimron (generic name), Methyl iodide (common name) ), Metbenzuron (metobenzuron / generic name), metolachlor (metolachlor / generic name), Smetolachlor (metolachlor-S / generic name), metoslam (metosuram / generic name), metribuzine (metribuzin / generic name), metsulfuron methyl (Metsulfuron-methyl / generic name), methoxuron (generic name / generic name), molinate (generic name / generic name), monolini Uron (monolinuron / generic name), monosulfuron (monosulfuron / generic name), monosulfuron methyl (monosulfuron-methyl / generic name), MSMA / generic name, naproanilide (generic name), napropamide (generic name), napropamide (Naptalam / generic name), naptalam sodium (naptalam-sodium / generic name), nebulon (neburon / generic name), nicosulfuron (nicosulfuron / generic name), norflurazon (norflurazon / generic name), OK-701 (test name) ), Oleic acid (oleic acid / generic name), olven curve (orbencarb / generic name), orthosulfamlone (ort) hosulfamuron / generic name), oryzalin (ordinary / generic name), oxadialgyl (oxadiargyl / generic name), oxadiazon (oxadiazon / generic name), oxasulfuron (generic name), oxadichromemefone / generic name (Oxyfluorfen / generic name), paraquat (paraquat / generic name), pelargonic acid (pelargonic acid / generic name), pendimethalin (pendimethalin / generic name), penoxslam (penoxslam / generic name), pentanochlor (pentanochlor) ), Pentoxazone (general name), petoxamide (petho) amid / generic name), phenmedifam-ethyl / (generic name), picloram (picloram / generic name), salts and esters of picloram (picloram-salts and esters), picolinafen (generic name), pinoxaden ( pinoxaden / generic name), piperophos (piperophos / generic name), pretilachlor (pretilachlor / generic name), primisulfuron-methyl / generic name, prodiamine (generic name), profluazole (profluzol) (Generic name), propoxydim (profoxydim / generic name), prometon (promethon / general) Name), promethrin (prometryn / generic name), propachlor (propachlor / generic name), propanil (propanil / generic name), propoxafop (propaquafop / generic name), propazin (propazin / generic name), profam (profaph) (Generic name), propisochlor (propisochlor / generic name), propoxycarbazone sodium (propoxycarbazone-sodium / generic name), propyrisulfuron (generic name), propizamide (general name), pullulofurbo / General name), prosulfuron (prosulfuron / generic name), pyraclonil / (Generic name), pyraflufen-ethyl (generic name), pyrasulfotol (generic name), pyrazolinate (general name), pyrazosulfuron (generic name), pyrazosulfuron ethyl (pyrazolsulfurethyl) ethyl / generic name), pyrazoxifene (pyrazoxyphen / generic name), pyribenzoxim (pyribenzoxim / generic name), pyributicalcarb (generic name), pyridafol (generic name) Generic name), pyriminobac-methyl / (Generic name), pyrimisulfan (pyrimisulfan / generic name), pyrithiobac sodium (pyrithiobac-sodium / generic name), pyroxasulfone (pyroxasulfone / generic name), piroxisulfam (generic name), quinclorac / quincloclac (Generic name), quinmerac (common name), quinoclamin (common name), quizalofop (common name), quizalofop-ethyl (generic name), quizalofop tefryl tefuryl / generic name), P quizalofop-P / generic name, P quizalofop-P-et hyl / generic name), P quizalofop-p-tefuryl / generic name, rimsulfuron (rimsulfuron / generic name), saflufenacil (saflufenacil / generic name), cetoxydim / generic name siduron / generic name), simazine (simazine / generic name), simethrin (simetlyn / generic name), SL-261 (test name), sulcotrione (sulcotrione / generic name), sulfentrazone (sulfentrazone / generic name), Sulfomethuron methyl (sulfomethuron-methyl / generic name), sulfosulfuron (sulfosulfuron / generic name), TCBA (2,3,6-TBA / generic name), T BA salts and esters (2,3,6-TBA-salts and esters), TCTP (chlor-dimethyl, tetrachlorothiophene / generic name), tebutam (general name), tebuthiuron / generic name, tefril trione (Tefuryltrione / generic name), tembotrione (general name), tepraxidim (general name), terbacil (general name), terbumeton (general name), terbuthylazine (general name) (Terbutryn / generic name), tetrapion (tetrapion / flupropana) te / generic name), tenilchlor (tenylchlor / generic name), thiafluuron (thiazfluron / generic name), thiazopyr (thiazopyr / generic name), thidiazimin (generic name), thidiazuron / generic name (Thiencarbazone-methyl / generic name), thifensulfuron-methyl (generic name), tolpyralate (generic name), topramezone (general name), toloxydim (generic name) / Generic name), trialate (general name), triasulf (Triasulfuron / generic name), triazifram (generic name), tribenuron methyl (tribenuron-methyl / generic name), triclopyr (tricyclopyr / generic name), triclopyr salts and esters (tricropyr-salts) , Tridiphane (triidiphane / generic name), trietadine (trietazine / generic name), trifludimoxazine (trifludimoxadin / generic name), trifloxysulfuron / generic name, trifluralin (trifluralin / generic name) Sulfuron methyl (triflusulfuron-methyl / generic name), tritosulfuron (tr itosulfuron / generic name), 2,4-PA (generic name), salts and esters of 2,4-PA (2,4-PA-salts and esters), 2,4-D (generic name), 2,4 -D salts and esters (2,4-D-salts and esters), 2,4-DB (generic name), 2,4-DB salts and esters (2,4-DB-salts and esters) and the like Can be mentioned. These components can be used alone or in admixture of two or more, and the ratio in the case of mixing can also be freely selected.

  As the safener, for example, AD-67, Benoxacol (benoxacor / generic name), cloquintocet-mexyl (generic name), ciomethrinil (cyomerinil / generic name), dichlormid (dichlormid / generic name), Dicyclonone (common name), cyprosulfamide (generic name), dietrate (generic name), DKA-24, dimron (common name), fenchlorazole-ethyl (general name) ), Fencrolim (general name), hexime (general name), flurazole (generic name), fluxofeni (Fluxofenim / generic name), flirazole (furilazole / generic name), isoxadifen (isoxadifen / generic name), isoxadifen-ethyl (isoxadifen-ethyl / generic name), MCPA, mecoprop (generic name), mefenpyr (mefenpy) / Generic name), mefenpyr-ethyl (mefenpyr-ethyl / generic name), mefenpyr-diethyl (mefenpyr-diethyl / generic name), mephenate (mephenate / generic name), MG-191, NA (Naphtalic anhydride), OM (Octamethylene-diamin), oxabetrinyl (oxabetrilin / generic name), PPG-1292, R-29148, etc. Can be mentioned. These components can be used alone or in admixture of two or more, and the ratio in the case of mixing can also be freely selected.

  In applying the compound of the present invention as a herbicide, it is usually mixed with a suitable solid carrier or liquid carrier, and if desired, a surfactant, a penetrating agent, a spreading agent, a thickening agent, an antifreezing agent, a binder, a solid carrier. Add anti-caking agent, disintegrant, anti-decomposition agent, etc., and put to practical use in any dosage form such as wettable powder, emulsion, flowable, dry flowable, liquid, powder, granule or gel. be able to. In addition, from the viewpoint of labor saving and safety improvement, the preparation of any dosage form can be enclosed in a water-soluble package.

  Examples of solid carriers include quartz, kaolinite, pyrophyllite, sericite, talc, bentonite, acid clay, attapulgite, zeolite, and diatomaceous earth, and other minerals, calcium carbonate, ammonium sulfate, sodium sulfate, and potassium chloride. Examples include salts, synthetic silicic acid and synthetic silicates.

  Examples of the liquid carrier include alcohols such as ethylene glycol, propylene glycol and isopropanol, aromatic hydrocarbons such as xylene, alkylbenzene and alkylnaphthalene, ethers such as butyl cellosolve, ketones such as cyclohexanone, and esters such as γ-butyrolactone. And acid amides such as N-methylpyrrolidone and N-octylpyrrolidone, vegetable oils such as soybean oil, rapeseed oil, cottonseed oil and castor oil, and water.

  These solid and liquid carriers may be used alone or in combination of two or more.

  Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene fatty acid ester, sorbitan fatty acid ester and polyoxyethylene sorbitan. Nonionic surfactant such as fatty acid ester, alkyl sulfate, alkylbenzene sulfonate, lignin sulfonate, alkyl sulfosuccinate, naphthalene sulfonate, alkyl naphthalene sulfonate, salt of formalin condensate of naphthalene sulfonate, Salt of formalin condensate of alkylnaphthalenesulfonic acid, polyoxyethylene alkylaryl ether sulfate and phosphate, polyoxyethylene polystyrene Anionic surfactants such as phenyl ether sulfate and phosphate, polycarboxylate and polystyrene sulfonate, cationic surfactants such as alkylamine salt and alkyl quaternary ammonium salt, and amphoteric interfaces such as amino acid type and betaine type An activator is mentioned.

  The content of these surfactants is not particularly limited, but is usually in the range of 0.05 to 20 parts by mass with respect to 100 parts by mass of the preparation of the present invention. These surfactants may be used alone or in combination of two or more.

  The compound of the present invention may be mixed and applied with other types of herbicides, various insecticides, fungicides, plant growth regulators, synergists, and the like, as necessary, during formulation or spraying.

  In particular, when mixed with other herbicides, cost reduction due to a decrease in the amount of applied medicine, expansion of the herbicidal spectrum due to the synergistic action of the mixed drugs, and higher herbicidal effects can be expected. At this time, a combination with a plurality of known herbicides is also possible.

  The application dose of the compound of the present invention varies depending on the application scene, application time, application method, cultivated crops, etc., but generally an amount of 0.005 to 50 kg per hectare (ha) is appropriate as the amount of active ingredient.

Next, formulation examples of the preparation when the compound of the present invention is used are shown. However, the formulation examples of the present invention are not limited to these. In the following formulation examples, “part” means part by mass.
Wettable compound of the present invention 0.1-80 parts Solid carrier 5-98.9 parts Surfactant 1-10 parts Others 0-5 parts Others include, for example, anti-caking agents and decomposition inhibitors.
Emulsified compound of the present invention 0.1-30 parts Liquid carrier 45-95 parts Surfactant 4.9-15 parts Others 0-10 parts Others include, for example, spreading agents, decomposition inhibitors and the like.
Flowable agent compound of the present invention 0.1 to 70 parts Liquid carrier 15 to 98.89 parts Surfactant 1 to 12 parts Others 0.01 to 30 parts Others include, for example, antifreezing agents and thickeners. It is done.
Dry flowable agent compound of the present invention 0.1-90 parts Solid carrier 0-98.9 parts Surfactant 1-20 parts Others 0-10 parts Others include, for example, binders, decomposition inhibitors, etc. .
Liquid compound of the present invention 0.01 to 70 parts Liquid carrier 20 to 99.99 parts Others 0 to 10 parts Others include, for example, antifreezing agents and spreading agents.
Granules of the present invention compound 0.01 to 80 parts Solid carrier 10 to 99.99 parts Others 0 to 10 parts Others include, for example, binders and decomposition inhibitors.
Powder Compound of the Present Invention 0.01-30 parts Solid carrier 65-99.99 parts Others 0-10 parts Others include, for example, drift inhibitors and decomposition inhibitors.

  In use, the preparation is sprayed as it is or diluted 1 to 10,000 times with water.

Formulation Examples Next, specific examples of agrochemical formulations containing the compound of the present invention as an active ingredient are shown, but the invention is not limited thereto. In the following formulation examples, “parts” means parts by weight.
[Formulation Example 1] Wetting Agent Compound No. 1-001 20 parts Pyrophyllite 76 parts Solpol 5039 2 parts (Anionic surfactant: Toho Chemical Industries, Ltd. trade name)
Carplex # 80 2 parts (Synthetic hydrous silicate: Shionogi Pharmaceutical Co., Ltd. trade name)
The above is uniformly mixed and ground to obtain a wettable powder.
[Composition Example 2] Milk Compound No. of the present invention. 1-001 5 parts Xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (anionic surfactant: Toho Chemical Industries, Ltd. trade name)
The above is uniformly mixed to obtain an emulsion.
[Composition Example 3] Flowable Agent Compound No. 1-001 25 parts Agrisol S-710 10 parts (Nonionic surfactant: trade name of Kao Corporation)
Lnox 1000C 0.5 part (anionic surfactant: Toho Chemical Co., Ltd. trade name)
Xanthan gum 0.02 parts Water 64.48 parts After uniformly mixing the above, wet milling to obtain a flowable agent.
[Composition Example 4] Dry flowable agent Compound No. 1-001 75 parts Hightenol NE-15 5 parts (Anionic surfactant: Daiichi Kogyo Seiyaku Co., Ltd. trade name)
Vanillex N 10 parts (anionic surfactant: Nippon Paper Industries Co., Ltd. trade name)
Carplex # 80 10 parts (Synthetic hydrous silicic acid: Shionogi Pharmaceutical Co., Ltd. trade name)
After uniformly mixing and pulverizing the above, a small amount of water is added, and the mixture is stirred and kneaded, granulated with an extrusion granulator, and dried to obtain a dry flowable agent.
[Formulation Example 5] Granule The present compound No. 1-001 1 part Bentonite 55 parts Talc 44 parts After uniformly mixing and pulverizing the above, a small amount of water is added and mixed with stirring, kneaded, granulated with an extrusion granulator, and dried to form granules.

  In the present invention, the present invention will be described in more detail by specifically describing the synthesis examples and test examples of the heterocyclic amide compound represented by the formula (1) as examples, but the present invention is limited by these. Is not to be done.

  The medium pressure preparative liquid chromatography described in the synthesis examples and the reference examples used Yamazen Corporation medium pressure preparative device; YFLC-Wprep (flow rate 10 ml / min, silica gel 40 μm column).

Moreover, the proton nuclear magnetic resonance chemical shift value of the Example was measured at 300 MHz using Me ₄ Si (tetramethylsilane) as a reference material. Moreover, the solvent used for the measurement is described in the following synthesis examples. Moreover, the symbol in the proton nuclear magnetic resonance chemical shift value of an Example represents the following meaning.
s: singlet, d: doublet, dd: double doublet, dt: double triplet, t: triplet, q: quartet, m: multiplet, br: broad synthesis example [synthesis example 1]
3-[(6-Chloropyridin-3-yl) methyl] -N- (1,3,4-oxadiazol-2-yl) -5- (trifluoromethyl)-[1,2,4] triazolo Synthesis of [4,3-a] pyridine-8-carboxamide (Compound No. 1-017) 3-[(6-Chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2 , 4] triazolo [4,3-a] pyridine-8-carboxylic acid 200 mg (0.56 mmol), 1,3,4-oxadiazol-2-amine 70 mg (0.82 mmol), 1-hydroxy-7- To a mixed solution of 110 mg (0.81 mmol) of azabenzotriazole and 2 ml of N, N-dimethylformamide was added 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 160 at room temperature. mg (0.84 mmol) was added. After the addition was complete, the reaction mixture was stirred at room temperature for 15 hours. After completion of stirring, 10 ml of 0.1 mol / L hydrochloric acid aqueous solution was added to the reaction mixture to stop the reaction. The precipitated solid was washed with water and collected by filtration to obtain 145 mg of the desired product as a yellow solid.
Melting point: 209-211 ° C
[Synthesis Example 2]
3-[(6-Chloropyridin-3-yl) methyl] -N- (1-methyl-1H-tetrazol-5-yl) -5- (trifluoromethyl)-[1,2,4] triazolo [4 , 3-a] Synthesis of pyridine-8-carboxamide (Compound No. 3-023) 3-[(6-Chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2,4 ] To a mixed solution of triazolo [4,3-a] pyridine-8-carboxylic acid 200 mg (0.56 mmol), 1-methyl-1H-tetrazol-5-amine 110 mg (1.11 mmol) and pyridine 2 ml under ice-cooling. At 130 mg thionyl chloride (1.09 mmol) was added. After the addition was complete, the reaction mixture was stirred at room temperature for 15 hours. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. To the obtained residue, 10 ml of 0.1 mol / L hydrochloric acid aqueous solution was added at room temperature. The precipitated solid was washed with water and collected by filtration to obtain 200 mg of the desired product as a white solid.
Melting point: 170-171 ° C
The compound of the present invention can be synthesized according to the above synthesis examples. Although the example of this invention compound manufactured similarly to the synthesis example 1 thru | or the synthesis example 2 is shown to the 2nd table | surface thru | or a 4th table | surface, this invention is not limited only to these. In the table, “Me” represents a methyl group. Similarly, Ph represents phenyl, OMe represents methoxy, CO ₂ Me represents methoxycarbonyl, and CO ₂ Et represents ethoxycarbonyl.

  In the table, “mp” represents a melting point, and “* 1” represents “resin”.

  In the table, U-1a, U-1b, U-1c, U-3a, U-7a, U-7b, U-7c, U-8a, U-11a, U-11b, U-12a, U- 12b, U-12c, U-12d, U-12e, U-12f, U-13a, U-13b, U-15a, U-16a, U-17a, U-21a, U-22a, U-22b, U-23a, U-24a, U-25a, U-25b, U-26a, U-26b, U-27a, U-31a, U-32a, U-33a, U-38a, D-1 Each of the substituents represents the following structure.

[Table 2]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
1-001 U-1a 203-204
1-002 U-3a 221-225
1-003 CH ₂ (U-3a) 160-165
1-004 CH ₂ (U-8a) 178-182
1-005 U-7a 224-228
1-006 U-7b 240-244
1-007 U-7c 255-256
1-008 SCH ₂ CH ₂ OC (O) Me 196-205
1-009 S (U-16a) 229-231
1-010 SCH ₂ (U-17a) 163-165
1-011 SPh 198-200
1-012 S (4-OMe-Ph) 195-199
1-013 S [3,4-di (OMe) -Ph] 181-185
1-014 S (U-12a) 182-184
1-015 U-22a CO ₂ Et 152-155
1-016 U-22b CO ₂ Et 56-57
1-017 CH ₂ (U-12b) Cl 209-211
1-018 CH ₂ (U-12b) OMe 202-203
1-019 NH (U-16a) 150-155
1-020 CH ₂ (U-26a) 168-170
1-021 CH ₂ (U-26b) 208-210
1-022 CH ₂ (U-11a) * 1
1-023 CH ₂ (U-11b) Cl 177-178
1-024 CH ₂ (U-11b) Br 157-159
1-025 CH ₂ (U-12a) 255-260
1-026 CH ₂ (U-13a) 241-245
1-027 CH ₂ (U-25b) 237-239
1-028 OCH ₂ CH ₂ OMe 138-140
1-029 O (4-OMe-Ph) 171-173
1-030 S (4-CN-Ph) 242-244
1-031 S (U-11a) 197-199
1-032 S (U-11b) Cl 193-195
1-033 S (U-11b) OMe 256-258
1-034 S (U-12b) Me 175-177
1-035 S (U-12b) Cl 208-210
1-036 S (U-12b) OMe 230-232
1-037 S (U-12b) CF ₃ 201-203
1-038 S (O) (U-12a) 222-224
1-039 S (O) (U-12c) 119-121
1-040 S (U-13a) 195-197
1-041 S (U-13b) Cl 207-209
1-042 S (U-13b) OMe 173-175
1-043 S (U-32a) 143-145
1-044 S (U-31a) 218-220
1-045 S (U-23a) 224-226
1-046 S (U-24a) 183-185
1-047 S (U-25a) 223-225
1-048 S (U-33a) 223-225
1-049 S (U-15a) 164-166
1-050 S (U-38a) 199-201
―――――――――――――――――――――――――――――
[Table 3]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
2-001 U-1a 119-121
2-002 U-3a 195-197
2-003 CH ₂ (U-3a) 180-182
2-004 CH ₂ (U-8a) 206-209
2-005 U-7a 189-190
2-006 U-7b 235-240
2-007 U-7c 247-251
2-008 SCH ₂ CH ₂ OC (O) Me 137-138
2-009 S (U-16a) 171-172
2-010 SCH ₂ (U-17a) 135-138
2-011 SPh 182-184
2-012 S (4-OMe-Ph) 165-168
2-013 S [3,4-di (OMe) -Ph] 189-192
2-014 S (U-12a) 141-143
2-015 U-21a CO ₂ Me 137-138
2-016 U-22a OMe 168-171
2-017 U-22a CO ₂ Et 184-186
2-018 U-22b CO ₂ Et * 1
2-019 NH (D-1) 225-228
2-020 CH ₂ O (4-OMe-Ph) 160-161
2-021 CH ₂ (U-12b) Cl 167-168
2-022 CH ₂ (U-12b) OMe 135-137
2-023 CH ₂ S [3,4-di (OMe) -Ph] 175-176
2-024 CH ₂ S (O) [3,4-di (OMe) -Ph] 197-198
2-025 CH ₂ SO ₂ [3,4-di (OMe) -Ph] 233-235
2-026 N (Me) OMe 149-150
2-027 NH (U-23a) 230-232
2-028 NH (U-16a) 138-142
2-029 CH ₂ (U-26a) 181-183
2-030 CH ₂ (U-26b) 194-196
2-031 CH ₂ (U-11a) 130-135
2-032 CH ₂ (U-11b) Cl 154-155
2-033 CH ₂ (U-11b) Br 166-167
2-034 CH ₂ (U-12a) 105-108
2-035 CH ₂ (U-13a) 232-245
2-036 CH ₂ (U-13b) Cl 186-188
2-037 CH ₂ (U-25b) 226-228
2-038 CH ₂ (U-27a) 163-164
2-039 OCH ₂ CH ₂ OMe 112-113
2-040 OCH ₂ CF ₃ 160-163
2-041 O (4-OMe-Ph) 133-134
2-042 S (4-CN-Ph) 199-201
2-043 S (U-11a) 210-212
2-044 S (U-11b) Cl 188-190
2-045 S (U-11b) OMe 261-263
2-046 S (U-12b) Me 109-111
2-047 S (U-12b) Cl 173-175
2-048 S (U-12b) OMe 149-151
2-049 S (U-12b) CF ₃ 160-162
2-050 S (U-13a) 204-206
2-051 S (U-13b) Cl 168-170
2-052 S (U-13b) OMe 155-157
2-053 S (U-32a) 167-169
2-054 S (U-31a) 151-153
2-055 S (U-23a) 198-200
2-056 S (U-24a) 192-194
2-057 S (U-25a) 188-190
2-058 S (U-15a) 148-150
2-059 S (U-38a) 198-200
―――――――――――――――――――――――――――――
[Table 4]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
3-001 U-1a 175-176
3-002 U-1b * 1
3-003 U-1c * 1
3-004 U-3a 160-161
3-005 CH ₂ (U-3a) 179-181
3-006 CH ₂ (U-8a) 219-222
3-007 U-7a 230-233
3-008 U-7b 195-200
3-009 U-7c 224-226
3-010 SCH ₂ CH ₂ OC (O) Me 96-100
3-011 S (O) CH ₂ CH ₂ OC (O) Me 222-225
3-012 S (U-16a) 183-185
3-013 SCH ₂ (U-17a) * 1
3-014 SPh 167-170
3-015 S (4-OMe-Ph) 168-170
3-016 S [3,4-di (OMe) -Ph] 219-222
3-017 S (U-12a) 143-145
3-018 U-21a CO ₂ Me 101-102
3-019 U-22a CO ₂ Et 213-215
3-020 U-22b CO ₂ Et 139-140
3-021 NH (D-1) 210-214
3-022 CH ₂ O (4-OMe-Ph) 170-171
3-023 CH ₂ (U-12b) Cl 170-171
3-024 CH ₂ (U-12b) OMe 186-187
3-025 N (Me) OMe 171-172
3-026 NH (U-23a) 260-263
3-027 NH (U-16a) 160-165
3-028 CH ₂ (U-26a) 143-145
3-029 CH ₂ (U-26b) 197-199
3-030 CH ₂ (U-11a) 181-186
3-031 CH ₂ (U-11b) Cl 162-163
3-032 CH ₂ (U-11b) Br 159-161
3-033 CH ₂ (U-12a) 99-101
3-034 CH ₂ (U-13a) 191-195
3-035 CH ₂ (U-13b) Cl 70-73
3-036 CH ₂ (U-25b) 218-220
3-037 CH ₂ (U-27a) 171-173
3-038 OCH ₂ CH ₂ OMe 127-128
3-039 OCH ₂ CF ₃ * 1
3-040 O (4-OMe-Ph) 153-154
3-041 S (4-CN-Ph) 264-266
3-042 S (U-11a) 175-177
3-043 S (U-11b) Cl 214-216
3-044 S (U-11b) OMe 215-217
3-045 S (U-12b) Me 154-156
3-046 S (U-12d) 178-179
3-047 S (U-12e) 179-180
3-048 S (U-12f) 110-114
3-049 S (U-12b) Cl 185-187
3-050 S (U-12b) OMe 197-199
3-051 S (U-12b) CF ₃ 198-200
3-052 S (O) (U-12a) 101-103
3-053 S (O) (U-12c) 138-140
3-054 S (U-13a) 217-219
3-055 S (U-13b) Cl 189-192
3-056 S (U-13b) OMe 115-117
3-057 S (U-32a) 133-135
3-058 S (U-31a) 144-146
3-059 S (U-23a) 189-191
3-060 S (U-24a) 149-151
3-061 S (U-25a) 209-211
3-062 S (U-33a) 191-193
3-063 S (U-15a) 97-99
3-064 S (U-38a) 178-180
―――――――――――――――――――――――――――――
Table ¹ shows the ¹ H-NMR data of the compounds of the present invention that have no melting point.
[Table 5]
―――――――――――――――――――――――――――――――――――――――
No. ¹ H-NMR (CDCl ₃ , Me ₄ Si, 300 MHz)
―――――――――――――――――――――――――――――――――――――――
1-022 δ12.80 (brs, 1H), 8.40-8.30 (m, 2H), 8.21 (d, 1H, J = 7.4Hz), 7.94 (d, 1
H, J = 7.4Hz), 7.85-7.77 (m, 1H), 7.39-7.28 (m, 2H), 4.82 (s, 2H).
2-018 δ12.70 (brs, 1H), 8.37 (d, 1H, J = 6.8Hz), 7.57 (d, 1H, J = 6.8Hz), 4.18
(q, 2H, J = 7.4Hz), 3.31-3.11 (m, 4H), 2.57 (s, 3H), 2.56-2.50 (m, 1H),
2.20-2.09 (m, 2H), 2.05-1.81 (m, 2H), 1.29 (t, 3H, J = 7.4Hz).
3-002 δ12.27 (brs, 1H), 8.45 (d, 1H, J = 7.5Hz), 7.72 (d, 1H, J = 7.5Hz), 4.87-
4.83 (m, 1H), 4.10 (s, 3H), 3.47-3.33 (m, 1H), 3.21-3.04 (m, 2H),
2.91-2.79 (m, 1H), 2.69-2.48 (m, 2H).
3-003 δ12.32 (brs, 1H), 8.45 (d, 1H, J = 7.5Hz), 7.71 (d, 1H, J = 7.5Hz), 5.01-
4.97 (m, 1H), 4.11 (s, 3H), 3.40-3.17 (m, 3H), 3.00-2.78 (m, 2H),
2.49-2.40 (m, 1H).
3-013 δ12.29 (brs, 1H), 8.37 (d, 1H, J = 7.5Hz), 7.62 (d, 1H, J = 7.5Hz), 4.11
(s, 3H), 3.85-3.79 (m, 1H), 3.63-3.56 (m, 1H), 3.43 (q, 1H, J = 5.4Hz),
2.61 (d, 1H, J = 6.3Hz), 2.40 (dd, 1H, J = 5.4Hz, J = 1.2Hz).
3-039 δ11.94 (brs, 1H), 8.31 (d, 1H, J = 6.6Hz), 7.51 (d, 1H, J = 6.6Hz), 5.10
(q, 2H, J = 7.7Hz), 4.11 (s, 3H).
―――――――――――――――――――――――――――――――――――――――
[Reference Example 1]
Synthesis of 3-[(tetrahydro-2H-pyran-4-yl) thio] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid Step 1 Synthesis of methyl 3-thioxo-5- (trifluoromethyl) -2,3-dihydro- [1,2,4] triazolo [4,3-a] pyridine-8-carboxylate 2-hydrazinyl-6- ( To a mixed solution of 12.0 g (51.03 mmol) of methyl trifluoromethyl) nicotinate and 240 ml of 1,4-dioxane, 9.54 g (53.53 mmol) of 1,1′-thiocarbonyldiimidazole was added at room temperature. . After completion of the addition, the reaction mixture was stirred at 60 ° C. for 3 hours. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. The precipitated solid was washed with diisopropyl ether and collected by filtration to obtain 18.42 g of a mixture of the target compound and imidazole as a red solid.

Step 2: methyl 3-[(tetrahydro-2H-pyran-4-yl) thio] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate Synthesis of 3-thioxo-5- (trifluoromethyl) -2,3-dihydro- [1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid containing imidazole obtained in Step 1 To a solution of methyl 852 mg in N, N-dimethylformamide 10 ml, 500 mg (3.03 mmol) of 4-bromotetrahydro-2H-pyran was added at room temperature. After the addition was complete, the reaction mixture was stirred at 110 ° C. for 15 hours. After completion of the stirring, 50 ml of water was added to the reaction mixture to stop the reaction, followed by extraction with chloroform (30 ml × 3 times). The obtained organic layer was washed with water and then dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate [7: 3 to 1: 9 (volume ratio, the same applies hereinafter) gradient], and 100 mg of the desired product. Was obtained as a white solid.
¹ H-NMR (CDCl ₃ ); δ 7.98 (d, 1H, J = 7.2 Hz), 7.45 (d, 1H, J = 7.2 Hz), 4.22-4.13 (m, 1H) ), 4.10 (s, 3H), 3.99 (dt, 2H, J = 3.6 Hz, 11.7 Hz), 3.52 (dt, 2H, J = 2.4 Hz, 11.1 Hz), 2 .16-2.11 (m, 2H), 1.90-1.77 (m, 2H).
Melting point: 103-105 ° C
Step 3; of 3-[(Tetrahydro-2H-pyran-4-yl) thio] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid Synthesis 100 mg of methyl 3-[(tetrahydro-2H-pyran-4-yl) thio] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate ( 0.28 mmol) and 2 ml of methanol were added 1.2 ml of 0.5 mol / L sodium hydroxide aqueous solution under ice cooling. After completion of the addition, the reaction mixture was stirred for 1 hour under ice cooling. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. To the obtained residue, 10 ml of a 0.1 mol / L hydrochloric acid aqueous solution was added under ice cooling. The precipitated solid was washed with water and collected by filtration to obtain 90 mg of the desired product as an orange solid.
Melting point: 96-97 ° C
[Reference Example 2]
Synthesis of 3- (phenylthio) -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid Step 1; 3- (phenylthio) -5- (tri Synthesis of methyl fluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate 138 mg (0.72 mmol) of copper iodide (monovalent), 260 mg of 1,10-phenanthroline (1 .44 mmol), potassium carbonate 649 mg (4.69 mmol) and N, N-dimethylformamide 15 ml in a mixed solution at room temperature, 883 mg (4.33 mmol) and 3-thioxo-5- (trifluoromethyl) -2 , 3-Dihydro- [1,2,4] triazolo [4,3-a] pyridine-8-carboxylate methyl 1.00 g (3.61 mmol) It was added. After completion of the addition, the air in the reaction vessel was replaced with nitrogen gas. After completion of the substitution, the reaction mixture was stirred at 70 ° C. under a nitrogen gas atmosphere for 7 hours. After completion of the stirring, 50 ml of water was added to the reaction mixture to stop the reaction, followed by extraction with chloroform (50 ml × 3 times). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate (gradient of 7: 3 to 1: 9) to obtain 312 mg of the objective product as a pale yellow solid.
Melting point: 109-111 ° C
Step 2: Synthesis of 3- (phenylthio) -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid 3- (phenylthio) -5- (tri Fluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate (270 mg, 0.77 mmol) and methanol (3 ml) were mixed with 0.5 mol / L under ice-cooling. 2 ml of aqueous sodium hydroxide was added. After completion of the addition, the reaction mixture was stirred for 1 hour under ice cooling. After completion of stirring, 2 ml of a 1 mol / L hydrochloric acid aqueous solution was added to the reaction mixture. The precipitated solid was washed with water and collected by filtration to obtain 229 mg of the desired product as a pale yellow solid.
Melting point: 149-152 ° C
[Reference Example 3]
Synthesis of 3-[(6-chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid Step 1; Synthesis of ethyl 2- [2- {2- (6-chloropyridin-3-yl) acetyl} hydrazinyl] -6- (trifluoromethyl) nicotinate 600 mg of ethyl 2-hydrazinyl-6- (trifluoromethyl) nicotinate (2.41 mmol), 2- (6-chloropyridin-3-yl) acetic acid 610 mg (3.56 mmol), triethylamine 360 mg (3.56 mmol) and N, N-dimethylformamide 15 ml in a mixed solution at room temperature. 680 mg (3.55 mmol) of ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride was added. After the addition was complete, the reaction mixture was stirred at room temperature for 15 hours. After completion of the stirring, 50 ml of water was added to the reaction mixture to stop the reaction, and extraction with ethyl acetate (50 ml × 3 times) was performed. The obtained organic layer was washed with water and dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate (gradient 7: 3 to 1: 9) to obtain 860 mg of the desired product as a white solid.
Melting point: 162-163 ° C
Step 2; of ethyl 3-[(6-chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate Synthesis To a mixed solution of ethyl 860 mg (2.14 mmol) 2- [2- {2- (6-chloropyridin-3-yl) acetyl} hydrazinyl] -6- (trifluoromethyl) nicotinate and 20 ml toluene at room temperature 970 mg (6.39 mmol) of phosphoryl chloride was added. After completion of the addition, the reaction mixture was stirred for 8 hours under heating to reflux. After completion of the stirring, the reaction mixture was added to ice water to stop the reaction, and sodium bicarbonate was added to adjust the pH to 8-9, followed by extraction with ethyl acetate (50 ml × 3 times). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate (1: 1 to 1: 9 gradient) to obtain 630 mg of the desired product as a white solid.
Melting point: 144-145 ° C
Step 3; Synthesis of 3-[(6-chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid 630 mg of ethyl 3-[(6-chloropyridin-3-yl) methyl] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate (1. 64 mmol) and 15 ml of ethanol were added 2 ml of a 1 mol / L aqueous sodium hydroxide solution under ice cooling. After completion of the addition, the reaction mixture was stirred for 1 hour under ice cooling. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. To the obtained residue, 20 ml of 0.1 mol / L hydrochloric acid aqueous solution was added under ice cooling. The precipitated solid was washed with water and collected by filtration to obtain 550 mg of the desired product as a white solid.
Melting point: 69-70 ° C
[Reference Example 4]
Synthesis of 3-[(1-cyanocyclopropyl) amino] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid Step 1; 3-oxo Synthesis of ethyl 5- (trifluoromethyl) -2,3-dihydro- [1,2,4] triazolo [4,3-a] pyridine-8-carboxylate 2-hydrazinyl-6- (trifluoromethyl) To a mixed solution of 7.00 g (28.09 mmol) of ethyl nicotinate and 70 ml of tetrahydrofuran, 5.01 g (30.90 mmol) of 1,1′-carbonyldiimidazole was added at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 2 hours. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. To the obtained residue, 100 ml of 0.1 mol / L hydrochloric acid aqueous solution was added at room temperature, and the reaction mixture was extracted with ethyl acetate (100 ml × 2 times). The obtained organic layer was washed with water, dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 6.79 g of the desired product as a yellow solid.
Melting point: 156-157 ° C
Step 2: Synthesis of ethyl 2- [2-{(1-cyanocyclopropyl) carbamoyl} hydrazinyl] -6- (trifluoromethyl) nicotinate 3-oxo-5- (trifluoromethyl) -2,3-dihydro -To a mixed solution of 500 mg (1.82 mmol) of ethyl [1,2,4] triazolo [4,3-a] pyridine-8-carboxylate, 370 mg (3.66 mmol) of triethylamine and 10 ml of tetrahydrofuran at room temperature, 430 mg (3.63 mmol) of aminocyclopropanecarbonitrile hydrochloride was added. After completion of the addition, the reaction mixture was stirred for 3 hours under heating to reflux. After completion of the stirring, 30 ml of water was added to the reaction mixture to stop the reaction, followed by extraction with chloroform (30 ml × 3 times). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate (gradient of 7: 3 to 1: 9) to obtain 600 mg of the objective product as a yellow solid.
Melting point: 162-168 ° C
Step 3: Synthesis of ethyl 3-[(1-cyanocyclopropyl) amino] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate 2- [2-{(1-cyanocyclopropyl) carbamoyl} hydrazinyl] -6- (trifluoromethyl) ethyl nicotinate 590 mg (1.65 mmol), 2-methoxypyridine 200 mg (1.83 mmol) and methylene chloride 10 ml mixed solution Was added 560 mg (1.98 mmol) of trifluoromethanesulfonic anhydride at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 4 hours. After completion of the stirring, 30 ml of water was added to the reaction mixture to stop the reaction, followed by extraction with chloroform (30 ml × 3 times). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography eluting with n-hexane: ethyl acetate (1: 1 to 1: 9 gradient) to obtain 360 mg of the desired product as a yellow solid.
Melting point: 65-66 ° C
Step 4: Synthesis of 3-[(1-cyanocyclopropyl) amino] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylic acid 3- [ 350 mg (1.03 mmol) of ethyl (1-cyanocyclopropyl) amino] -5- (trifluoromethyl)-[1,2,4] triazolo [4,3-a] pyridine-8-carboxylate and 1,4 -To a mixed solution of 10 ml of dioxane, 3 ml of a 1 mol / L aqueous sodium hydroxide solution was added under ice cooling. After completion of the addition, the reaction mixture was stirred for 1 hour under ice cooling. After completion of the stirring, the solvent in the reaction mixture was distilled off under reduced pressure. To the obtained residue, 20 ml of 0.1 mol / L hydrochloric acid aqueous solution was added under ice-cooling, followed by extraction with chloroform (30 ml × 3 times). The obtained organic layer was dried over anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure to obtain 170 mg of the desired product as a yellow solid.
Melting point: 235-240 ° C
The compounds shown in Tables 6 to 9 were synthesized in the same manner as in Reference Examples 1 to 4. In the table, “Me” represents methyl, and similarly, Ph represents phenyl, OMe represents methoxy, CO ₂ Me represents methoxycarbonyl, and CO ₂ Et represents ethoxycarbonyl.

  In the table, “mp” represents a melting point, and “* 1” represents “resin”.

  In the table, U-1a, U-1b, U-1c, U-3a, U-7a, U-7b, U-7c, U-8a, U-11a, U-11b, U-12a, U- 12b, U-12c, U-12d, U-12e, U-12f, U-13a, U-13b, U-15a, U-16a, U-17a, U-21a, U-22a, U-22b, U-23a, U-24a, U-25a, U-25b, U-26a, U-26b, U-27a, U-31a, U-32a, U-33a, U-38a, D-1 Each of the substituents represents the following structure.

[Table 6]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
A-001 U-1a 146-148
A-002 U-3a 194-196
A-003 CH ₂ (U-3a) 186-188
A-004 CH ₂ (U-8a) 96-100
A-005 U-7a 174-177
A-006 SCH ₂ CH ₂ OC (O) Me 83-84
A-007 S (U-16a) 96-97
A-008 SCH ₂ (U-17a) 96-99
A-009 SPh 149-152
A-010 S (4-OMe-Ph) 125-129
A-011 S [3,4-di (OMe) -Ph] 61-62
A-012 S (U-12a) 228-230
A-013 U-21a CO ₂ Me 150-151
A-014 U-22a OMe 158-159
A-015 U-22a CO ₂ Et 180-183
A-016 U-22b CO ₂ Et 135-140
A-017 NH (D-1) 235-240
A-018 CH ₂ O (4-OMe-Ph) 155-156
A-019 CH ₂ (U-12b) Cl 69-70
A-020 CH ₂ (U-12b) OMe 55-56
A-021 CH ₂ S [3,4-di (OMe) -Ph] 124-125
A-022 N (Me) OMe 172-174
A-023 NH (U-23a) 209-210
A-024 NH (U-16a) 66-69
A-025 CH ₂ (U-26a) 211-213
A-026 CH ₂ (U-26b) 203-205
A-027 CH ₂ (U-11a) 60-61
A-028 CH ₂ (U-11b) Cl 171-173
A-029 CH ₂ (U-11b) Br 156-157
A-030 CH ₂ (U-12a) 211-212
A-031 CH ₂ (U-13a) 147-149
A-032 CH ₂ (U-13b) Cl 63-64
A-033 CH ₂ (U-25b) 227-229
A-034 CH ₂ (U-27a) * 1
A-035 OCH ₂ CH ₂ OMe 110-111
A-036 OCH ₂ CF ₃ 179-180
A-037 O (4-OMe-Ph) 172-173
A-038 S (4-CN-Ph) 198-200
A-039 S (U-11a) 213-215
A-040 S (U-11b) Cl 213-215
A-041 S (U-11b) OMe 194-196
A-042 S (U-12b) Me 185-187
A-043 S (U-12d) * 1
A-044 S (U-12e) * 1
A-045 S (U-12f) 203-204
A-046 S (U-12b) Cl 183-185
A-047 S (U-12b) OMe 200-202
A-048 S (U-12b) CF ₃ 196-198
A-049 S (U-13a) 221-223
A-050 S (U-13b) Cl 164-166
A-051 S (U-13b) OMe 133-135
A-052 S (U-32a) 90-92
A-053 S (U-31a) 146-148
A-054 S (U-23a) 188-190
A-055 S (U-24a) 221-223
A-056 S (U-25a) 169-171
A-057 S (U-33a) * 1
A-058 S (U-15a) 132-134
A-059 S (U-38a) 135-137
―――――――――――――――――――――――――――――
[Table 7]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
B1-001 U-1a 185-188
B1-002 U-3a 160-164
B1-003 CH ₂ (U-3a) 151-153
B1-004 CH ₂ (U-8a) 127-129
B1-005 U-7a 152-154
B1-006 S (U-16a) 103-105
B1-007 SCH ₂ (U-17a) 81-83
B1-008 SPh 109-111
B1-009 S [3,4-di (OMe) -Ph] 115-116
B1-010 S (U-12a) 119-121
B1-011 CH ₂ (U-26a) 153-155
B1-012 CH ₂ (U-26b) 168-170
B1-013 CH ₂ (U-25b) 184-186
B1-014 S (4-CN-Ph) 162-164
B1-015 S (U-11a) 82-84
B1-016 S (U-11b) Cl * 1
B1-017 S (U-11b) OMe 139-141
B1-018 S (U-12b) Cl 184-186
B1-019 S (U-12b) OMe 147-150
B1-020 S (U-13a) 131-133
B1-021 S (U-24a) 43-45
B1-022 S (U-15a) 103-105
B1-023 S (U-38a) 118-120
―――――――――――――――――――――――――――――
[Table 8]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
B2-001 S (4-OMe-Ph) * 1
B2-002 U-22a OMe 87-88
B2-003 NH (D-1) 65-66
B2-004 CH ₂ O (4-OMe-Ph) 79-80
B2-005 CH ₂ (U-12b) Cl 144-145
B2-006 CH ₂ (U-12b) OMe 151-152
B2-007 CH ₂ S [3,4-di (OMe) -Ph] 130-131
B2-008 N (Me) OMe 92-93
B2-009 NH (U-23a) 93-98
B2-010 NH (U-16a) * 1
B2-011 CH ₂ (U-11a) * 1
B2-012 CH ₂ (U-11b) Cl 121-122
B2-013 CH ₂ (U-11b) Br 126-127
B2-014 CH ₂ (U-12a) 117-118
B2-015 CH ₂ (U-13a) 133-134
B2-016 CH ₂ (U-13b) Cl * 1
B2-017 OCH ₂ CH ₂ OMe 72-73
B2-018 OCH ₂ CF ₃ 120-121
B2-019 O (4-OMe-Ph) 117-118
B2-020 S (U-12b) Me 89-91
B2-021 S (U-12b) CF ₃ 120-122
B2-022 S (U-13b) Cl 85-87
B2-023 S (U-13b) OMe 101-103
B2-024 S (U-32a) 105-107
B2-025 S (U-31a) 117-119
B2-026 S (U-23a) * 1
B2-027 S (U-25a) 114-116
―――――――――――――――――――――――――――――
[Table 9]

―――――――――――――――――――――――――――――
No. R ^1a R ⁸ mp (℃)
―――――――――――――――――――――――――――――
B3-001 U-21a CO ₂ Me * 1
B3-002 U-22a CO ₂ Et * 1
B3-003 U-22b CO ₂ Et * 1
―――――――――――――――――――――――――――――
Tables 10 to 9 show ¹ H-NMR data of compounds having no melting point in Tables 6 to 9.
[Table 10]
―――――――――――――――――――――――――――――――――――――――
No. ¹ H-NMR (CDCl ₃ , Me ₄ Si, 300 MHz)
―――――――――――――――――――――――――――――――――――――――
A-034 δ8.29 (d, 1H, J = 7.4Hz), 7.70 (d, 1H, J = 3.3Hz), 7.64 (d, 1H, J = 7.4Hz),
7.35 (d, 1H, J = 3.3Hz), 5.08 (s, 2H). (The proton peak of CO ₂ H was not observed.)
A-043 δ8.54 (d, 1H, J = 3.7Hz), 8.28 (d, 1H, J = 7.4Hz), 7.70 (d, 1H, J = 7.4Hz),
7.66 (d, 1H, J = 7.7Hz), 7.17 (dd, 1H, J = 7.7Hz, 4.8Hz), 2.73 (s, 3H).
(The proton peak of CO ₂ H was not observed.)
A-044 δ8.48 (s, 1H), 8.37 (s, 1H), 8.17 (d, 1H, J = 7.0Hz), 7.68 (s, 1H), 7.58
(d, 1H, J = 7.0Hz), 2.31 (s, 3H). (The proton peak of CO ₂ H was not observed.)
A-057 δ8.23 (d, 1H, J = 7.5Hz), 7.62 (d, 1H, J = 7.5Hz), 7.51 (s, 1H), 7.39 (s,
1H), 3.74 (s, 3H). (The proton peak of CO ₂ H was not observed.)
B1-016 δ8.19-8.11 (m, 2H), 7.59-7.48 (m, 2H), 7.12 (d, 1H, J = 8.6Hz), 4.14 (s,
3H).
B2-001 δ7.96 (d, 1H, J = 7.1Hz), 7.57-7.45 (m, 3H), 6.86-6.81 (m, 2H), 4.54 (q,
2H, J = 7.1Hz), 3.78 (s, 3H), 1.44 (t, 3H, J = 7.1Hz).
B2-010 δ7.73 (d, 1H, J = 7.4Hz), 7.23 (d, 1H, J = 7.4Hz), 4.54 (q, 2H, J = 7.1Hz),
4.22-4.18 (m, 2H), 4.05-3.97 (m, 2H), 3.67-3.55 (m, 2H), 2.29-2.23 (m,
2H), 1.79-1.65 (m, 2H), 1.48 (t, 3H, J = 7.1Hz).
B2-011 δ8.49 (d, 1H, J = 4.8Hz), 7.98 (d, 1H, J = 6.8Hz), 7.66-7.57 (m, 1H), 7.45
(d, 1H, J = 7.4Hz), 7.19-7.12 (m, 2H), 4.90 (s, 2H), 4.58 (q, 2H, J = 7.1
Hz), 1.50 (t, 3H, J = 7.1Hz).
B2-016 δ8.31 (d, 1H, J = 5.1Hz), 8.01 (d, 1H, J = 7.5Hz), 7.49 (d, 1H, J = 7.5Hz),
7.20-7.07 (m, 2H), 4.67 (s, 2H), 4.59 (q, 2H, J = 7.2Hz), 1.50 (t, 3H,
J = 7.2Hz).
B2-026 δ7.98 (d, 1H, J = 7.4Hz), 7.49 (d, 1H, J = 7.4Hz), 7.33 (d, 1H, J = 2.4Hz),
6.50 (d, 1H, J = 2.4Hz), 4.54 (q, 2H, J = 7.1Hz), 3.86 (s, 3H), 1.46 (t,
3H, J = 7.1Hz).
B3-001 δ7.95 (d, 1H, J = 7.2Hz), 7.57 (d, 1H, J = 6.6Hz), 7.44-7.33 (m, 5H), 5.53
(s, 2H), 4.57-4.50 (m, 1H), 3.62-3.51 (m, 4H), 3.25-3.12 (m, 1H),
2.50-2.32 (m, 1H), 2.29-2.09 (m, 3H).
B3-002 δ7.95 (d, 1H, J = 7.1Hz), 7.57 (d, 1H, J = 6.6Hz), 7.44-7.33 (m, 5H), 5.55
(s, 2H), 4.14 (q, 2H, J = 7.1Hz), 3.49-3.12 (m, 4H), 2.83-2.69 (m, 1H),
2.29-2.19 (m, 1H), 1.92-1.75 (m, 3H), 1.23 (t, 3H, J = 7.1Hz).
B3-003 δ7.95 (d, 1H, J = 6.8Hz), 7.57 (d, 1H, J = 6.6Hz), 7.44-7.33 (m, 5H), 5.54
(s, 2H), 4.29-4.11 (m, 3H), 3.32-3.15 (m, 4H), 2.59-2.48 (m, 1H),
2.12-1.88 (m, 3H), 1.28 (t, 3H, J = 7.1Hz).
―――――――――――――――――――――――――――――――――――――――
Test Example Next, the usefulness of the compound of the present invention as a herbicide will be specifically described in the following test examples, but the present invention is not limited thereto.
[Test Example 1] Herbicidal effect test by pretreatment of weed generation under flooded conditions After alluvial soil was put into a 1/10000 are Wagner pot, water was added and mixed to create a flooded condition with a depth of 4 cm. After seeding nobies, firefly and koigi in the cup, rice seedlings at the 2.5 leaf stage were transplanted. On the day of sowing, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose and treated on the water surface. Plants were grown by placing the cup in a greenhouse at 25 to 30 ° C., and after 3 weeks of drug treatment, the effects on various plants were investigated according to the following criteria. The results are shown in Table 11.

Criterion 5 ... More than 90% of herbicide rate (almost completely dead)
4 ... Herbicidal Rate 70% or more and less than 90% 3 ... Herbicidal Rate 40% or more and less than 70% 2 ... Herbicidal Rate 20% or more and less than 40% 1 ... Herbicidal Rate 5% or more but less than 20% 0 ... Herbicidal Rate 5% or less (almost effective) None)
[Test Example 2] Herbicidal effect test by treatment with weed growing season in flooded condition After alluvial soil was put into a 1/10000 are Wagner pot, water was added and mixed to obtain a flooded condition of 4 cm in water depth. Nobies, firefly, and oak seeds were mixed in the cup and placed in a greenhouse at 25-30 ° C. to grow plants. When Nobies, Firefly and Konagi reached the 1st to 2nd leaf stage, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water so as to have a predetermined dosage and treated on the water surface. Three weeks after the drug treatment, the influence on various plants was investigated according to the criteria of Test Example 1. The results are shown in Table 12.
[Test Example 3] Herbicidal effect test by foliar treatment After alluvial soil was put into a 1/10000 are Wagner pot, water was added and mixed to obtain a condition of water depth of 0.1 to 0.5 cm. Inobie, Azegaya, Kogomegatsutsu and rice seeds were sown and placed in a greenhouse at 25 to 30 ° C. to grow plants. After growing for 14 days, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose, and uniformly treated with a small spray on the foliage. Three weeks after the drug treatment, the influence on various plants was investigated according to the criteria of Test Example 1. The results are shown in Table 13.
[Test Example 4] Herbicidal effect test by soil treatment Put sterilized large soil in a plastic box 21cm long, 13cm wide and 7cm deep, and then weed bark, Enocorosa, Inobie, oats, blackgrass, Italian ryegrass, Atlantic cabbage, The seeds of Ichibi, Aogateto, Shiroza, Jacobe, Yamgra, Giant corn, corn, soybean, rice, wheat, beet and rapeseed were sown in a spot shape and covered with about 1.5 cm of soil. Next, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose, and uniformly treated with a small spray on the soil surface. Plants were grown by placing plastic boxes in a greenhouse at 25 to 30 ° C., and after 3 weeks of chemical treatment, the effects on various plants were investigated according to the criteria of Test Example 1. The results are shown in Table 14.
[Test Example 5] Herbicidal effect test by foliar treatment Put sterilized piled soil in a plastic box 21cm long, 13cm wide, 7cm deep, and pearl bark, green croaker, barnyardgrass, oats, blackgrass, Italian ryegrass, yellow croaker, Seeds of Ichibi, Aogateto, Shiroza, Jacobe, Jaegula, Giant corn, corn, soybean, rice, wheat, beet, and rapeseed are spotted, covered with about 1.5 cm, and then planted in a greenhouse at 25 to 30 ° C. Nurtured. After growing for 14 days, the emulsion of the compound of the present invention prepared according to Formulation Example 2 was diluted with water to a predetermined dose, and uniformly treated with a small spray on the foliage. Three weeks after the drug treatment, the influence on various plants was investigated according to the criteria of Test Example 1. The results are shown in Table 15.

The symbols in Tables 11 to 15 represent the following meanings.
A: Nobies, B: Firefly, C: Konagi, D: Azegaya, E: Kogomegatsuri, F: Barbet, G: Enokirogusa, H: Inubie, I: Oats, J: Blackgrass, K: Italian ryegrass, L: Atlantic calyx , M: Ichibi, N: Blue-headed toe, O: Shiroza, P: Jacobe, Q: Yamgra, R: Giant corn, a: Transplanted rice, b: Directly sown rice, c: Corn, d: Soy, e: Wheat, f: Beet , G: rapeseed The treatment dose (g / ha) represents that the concentration was adjusted so that the number of grams (g) described was processed when converted per hectare (1 ha). .
[Table 11]
―――――――――――――――――――――――――
No. Treatment dose A B C a
(G / ha)
―――――――――――――――――――――――――
1-001 320 5 5 4 4
1-002 320 5 5 5 4
1-003 320 0 2 3 0
1-004 320 0 3 3 0
1-005 320 1 3 1 2
1-006 320 0 3 3 3
1-007 320 2 3 3 2
1-008 320 0 1 0 0
1-009 320 5 5 5 0
1-011 320 0 5 3 2
1-012 320 3 4 3 1
1-013 320 3 4 2 0
1-014 320 4 4 3 0
1-015 320 0 2 3 0
1-016 320 4 4 4 1
1-017 320 5 5 4 1
1-018 320 5 5 4 2
1-019 320 4 3 2
1-020 320 4 4 4 0
1-021 320 2 3 4 1
1-022 320 4 4 3 0
1-023 320 5 5 4 2
1-024 320 5 5 4 0
1-025 320 2 3 2 1
1-026 320 1 3 3 1
1-027 320 4 4 4 3
1-028 320 3 3 1
1-029 320 4 2 2
1-030 320 2 0 0
1-031 320 5 5 3 1
1-032 320 4 5 3 0
1-033 320 1 2 1 0
1-034 320 5 4 4 0
1-035 320 5 2 0
1-036 320 5 3 0
1-037 320 5 4 3 1
1-038 320 2 3 4 0
1-039 320 0 1 0 0
1-040 320 0 3 3 1
1-041 320 5 5 3 0
1-042 320 5 5 1 0
1-043 320 5 4 4 0
1-044 320 0 4 0 0
1-045 320 4 5 4 0
1-046 320 4 5 4 3
1-047 320 4 4 3 0
1-048 320 1 3 4 0
1-049 320 3 5 4 3
1-050 320 4 4 4 0
2-001 320 5 4 4 5
2-002 320 5 5 5 3
2-003 320 2 3 2 0
2-004 320 0 2 2 0
2-005 320 2 1 2 1
2-006 320 0 3 1 0
2-008 320 3 3 4 0
2-009 320 5 5 4 0
2-011 320 3 4 0 2
2-012 320 3 3 3 0
2-013 320 3 3 2 0
2-014 320 3 3 3 0
2-015 320 5 5 4 3
2-016 320 5 5 4 1
2-018 320 0 2 3 0
2-019 320 4 3 4 4
2-021 320 4 4 2 0
2-022 320 4 4 3 2
2-024 320 3 0 0 1
2-026 320 3 4 4 2
2-028 320 3 3 0 1
2-029 320 3 3 4 1
2-030 320 3 3 2 3
2-031 320 4 4 2 0
2-032 320 5 4 3 0
2-033 320 4 4 2 0
2-034 320 3 0 0 2
2-036 320 4 4 3 0
2-037 320 4 3 3 4
2-038 320 4 3 3 2
2-039 320 3 2 0
2-040 320 3 3 0 0
2-041 320 5 3 1
2-042 320 3 1 1
2-043 320 4 4 3 0
2-044 320 5 1
2-045 320 2 2 1 0
2-046 320 4 4 3 0
2-047 320 4 0
2-048 320 5 3 0
2-049 320 4 5 3 0
2-050 320 0 3 2 0
2-051 320 4 3 2 0
2-052 320 4 4 0 0
2-053 320 4 4 4 0
2-054 320 1 3 0 0
2-055 320 4 3 4 1
2-056 320 4 4 3 3
2-057 320 3 4 3 0
2-058 320 3 4 3 2
2-059 320 5 4 3 0
3-001 320 5 5 5 5
3-002 320 4 4 4 5
3-003 320 5 5 5 5
3-004 320 5 5 5 5
3-005 320 4 4 5 3
3-006 320 4 5 4 3
3-007 320 3 4 2 4
3-008 320 3 4 3 3
3-009 320 3 4 3 3
3-010 320 5 5 2
3-011 320 2 2 3 0
3-012 320 5 5 5 2
3-014 320 5 5 5 0
3-015 320 5 5 4 1
3-016 320 3 3 4 0
3-017 320 5 5 4 1
3-018 320 5 5 5 4
3-019 320 0 4 5 0
3-020 320 4 5 5 1
3-021 320 4 5 4 5
3-022 320 0 0 3 0
3-023 320 5 5 5 3
3-024 320 5 5 5 4
3-025 320 5 5 5 4
3-026 320 0 2 3 0
3-027 320 5 5 5 4
3-028 320 5 5 4 4
3-029 320 5 4 4 4
3-030 320 5 5 4 3
3-031 320 5 5 5 4
3-032 320 5 5 4 3
3-033 320 3 4 4 3
3-034 320 3 2 4 1
3-035 320 5 5 5 4
3-036 320 5 5 4 5
3-037 320 5 5 5 2
3-038 320 5 5 4 4
3-039 320 5 4 3 1
3-040 320 4 5 4 2
3-041 320 3 3 1
3-042 320 5 5 5 3
3-043 320 5 5 4 3
3-044 320 5 4 4 1
3-045 320 5 5 4 1
3-046 320 5 5 5 3
3-047 320 3 4 3 1
3-048 320 3 4 4 3
3-049 320 4 1
3-050 320 5 5 4 2
3-051 320 5 5 4 2
3-052 320 3 4 4 3
3-053 320 3 3 4 2
3-054 320 0 4 4 1
3-055 320 5 5 4 3
3-056 320 5 5 4 0
3-057 320 5 5 5 3
3-058 320 4 4 3 1
3-059 320 5 5 5 4
3-060 320 5 5 4 2
3-061 320 5 5 4 1
3-062 320 2 3 4 3
3-063 320 4 5 4 2
3-064 320 5 5 5 3
―――――――――――――――――――――――――
[Table 12]
―――――――――――――――――――――――――
No. Treatment dose A B C
(G / ha)
―――――――――――――――――――――――――
1-001 320 5 3 4
1-002 320 5 4 4
1-003 320 0 1 3
1-004 320 2 3 3
1-005 320 2 3 3
1-006 320 2 3 1
1-007 320 2 2 0
1-009 320 5 5 4
1-011 320 2 4 2
1-012 320 3 3 3
1-013 320 2 3 2
1-014 320 3 4 4
1-015 320 3 3 2
1-016 320 2 2 3
1-017 320 5 4 3
1-018 320 4 5 4
1-019 320 3 4 2
1-020 320 4 4 4
1-021 320 4 3 1
1-022 320 3 3 4
1-023 320 4 5 3
1-024 320 4 5 4
1-025 320 0 2 3
1-026 320 1 3
1-027 320 5 4 4
1-028 320 4 2 2
1-029 320 3 3 2
1-030 320 1 0
1-031 320 4 4 1
1-032 320 3 4 3
1-033 320 0 3 0
1-034 320 4 5 4
1-035 320 4
1-036 320 4
1-037 320 4 4 4
1-038 320 3 4 2
1-039 320 1 0 0
1-040 320 1 4 4
1-041 320 4 4 3
1-042 320 3 3 2
1-043 320 3 4 2
1-044 320 0 4 0
1-045 320 4 5 3
1-046 320 4 5 4
1-047 320 3 4 3
1-048 320 0 3 4
1-049 320 1 5 4
1-050 320 3 4 2
2-001 320 5 3 4
2-002 320 5 4 4
2-003 320 1 2 1
2-004 320 2 2 0
2-005 320 0 2 2
2-006 320 0 2 0
2-008 320 0 1 0
2-009 320 4 4 4
2-011 320 1 1 0
2-012 320 2 2 2
2-013 320 2 2 0
2-014 320 2 3 3
2-015 320 3 3 3
2-016 320 3 2 3
2-018 320 0 3 2
2-019 320 3 2 2
2-021 320 4 4 3
2-022 320 3 4 3
2-026 320 1 4 3
2-028 320 2 0
2-029 320 4 4
2-030 320 1 1 0
2-031 320 3 3 3
2-032 320 4 4 2
2-033 320 3 3 2
2-034 320 3 1 0
2-035 320 0 1 0
2-036 320 3 3 3
2-037 320 4 3 3
2-038 320 3 4 2
2-039 320 4 2
2-040 320 3
2-041 320 4 5 3
2-042 320 2 4 2
2-043 320 4 4 2
2-044 320 3 4 3
2-045 320 0 1 0
2-046 320 3 4 2
2-047 320 3
2-048 320 3
2-049 320 3 4 4
2-050 320 0 2 1
2-051 320 3 4 3
2-052 320 3 1 0
2-053 320 4 3 3
2-054 320 1 3 0
2-055 320 3 4 4
2-056 320 3 3 2
2-057 320 2 4 2
2-058 320 1 4 3
2-059 320 3 3 3
3-001 320 5 5 5
3-002 320 2 3 4
3-003 320 5 5 5
3-004 320 5 5 5
3-005 320 4 3 4
3-006 320 2 3 4
3-007 320 4 5 4
3-008 320 2 3 1
3-009 320 3 4 4
3-010 320 1 2 4
3-011 320 3 2 2
3-012 320 5 5 5
3-014 320 4 5 3
3-015 320 3 5 4
3-016 320 2 3 2
3-017 320 4 5 4
3-018 320 5 5 5
3-019 320 1 3 4
3-020 320 3 4 4
3-021 320 4 5 4
3-022 320 2 1 3
3-023 320 4 5 4
3-024 320 5 5 4
3-025 320 5 5 5
3-026 320 2 3 2
3-027 320 4 4 3
3-028 320 4 5 5
3-029 320 4 4 4
3-030 320 4 5 4
3-031 320 5 5 4
3-032 320 5 5 4
3-033 320 2 3
3-034 320 2 3 3
3-035 320 5 5 4
3-036 320 5 5 4
3-037 320 4 5 5
3-038 320 5 5 4
3-039 320 4
3-040 320 5 3
3-041 320 3 4 2
3-042 320 5 5 4
3-043 320 4 5 4
3-044 320 3 4 4
3-045 320 4 5 4
3-046 320 4 5 4
3-047 320 3 4 4
3-048 320 3 5 4
3-049 320 4
3-050 320 5
3-051 320 3 5 4
3-052 320 1 3 2
3-053 320 2 3 3
3-054 320 3 4 4
3-055 320 5 4 4
3-056 320 4 4 4
3-057 320 5 5 5
3-058 320 3 4 4
3-059 320 5 5 5
3-060 320 5 5 4
3-061 320 4 5 4
3-062 320 3 4 3
3-063 320 4 4 3
3-064 320 5 5 4
―――――――――――――――――――――――――
[Table 13]
―――――――――――――――――――――――――
No. Treatment dose H D E b
(G / ha)
―――――――――――――――――――――――――
1-001 320 5 5 5 5
1-002 320 5 4 5 4
1-003 320 4 4 5 1
1-004 320 4 5 5 3
1-005 320 5 5 5 3
1-006 320 5 5 5 3
1-007 320 3 5 5 2
1-008 320 5 2 5 0
1-009 320 4 5 5 0
1-010 320 3 3 4 0
1-011 320 2 0 3 0
1-012 320 4 2 5 0
1-013 320 4 4 5 0
1-014 320 5 4 5 0
1-015 320 1 5 4 0
1-016 320 5 5 5 3
1-017 320 5 5 5 3
1-018 320 5 5 5 0
1-019 320 5 5 4 3
1-020 320 5 5 5 3
1-021 320 5 4 4 3
1-022 320 5 5 5 2
1-023 320 5 5 5 3
1-024 320 5 5 4 2
1-025 320 4 5 4 0
1-026 320 4 5 4 0
1-027 320 5 5 5 4
1-028 320 5 4 2 2
1-029 320 4 3 4 0
1-030 320 3 0 3 0
1-031 320 5 4 4 0
1-032 320 4 3 5 0
1-033 320 3 3 3 0
1-034 320 5 4 5 0
1-035 320 5 4 5 1
1-036 320 4 5 5 0
1-037 320 5 3 4 0
1-038 320 5 4 5 0
1-039 320 4 4 4 0
1-040 320 5 0 4 1
1-041 320 5 3 4 0
1-042 320 5 3 5 0
1-043 320 4 4 5 0
1-044 320 3 0 5 0
1-045 320 5 5 5 0
1-046 320 5 5 5 1
1-047 320 5 4 5 0
1-048 320 4 4 4 0
1-049 320 5 4 5 0
1-050 320 5 4 4 0
2-001 320 5 5 5 5
2-002 320 5 5 5 4
2-003 320 5 4 5 3
2-004 320 5 4 5 4
2-005 320 5 5 5 4
2-006 320 5 5 5 3
2-007 320 5 5 5 2
2-008 320 5 3 5 0
2-009 320 5 4 5 0
2-010 320 4 3 4 0
2-011 320 3 0 4 0
2-012 320 4 0 5 0
2-013 320 5 0 4 0
2-014 320 5 3 5 1
2-015 320 5 5 4 0
2-016 320 5 2 3 3
2-017 320 2 3 2 0
2-018 320 5 5 5 1
2-019 320 5 5 5 4
2-020 320 3 0 3 0
2-021 320 5 5 5 1
2-022 320 5 5 5 1
2-023 320 2 3 1 0
2-024 320 5 4 5 4
2-026 320 5 5 5 2
2-027 320 3 3 4 2
2-028 320 5 5 4 3
2-029 320 5 5 4 2
2-030 320 4 4 4 0
2-031 320 5 5 5 1
2-032 320 5 5 5 1
2-033 320 5 5 5 1
2-034 320 4 4 4 1
2-035 320 4 4 4 0
2-036 320 5 5 4 0
2-037 320 5 5 4 3
2-038 320 5 5 5 3
2-039 320 5 5 4 1
2-040 320 4 4 4 0
2-041 320 5 5 5 3
2-042 320 4 3 4 0
2-043 320 5 4 4 0
2-044 320 5 3 4 0
2-045 320 4 3 4 1
2-046 320 5 2 5 0
2-047 320 5 4 4 0
2-048 320 5 4 4 0
2-049 320 5 3 4 0
2-050 320 5 0 4 0
2-051 320 5 4 5 0
2-052 320 5 2 5 0
2-053 320 5 4 4 0
2-054 320 5 1 5 0
2-055 320 5 4 5 0
2-056 320 5 4 4 0
2-057 320 5 3 5 0
2-058 320 4 4 4 0
2-059 320 5 5 5 0
3-001 320 5 5 5 5
3-002 320 5 5 5 5
3-003 320 5 5 5 5
3-004 320 5 5 5 5
3-005 320 4 4 5 3
3-006 320 4 5 5 3
3-007 320 5 5 5 5
3-008 320 5 5 5 4
3-009 320 5 5 5 5
3-010 320 5 5 5 4
3-011 320 5 5 5 4
3-012 320 5 5 5 1
3-013 320 5 4 4 2
3-014 320 4 5 5 1
3-015 320 5 5 5 2
3-016 320 3 4 5 0
3-017 320 5 5 5 3
3-018 320 5 5 5 4
3-019 320 1 5 5 0
3-020 320 5 5 5 4
3-021 320 5 5 5 5
3-022 320 2 5 2 0
3-023 320 5 5 5 5
3-024 320 5 5 5 4
3-025 320 5 5 5 5
3-026 320 4 4 4 3
3-027 320 5 5 5 5
3-028 320 5 5 5 5
3-029 320 5 4 5 4
3-031 320 5 5 5 5
3-032 320 5 5 5 4
3-033 320 5 5 5 4
3-034 320 4 5 4 3
3-035 320 5 5 5 5
3-036 320 5 5 5 5
3-037 320 5 5 5 4
3-038 320 5 5 5 5
3-039 320 4 5 4 1
3-040 320 5 5 5 3
3-041 320 4 4 4 0
3-042 320 5 5 5 1
3-043 320 5 5 5 2
3-044 320 5 4 3 3
3-045 320 5 5 5 2
3-046 320 5 5 5 5
3-047 320 5 5 5 3
3-048 320 5 5 5 5
3-049 320 5 5 5 1
3-050 320 5 5 5 1
3-051 320 4 5 5 3
3-052 320 5 5 5 3
3-053 320 5 5 5 3
3-054 320 5 5 5 4
3-055 320 5 4 5 4
3-056 320 5 5 5 0
3-057 320 5 5 5 3
3-058 320 5 4 5 0
3-059 320 5 5 5 5
3-060 320 5 5 5 3
3-061 320 5 5 5 4
3-062 320 5 5 4 4
3-063 320 5 4 5 2
3-064 320 5 5 5 4
―――――――――――――――――――――――――
[Table 14]
―――――――――――――――――――――――――――――――――――――
No. Treatment dose FGHIJKLMNOPPQR b cd def g
(G / ha)
―――――――――――――――――――――――――――――――――――――
1-001 320 2 0 0 0 0 0 0 0 3 2 0 0 0 0 0 0 0 0 0
1-002 320 2 0 0 0 0 0 3 0 3 4 0 0 0 0 0 0 2 1
1-003 320 0 0 0 0 0 0 0 0 0 1 0 0 0 0 0 0 0 0 0
1-008 320 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0
1-009 320 1 0 0 0 0 0 0 0 3 3 3 0 0 0 0 0 0 0 0
1-011 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 4 0
1-012 320 0 0 0 0 0 0 0 0 0 2 0 0 0 0 0 0 0 0 0
1-017 320 3 0 0 0 0 0 0 2 0 0 0 0 2
2-001 320 3 0 0 0 0 0 0 0 3 5 0 0 3 0 0 0 0 0 0
2-002 320 2 0 0 0 0 0 0 0 1 5 0 0 0 0 0 0 0 0 0
2-003 320 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0 0
2-006 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0
2-008 320 0 0 0 0 0 0 0 0 0 5 3 0 0 0 0 0 0 0 0
2-009 320 3 0 0 0 0 0 0 0 0 0 0 0 0 0
2-012 320 0 0 0 0 0 0 0 0 0 2 0 0 1 0 0 0 0 0 0
2-013 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0
2-016 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0
2-019 320 0 0 0 0 0 0 0 0 0 5 0 0 0 0 0 0 0 0
2-020 320 0 0 0 0 0 0 0 0 0 3 0 0 1 0 0 0 0 0 0
2-022 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 3 0
3-001 320 3 0 1 0 0 0 0 1 4 2 0 0 0 0 0 0 0 0 0
3-002 320 0 0 0 0 0 0 0 0 0 4 2 0 0 0 0 0 0 4 0
3-003 320 2 0 0 0 3 2 4 2 0 0 0 0 0 0
3-004 320 1 1 0 0 0 0 0 1 4 5 4 0 0 0 0 0 0
3-005 320 0 0 0 0 0 0 0 0 0 5 0 0 2 0 0 0 0 0 0
3-006 320 0 0 0 0 0 0 0 0 0 5 3 0 3 0 0 0 0 5 0
3-007 320 0 0 0 0 0 0 0 0 0 3 0 2 0 0 0 0
3-008 320 0 0 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0
3-010 320 0 0 0 0 0 0 0 0 0 5 3 0 0 0 0 0 0 0 0
3-011 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 0 0
3-012 320 4 5 5 0 0 1 2 3 5 2 0 0 0 0 0
3-014 320 0 0 0 0 0 0 0 0 0 5 4 0 1 0 0 0 0 5 0
3-015 320 0 0 0 0 0 0 0 0 0 3 0 0 4 0 0 0 0 2 0
3-016 320 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0
3-017 320 0 0 0 0 0 0 0 0 0 3 0 0 0 0 0 0 0 0
3-019 320 0 0 0 0 0 0 0 0 0 4 0 0 0 0 0 0 0 4 1
3-020 320 0 0 0 0 0 0 0 0 0 4 2 3 0 0 0 0 3 1
3-021 320 3 1 3 0 0 0 0 0 2 4 3 3 0 0 0 0 3 3
3-022 320 0 0 0 0 0 0 0 0 0 5 0 0 1 0 0 0 0 3 0
3-023 320 2 0 0 0 0 0 0 2 1 5 4 3 4 0 0 0 0 5 0
―――――――――――――――――――――――――――――――――――――
[Table 15]
―――――――――――――――――――――――――――――――――――――
No. Treatment dose FGHIJKLMNOPPQR b cd def g
(G / ha)
―――――――――――――――――――――――――――――――――――――
1-001 320 5 5 5 4 2 3 4 5 5 5 5 3 5 5 0 5 4 5 5
1-002 320 3 4 4 4 3 3 4 5 5 5 5 3 5 2 0 4 4 5 5
1-003 320 3 3 4 1 0 1 1 4 4 5 4 3 3 0 0 3 2 5 4
1-004 320 3 3 4 3 1 1 3 5 5 5 4 4 4 0 0 2 2 5 4
1-005 320 5 5 5 1 1 2 4 5 5 5 5 3 5 2 1 4 1 5 5
1-006 320 5 4 5 3 2 2 4 4 4 5 5 4 0 0 4 1 5 5
1-007 320 5 4 5 2 1 1 3 5 5 5 4 4 5 0 0 4 2 5 5
1-008 320 4 3 5 1 0 0 0 3 4 5 4 3 3 0 0 2 1 5 3
1-009 320 5 3 5 2 2 2 2 5 5 5 5 3 5 0 0 4 2 5 4
1-010 320 2 2 3 0 0 0 0 3 5 1 3 0 0 3 0 3
1-011 320 1 0 3 0 0 0 0 3 3 5 3 0 2 1 0 1 0 5 2
1-012 320 5 3 4 2 1 1 1 5 5 5 4 2 5 0 0 3 1 5 4
1-013 320 5 4 5 3 0 1 1 5 5 5 5 3 5 0 0 3 2 5 4
1-014 320 5 4 5 3 0 1 3 5 5 5 4 3 0 0 4 1 5 4
1-015 320 4 2 3 4 1 1 1 5 5 5 5 5 0 0 5 0 5 3
1-016 320 5 5 5 3 0 1 3 5 5 5 5 5 5 0 4 1 5 5
1-017 320 5 5 5 4 3 3 5 5 5 5 5 4 5 3 2 5 4 5 5
1-018 320 5 5 5 4 3 4 5 5 5 5 5 4 5 3 3 5 4 5 5
1-019 320 5 4 5 3 2 3 2 4 5 5 3 1 5 3 5 5
1-020 320 5 5 5 3 1 2 3 4 5 5 5 3 4 1 0 5 0 5 5
1-021 320 5 2 4 0 2 2 0 3 5 5 5 2 4 1 0 1 1 5 4
1-022 320 5 5 5 3 0 0 5 5 5 3 2 5 0 5 5
1-023 320 5 4 5 2 2 2 3 5 5 5 5 2 0 5 3 5 5
1-024 320 4 3 5 2 0 1 1 5 5 5 5 0 2 4 2 5 5
1-025 320 3 4 5 0 0 0 0 5 5 5 5 0 0 0 5 0 5 4
1-026 320 3 4 5 0 0 0 0 5 5 5 5 2 4 0 0 5 0 5 4
1-027 320 5 5 5 4 3 3 5 4 5 5 5 4 5 4 0 4 4 5 5
1-028 320 5 3 5 3 1 1 1 4 4 5 5 2 0 0 3 3 5 4
1-029 320 5 4 5 2 1 2 1 4 4 5 4 2 0 0 3 1 5 3
1-030 320 5 3 4 2 2 2 2 4 5 4 1 3 0 0 3 2 3 3
1-031 320 5 3 5 3 1 2 0 4 4 5 4 3 5 0 0 4 0 5 4
1-032 320 4 3 4 2 0 1 0 3 4 5 4 3 0 0 3 1 5 4
1-033 320 2 0 1 0 0 0 0 3 5 0 0 1 0 3 2
1-034 320 5 3 4 2 1 1 3 5 3 5 5 0 0 3 1 5 5
1-035 320 5 4 4 2 0 1 0 3 3 5 5 3 0 0 3 2 0 0
1-036 320 5 4 4 1 0 1 1 3 3 4 1 0 3 0 5 4
1-037 320 5 3 4 0 1 1 1 5 5 3 2 1 1 2 1 4 1
1-038 320 5 4 5 1 0 1 1 4 5 5 4 2 3 0 0 4 0 5 4
1-039 320 1 0 2 0 0 0 0 2 2 3 3 0 0 0 0 1 0 1 0
1-040 320 4 1 5 0 0 0 0 5 5 5 4 0 3 0 0 3 0 5 4
1-041 320 4 4 5 1 1 1 0 4 4 0 1 3 1 5 4
1-042 320 4 3 4 1 0 0 0 4 4 5 4 2 0 0 3 0 4 2
1-043 320 2 1 3 1 0 0 0 3 1 5 5 0 4 0 0 2 0 5 4
1-044 320 4 2 4 0 0 1 0 4 5 5 4 2 4 2 0 3 0 5 3
1-045 320 5 5 5 4 2 2 2 5 5 5 5 4 5 0 0 5 2 5 5
1-046 320 5 4 5 4 2 3 4 4 5 5 5 5 0 0 3 3 5 4
1-047 320 5 5 4 3 1 3 3 4 5 5 5 5 0 1 4 2 5 4
1-048 320 0 3 4 0 0 0 0 5 5 5 5 3 4 0 0 4 0 5 4
1-049 320 5 4 5 2 1 1 2 4 5 4 3 0 0 4 2 5 3
1-050 320 4 3 4 0 0 0 0 3 3 5 5 4 5 0 0 4 0 5 4
2-001 320 5 5 5 4 3 3 3 5 5 5 4 1 5 5 0 3 4 5 5
2-002 320 4 5 4 4 3 3 4 5 5 5 5 1 5 3 0 0 4 5 4
2-003 320 3 3 4 1 1 1 0 4 4 5 4 1 2 0 0 0 1 4 4
2-004 320 4 3 5 2 2 0 2 4 4 5 2 1 4 3 0 3 2 5 3
2-005 320 5 5 5 1 1 1 3 5 5 5 5 5 4 1 5 0 5 5
2-006 320 5 5 5 3 3 3 4 4 4 5 5 2 0 0 4 2 5 5
2-007 320 5 4 5 2 1 2 4 5 5 5 5 3 5 0 1 4 1 5 5
2-008 320 5 4 5 1 0 0 0 4 4 5 4 3 4 0 0 3 1 5 4
2-009 320 5 4 5 1 1 3 5 5 0 3 4 1 0
2-010 320 3 1 3 0 0 0 0 3 3 0 0 0 0 1 0 0
2-011 320 1 0 3 0 0 0 0 2 2 4 2 0 0 0 0 0 0 3 0
2-012 320 4 1 4 2 1 1 2 5 4 5 4 3 4 0 0 2 1 5 3
2-013 320 5 3 5 2 0 1 3 5 5 5 3 0 5 0 0 3 0 5 2
2-014 320 5 4 5 1 1 1 3 5 5 5 4 1 0 0 4 0 2
2-015 320 5 5 5 1 1 1 3 5 5 5 5 2 4 4 3 1 5 4
2-016 320 4 4 5 0 0 0 0 3 3 5 4 0 4 2 0 3 0 4 0
2-017 320 3 1 4 4 0 1 1 5 5 5 4 1 3 0 4 0 5 1
2-018 320 5 4 5 1 0 0 3 5 5 5 5 5 1 1 2 0 5 5
2-019 320 5 5 5 3 3 3 4 4 5 5 5 5 3 3 4 4 5 5
2-020 320 2 0 4 1 0 0 0 3 4 4 2 0 3 0 0 3 0 3 0
2-021 320 5 5 5 4 3 3 5 5 5 5 5 4 5 3 3 4 3 5 5
2-022 320 5 5 5 3 3 3 4 5 5 5 5 4 5 3 4 5 2 5 5
2-023 320 2 1 3 1 0 0 0 4 3 5 4 0 3 1 0 0 0 5 2
2-024 320 3 2 5 2 0 1 1 5 4 5 3 0 4 4 0 3 3 5 4
2-025 320 1 0 2 0 0 0 0 3 3 5 1 0 2 0 0 1 0 0 0
2-026 320 5 4 5 4 3 3 3 4 5 5 4 5 3 1 4 3 5 4
2-027 320 3 2 3 1 1 1 1 3 3 4 3 2 3 0 0 2 0 2 0
2-028 320 5 4 5 3 2 2 3 4 4 5 5 4 2 3 4 2 5 4
2-029 320 5 5 5 1 1 1 0 3 5 5 4 2 4 0 1 4 2 5 4
2-030 320 4 2 5 0 0 0 0 1 2 5 2 0 4 0 0 0 0 5 2
2-031 320 5 5 5 1 0 0 0 4 5 2 0 3 1 5 3
2-032 320 5 4 5 3 2 2 3 5 5 5 4 4 2 2 5 2 4 4
2-033 320 3 3 5 2 2 1 2 5 5 5 5 2 4 2 3 4 2 5 3
2-034 320 5 4 5 0 0 0 0 4 5 5 4 3 2 0 0 2 0 5 4
2-035 320 4 4 5 0 0 0 0 4 5 5 3 2 3 0 0 3 0 5 4
2-036 320 5 4 5 1 1 1 1 5 5 5 3 3 0 3 4 1 5 4
2-037 320 5 5 5 3 3 3 4 5 5 5 5 4 4 2 1 4 3 5 4
2-038 320 5 4 5 0 2 2 0 4 5 5 4 5 4 1 1 4 2 5 4
2-039 320 5 4 5 1 0 0 0 4 5 5 4 1 3 1 1 4 1 5 3
2-040 320 4 2 4 1 0 0 0 3 2 5 3 1 0 1 3 0 3 2
2-041 320 5 5 5 4 3 3 4 5 5 5 5 2 5 4 5 5 3 5 3
2-042 320 5 3 4 2 1 2 3 4 3 5 5 2 0 0 2 2 5 4
2-043 320 4 3 5 2 1 3 2 3 3 5 4 2 4 0 1 4 0 4 3
2-044 320 4 3 5 2 1 1 1 3 2 5 3 0 0 1 1 5 3
2-045 320 2 1 4 0 0 0 0 3 3 0 0 0 0 2 0 1 0
2-046 320 5 3 5 0 1 1 2 4 3 5 5 1 0 0 4 0 5 4
2-047 320 4 3 4 2 0 1 0 3 4 4 3 0 4 3 1 5 3
2-048 320 5 4 5 2 1 1 2 3 3 5 4 0 1 4 1 5 3
2-049 320 4 1 5 0 1 1 2 5 2 5 3 0 1 2 1 3 0
2-050 320 4 0 5 0 0 0 0 4 4 5 3 1 0 0 1 0 5 3
2-051 320 5 3 5 1 0 1 1 4 3 0 0 0 3 1 3 0
2-052 320 4 3 4 0 0 1 2 3 3 5 1 3 3 0 0 3 0 3 0
2-053 320 2 2 4 0 0 1 0 3 1 5 5 0 0 0 2 0 5 3
2-054 320 4 3 4 1 0 1 0 3 4 5 4 1 2 0 0 2 0 5 1
2-055 320 5 5 5 3 2 2 3 4 5 5 4 4 0 1 4 2 5 3
2-056 320 4 4 5 3 3 3 4 4 4 5 4 3 4 0 0 3 3 5 3
2-057 320 5 4 5 3 1 2 3 4 5 5 5 1 3 0 2 4 1 5 3
2-058 320 5 4 4 2 1 1 1 4 3 5 4 3 3 0 0 3 1 5 3
2-059 320 5 3 4 1 1 1 0 3 2 5 5 0 0 3 0 5 3
3-001 320 5 5 5 5 4 5 5 5 5 5 5 4 5 5 4 5 4 5 5
3-002 320 5 5 5 5 4 4 5 5 5 5 5 3 5 5 5 5 5 5 5
3-003 320 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5 5
3-004 320 4 5 5 4 4 4 4 5 5 5 5 3 5 5 0 5 4 5 5
3-005 320 5 3 4 1 1 1 3 4 5 5 4 2 5 2 0 2 2 5 4
3-006 320 5 2 3 2 1 1 3 5 5 5 5 3 4 3 0 3 2 5 4
3-007 320 5 5 5 5 5 4 5 5 5 5 5 5 5 1 4 4 5 5
3-008 320 5 5 5 4 4 4 5 5 5 5 5 4 5 4 0 5 4 5 5
3-009 320 5 5 5 5 4 4 5 5 5 5 5 5 5 2 5 4 5 5
3-010 320 5 5 5 3 2 2 4 5 5 5 5 4 5 4 0 4 3 5 4
3-011 320 5 5 5 3 3 4 5 5 5 5 5 1 5 4 0 4 3 5 4
3-012 320 5 5 5 1 4 5 4 5 5 5 5 4 5 3 4 4 3 5 2
3-013 320 5 5 5 0 0 0 0 5 5 5 3 0 2 0 0 3 0 5 0
3-014 320 4 3 5 0 0 0 0 5 5 5 4 1 4 1 0 1 0 5 1
3-015 320 5 5 5 3 3 3 4 5 5 5 5 2 4 3 0 4 3 5 3
3-016 320 5 4 5 2 1 2 3 5 5 5 5 5 1 0 3 1 5 4
3-017 320 5 5 5 4 4 4 5 5 5 5 5 4 5 3 3 5 4 5 5
3-018 320 5 5 5 4 4 3 5 5 5 5 5 4 5 5 3 4 3 5 4
3-019 320 4 3 3 4 1 2 2 5 5 5 5 3 5 0 0 5 0 5 2
3-020 320 5 5 5 3 1 1 4 5 5 5 5 4 5 5 0 4 1 5 5
3-021 320 5 5 5 4 4 4 5 5 5 5 5 4 5 5 4 5 4 5 5
3-022 320 3 2 3 1 0 0 0 4 4 3 3 0 3 0 0 2 1 3 0
3-023 320 5 5 5 5 4 4 5 5 5 5 5 4 5 5 3 5 5 5 5
3-024 320 5 5 5 5 5 5 5 5 5 5 5 5 5 5 4 5 5 5 5
3-025 320 5 5 5 4 4 4 4 5 5 5 5 5 5 5 3 5 4 5 5
3-026 320 3 2 3 3 2 2 3 4 4 5 4 3 4 2 0 2 2 5 4
3-027 320 5 5 5 4 4 4 4 5 5 5 5 4 5 3 5 4 5 5
3-028 320 5 4 5 3 2 3 0 5 5 5 5 0 4 5 2 5 2 5 5
3-029 320 5 4 5 3 3 2 3 5 5 5 4 0 4 3 0 1 3 5 4
3-030 320 4 5 5 3 2 1 5 5 5 5 3 4 5 3 5 3 5 5
3-031 320 5 5 5 4 3 3 4 5 5 5 5 5 4 3 5 3 5 5
3-032 320 5 4 5 4 3 3 3 5 5 5 5 4 1 4 3 5 2
3-033 320 3 5 5 0 3 3 3 5 4 5 5 2 3 2 0 3 0 5 5
3-034 320 5 5 5 0 0 0 0 5 5 5 5 3 4 1 1 4 1 5 5
3-035 320 4 3 5 4 3 3 3 5 5 4 3 4 4 5 5
3-036 320 5 5 5 5 5 5 5 5 5 5 5 4 5 5 1 5 5 5 5
3-037 320 5 4 5 3 3 3 3 5 5 5 5 2 5 2 2 5 3 5 5
3-038 320 5 5 5 4 3 3 4 5 5 5 5 1 5 5 3 5 3 5 4
3-039 320 4 3 4 3 1 1 1 3 3 5 4 0 2 4 2 5 4
3-040 320 5 5 5 3 3 3 4 3 4 5 4 2 3 3 3 3 5 2
3-041 320 5 4 5 3 2 1 2 4 4 5 5 3 0 0 3 0 4
3-042 320 5 5 5 4 4 4 4 4 4 5 5 4 5 3 3 4 3 5 4
3-043 320 5 4 5 2 1 1 3 4 5 4 4 2 0 2 1 5 4
3-044 320 3 3 5 1 0 0 0 3 4 2 1 3 0 1 3
3-045 320 5 5 5 4 3 4 4 5 4 5 5 3 0 2 5 4 5 4
3-046 320 5 5 5 3 4 5 5 5 5 5 5 5 5 2 5 4 3 5 5
3-047 320 5 5 5 3 3 3 4 5 5 5 4 0 3 1 0 4 1 5 2
3-048 320 4 5 5 4 2 3 4 5 5 5 5 3 4 4 0 3 2 5 5
3-049 320 4 4 4 3 1 2 3 3 4 5 5 3 4 0 0 4 1 5 3
3-050 320 5 4 5 3 1 2 3 4 4 5 5 0 1 4 1 4 3
3-051 320 5 3 5 1 1 1 2 5 5 5 4 1 2 0 1 1 5 2
3-052 320 5 5 5 4 3 3 4 5 5 5 5 3 4 0 0 4 2 5 5
3-053 320 5 3 4 1 0 1 0 4 4 5 4 2 2 0 4 0 4 3
3-054 320 5 3 5 1 1 1 4 5 5 5 4 3 4 3 0 4 1 5 4
3-055 320 4 4 5 2 1 1 2 5 5 0 0 3 2 1 3 1
3-056 320 4 4 5 2 3 2 4 4 4 5 0 2 0 0 0 3 3 0 3
3-057 320 4 4 5 2 1 1 0 4 3 5 5 2 3 0 3 1 5 5
3-058 320 4 3 5 1 0 1 0 5 5 5 4 0 1 3 0 5 3
3-059 320 5 5 5 5 4 4 5 5 5 5 5 4 5 5 3 4 4 5 5
3-060 320 4 3 4 3 0 1 2 3 5 0 0 4 2 5 4
3-061 320 5 5 5 4 4 4 4 5 5 5 5 5 1 2 3 3 5 5
3-062 320 5 5 5 2 3 3 4 5 5 5 5 2 4 3 3 5 2 5 3
3-063 320 5 4 5 2 2 2 3 5 4 5 5 2 5 3 0 4 2 5 3
3-064 320 5 5 5 1 3 3 4 5 4 5 5 3 2 5 1 5 4
―――――――――――――――――――――――――――――――――――――

  The heterocyclic amide compound of the present invention is a novel compound and is useful as a selective herbicide for rice, corn, soybean, wheat, beet and rapeseed.

Claims (4)

Formula (1):

[Wherein Q represents an aromatic heterocycle represented by any one of Q-1 to Q-7,

W represents an aromatic heterocyclic ring represented by W-1,

X represents an oxygen atom or a sulfur atom,
R ^1a is (C ₁ -C ₆ ) alkyl optionally substituted by R ⁶ , —N (R ³⁶ ) R ³⁷ , —OR ⁴⁰ , —S (O) _m1 R ⁷ , U-1, U-2 , U-3, U-4, U-5, U-6, U-7, U-21 or U-22,
R ^2a represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, —C (O) R ²⁵ , cyano, nitro, —OR ²⁶ or —S (O) _m5 R ²⁷ . , N represents an integer of 2 or more, each R ^2a may be the same as or different from each other,
Further, when two R ^2a are adjacent, the two adjacent R ^2a are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ^2a is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ³ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl or -C (O ) Represents R ²⁹
R ^4a , R ^4b , R ^4c , R ^4d , R ^4e , R ^4f , R ^4g and R ^4h are each independently optionally substituted with a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, or R ³¹ . _(C 1 _{~C 6)} represents _alkyl, C 3 -C ₆ cycloalkyl, phenyl substituted by phenyl or ^(R _{32) q2,}
R ^5a , R ^5b and R ^5c are each independently substituted with a hydrogen atom, C ₁ -C ₆ alkyl, (C ₁ -C ₆ ) alkyl, phenyl or (R ³² ) _q2 optionally substituted with R ³¹ Represented phenyl,
R ^{6 _{is, -OR 11, -S (O)}} m2 R 12, U-3, U-4, U-8, U-9, U-10, U-11, U-12, U-13, U -23, U-24, U-25, U-26, U-27, U-28 or U-29,
R ⁷ is optionally substituted by ^{R 9} _(C 1 ^~C ₆₎ alkyl, ^phenyl, phenyl substituted by _{^{(R 10) q1, U-}} 11, U-12, U-13, U'-11 , U′-12, U′-13, U-14, U-15, U-16, U-23, U-24, U-25, U-30, U-31, U-32, U-33 , U-34, U-35, U-36, U-37 or U-38,
R ⁸ is a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -C (O ) R ¹³ , cyano, —OR ¹⁴ , —N (R ¹⁵ ) R ¹⁶ or —S (O) _m3 R ^17, and when p4, p5, p7 or p9 represents an integer of 2 or more, each R ⁸ May be the same or different from each other,
Furthermore, when two R ⁸ are adjacent, the two adjacent R ⁸ are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ⁸ is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally is substituted by ₁ -C ₆₎ alkyl Even if well,
R ^8a represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ⁹ represents -OR ¹⁸ , U-17, U-18 or U-19,
U-1 to U-38 and U′-11 to U′-13 each represent a heterocyclic ring represented by the following structure,

R ¹⁰ is a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, C ₂ -C ₆ alkynyl, -C (O ) R ¹³ , cyano, —OR ²⁰ , —N (R ²¹ ) R ²² or —S (O) _m4 R ^23, and when q1 represents an integer of 2 or more, each R ¹⁰ is the same as each other Or different from each other,
Further, when two R ¹⁰ are adjacent, the two adjacent R ¹⁰ are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 Each of the two R ¹⁰ is formed by forming O—, —OCH ₂ CH ₂ O—, —CH ₂ CH ₂ CH ₂ S—, —OCH ₂ CH ₂ S— or —CH═CH—CH═CH—. May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ¹¹ and R ¹² each independently represent phenyl substituted by (R ¹⁰ ) _q1 ;
R ¹³ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ²⁴ ,
R ¹⁴ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ¹⁵ and R ¹⁶ each independently represent a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl, or R ¹⁵ together with R ¹⁶ is C ₂ -C ₆ represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to which R ¹⁵ and R ¹⁶ are bonded by forming an alkylene chain, in which case the alkylene chain has an oxygen atom, a sulfur atom or a nitrogen atom. may 1 comprise, and a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 -C _{6) alkyl,} C 1 -C ₆ alkoxy, _formyl, C 1 -C _{6 alkylcarbonyl,} C 1 -C ₆ alkoxy Optionally substituted by carbonyl, oxo or thioxo,
R ¹⁷ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ¹⁸ represents -C (O) R ¹⁹ ;
R ¹⁹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²¹ and R ²² each independently represent a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl, or R ²¹ together with R ²² represents C ₂ -C ₆ represents that a 3- to 7-membered ring may be formed together with the nitrogen atom to which R ²¹ and R ²² are bonded by forming an alkylene chain, and this alkylene chain has an oxygen atom, a sulfur atom or a nitrogen atom. may 1 comprise, and a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 -C _{6) alkyl,} C 1 -C ₆ alkoxy, _formyl, C 1 -C _{6 alkylcarbonyl,} C 1 -C ₆ alkoxy Optionally substituted by carbonyl, oxo or thioxo,
R ²³ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁴ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁵ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ²⁸ ;
R ²⁶ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or phenyl;
R ²⁷ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁸ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ²⁹ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ³⁰ ;
R ³⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³¹ represents a halogen atom, phenyl, —OR ³³ or —S (O) _m6 R ³⁴ ,
R ³² represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl or —OR ^35, and when q 2 represents an integer of 2 or more, each R ³² is the same as each other Or different from each other,
Furthermore, when two R ³² are adjacent, two adjacent R ³² are —CH ₂ CH ₂ CH ₂ —, —CH ₂ CH ₂ O—, —CH ₂ OCH ₂ —, —OCH ₂ O—, _{-CH 2 CH 2 S -, -} CH 2 SCH 2 -, - CH 2 CH 2 CH 2 CH 2 -, - CH 2 CH 2 CH 2 O -, - CH 2 CH 2 OCH 2 -, - CH 2 OCH 2 _{O -, - OCH 2 CH 2} O -, - CH 2 CH 2 CH 2 S -, - OCH by 2 _CH 2 S- or forming a -CH = CH-CH = CH-, each of the two ^{R 32} May form a 5-membered ring or a 6-membered ring together with the carbon atom to which is bonded, and in this case, the hydrogen atom bonded to each carbon atom forming the ring is a halogen atom, C ₁ -C ₆ alkyl or halo (C optionally by ₁ -C ₆₎ alkyl It may have been conversion,
R ³³ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁴ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁵ represents a hydrogen atom, C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ³⁶ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₃ -C ₆ cycloalkyl, C ₂ -C ₆ alkenyl, halo (C ₂ -C ₆ ) alkenyl, C Represents _2- C ₆ alkynyl, halo (C ₂ -C ₆ ) alkynyl, phenyl or phenyl substituted by (R ¹⁰ ) _{q 1} ;
R ³⁷ is (C ₃ -C ₆ ) cycloalkyl, —OH, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, U-16, U-23, optionally substituted by R ³⁸ . Represents U-24 or U-25,
R ³⁸ represents a halogen atom, cyano or —C (O) OR ³⁹ ;
R ³⁹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ⁴⁰ represents C ₁ -C ₆ alkyl optionally substituted with R ⁴¹ or phenyl substituted with (R ¹⁰ ) _q1 ,
R ⁴¹ represents a halogen atom, C ₁ -C ₆ alkoxy or halo (C ₁ -C ₆ ) alkoxy,
G ¹ and G ² each independently represent —S (O) _m —,
m, m1, m2, m3, m4, m5 and m6 each independently represents an integer of 0, 1 or 2;
n independently represents an integer of 0, 1, 2, or 3,
p2 represents an integer of 0, 1 or 2;
p3 represents an integer of 0, 1, 2, or 3,
p4 represents an integer of 0, 1, 2, 3 or 4;
p5 represents an integer of 0, 1, 2, 3, 4 or 5;
p7 represents an integer of 0, 1, 2, 3, 4, 5, 6 or 7,
p9 represents an integer of 0, 1, 2, 3, 4, 5, 6, 7, 8 or 9,
q1 and q2 each independently represent an integer of 1, 2, 3, 4 or 5;
r6 represents an integer of 1, 2, 3, 4, 5 or 6;
r8 represents an integer of 1, 2, 3, 4, 5, 6, 7 or 8;
r10 represents an integer of 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10. Or a salt thereof. Q represents Q-1 or Q-3,
X represents an oxygen atom,
R ^1a is (C ₁ -C ₆ ) alkyl optionally substituted with R ⁶ , —N (R ³⁶ ) R ³⁷ , —OR ⁴⁰ , —S (O) _m1 R ⁷ , U-1, U-3 , U-7, U-21 or U-22,
R ^2a represents halo (C ₁ -C ₆ ) alkyl;
R ³ represents a hydrogen atom,
R ^4a represents a hydrogen atom or C ₁ -C ₆ alkyl;
R ^5a represents C ₁ -C ₆ alkyl;
R ^{6 represents _{-OR 11, -S (O) m2}} R 12, U-3, U-8, U-11, U-12, U-13, U-25, U-26 or U-27 ,
R ⁷ is optionally substituted by ^{R 9} _(C 1 ^~C ₆₎ alkyl, ^phenyl, phenyl substituted by _{^{(R 10) q1, U-}} 11, U-12, U'-12, U-13 , U-15, U-16, U-23, U-24, U-25, U-31, U-32, U-33 or U-38,
R ⁸ represents a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, —C (O) R ¹³ or —OR ¹⁴ ;
R ^8a represents C ₁ -C ₆ alkyl;
R ⁹ represents -OR ¹⁸ or U-17,
R ¹⁰ represents cyano or —OR ²⁰ ,
R ¹³ represents —OR ²⁴ ;
R ¹⁴ , R ¹⁹ , R ²⁰ and R ²⁴ each independently represent C ₁ -C ₆ alkyl;
R ³⁶ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ³⁷ represents (C ₃ -C ₆ ) cycloalkyl, C ₁ -C ₆ alkoxy, U-16 or U-23, optionally substituted by R ³⁸ ,
R ³⁸ represents cyano,
R ⁴¹ represents a halogen atom or C ₁ -C ₆ alkoxy;
m1 represents an integer of 0 or 1,
n represents an integer of 1;
p2 represents an integer of 0 or 1,
p3 represents an integer of 0;
p4 represents an integer of 0 or 1,
p5, p7 and p9 represent an integer of 0;
q1 represents an integer of 1 or 2,
r8 and r10 represent an integer of 1; The heterocyclic amide compound of Claim 1 represented by this, or its salt.   An agrochemical containing one or more selected from the heterocyclic amide compounds according to claim 1 and a salt thereof as active ingredients.   The herbicide which contains 1 type, or 2 or more types chosen from the heterocyclic amide compound and its salt of Claim 1-2 as an active ingredient.