JP2018024660A - Amide compound and pest control agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a novel pest control agent that shows excellent pest control activity; has low toxicity, hardly affecting non-target organisms such as mammals, fish and beneficial insects; and low residual properties.SOLUTION: The present invention provides an amide compound represented by formula (1), or a salt thereof, or an N-oxide thereof; and a pest control agent containing the compound as an active ingredient. [Ris C-Calkyl or the like; Ris H, C-Calkyl or the like; G is a structure represented by G-G; Y2-Y4 independently represent H, halogen, halo (C-C) alkyl or the like; X-Xand Xindependently represent halo (C-C) alkyl or the like; Xis halogen or the like; n is an integer of 0-2].SELECTED DRAWING: None

Description

  The present invention relates to a novel amide compound and a salt thereof, and a pest control agent comprising the compound as an active ingredient.

  For example, Patent Documents 1 to 7 disclose amide compounds, but do not disclose any amide compounds according to the present invention. Furthermore, its usefulness as a pest control agent, in particular, an insecticide / acaricide, and an internal or ectoparasite control agent for mammals or birds is not known at all.

International Publication No. 2013/191041 International Publication No. 2014/002754 International Publication No. 2014/021468 International Publication No. 2015/072463 International Publication No. 2015/117912 International Publication No. 2015/068719 International Publication No. 2016/087265

  The development of pest control agents for the purpose of controlling various pests such as agricultural and horticultural pests, forest pests, and hygiene pests has progressed, and a wide variety of drugs have been put to practical use to date.

  However, due to the long-term use of such drugs, in recent years, pests have acquired drug resistance, making it difficult to control with existing insecticides and fungicides that have been used. In addition, some existing pest control agents are highly toxic, or some of them remain in the environment for a long time, and the problem of disturbing the ecosystem is becoming apparent. Under such circumstances, development of a novel pest control agent having not only high pest control activity but also low toxicity and low persistence is always expected.

  The object of the present invention is to provide a novel pest control which exhibits excellent pest control activity, has low toxicity and has little adverse effect on non-target organisms such as mammals, fish and beneficial insects. It is to provide an agent.

  As a result of intensive research aimed at solving the above-mentioned problems, the present inventors have found that the novel condensed heterocyclic compound represented by the following formula (1) according to the present invention has excellent pest control activity, particularly insecticide / The present invention was completed by discovering that it is an extremely useful compound that exhibits acaricidal activity 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 [14].

[1]
Formula (1):

[Wherein, R ¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ Alkynyl, halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl Represent,
R ² is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
G represents a structure represented by G ^{1 to} G ⁶ ;

Y2 and Y4 are each independently a hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkenyl, halo _(C 1 ~C ₆₎ alkenyl, C ₁ -C ₆ alkynyl, halo _(C 1 ~C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 -C ₆ ) Represents cycloalkenyl, —OR ⁴⁰ , —N (R ⁸⁰ ) R ⁸¹ , —C (O) OR ⁷⁰ , —S (O) _m R ⁵⁰ , cyano or nitro;
Y3 is hydrogen atom, halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkenyl, halo _(C 1 ~C _{6) alkenyl,} C 1 -C ₆ alkynyl, Halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl, halo (C ₃ -C ₆ ) cycloalkenyl, -OR ^{40, -N (R 60) R} 61, -C (O) oR 70, -S (O) m R 50, cyano or nitro,
X ¹ , X ² , X ³ , X ⁴ and X ⁶ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, Halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C Represents ₆ cycloalkenyl, halo (C ₃ -C ₆ ) cycloalkenyl, —OR ⁹⁰ , —N (R ¹⁰ ) R ¹¹ , —C (O) OR ⁷⁰ , —S (O) _p R ³⁰ , cyano or nitro. ,
R ¹⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ¹¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ³⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁴⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁵⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C ₆₎ cycloalkenyl or _C 1 -C ₁₀ alkoxycarbonyl _(C 1 ~C ₆₎ alkyl,
R ⁶⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ⁶¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁷⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁸⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ⁸¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁹⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
n represents an integer of 0, 1 or 2;
m represents an integer of 0, 1 or 2;
p represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides.

[2]
R ¹ represents C ₁ -C ₆ alkyl;
R ² represents a hydrogen atom or C ₁ -C ₆ alkyl,
Y2 and Y4 are each independently a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 80) R 81} , -C (O) OR 70, Represents —S (O) _m R ⁵⁰ , cyano or nitro,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 60) R 61} , -C (O) OR 70, -S (O) m R ⁵⁰ represents cyano or nitro,
X ¹ , X ² , X ³ , X ⁴ and X ⁶ each independently represent a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, —N (R ¹⁰ ) R ¹¹ or nitro,
R ¹⁰ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ¹¹ represents a hydrogen atom,
R ⁵⁰ represents C ₁ -C ₆ alkyl or C ₁ -C ₁₀ alkoxycarbonyl (C ₁ -C ₆ ) alkyl;
R ⁶⁰ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁶¹ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁷⁰ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ⁸⁰ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁸¹ represents a hydrogen atom, a C ₁ -C ₆ alkylcarbonyl, a C ₁ -C ₆ alkoxycarbonyl, or a C ₁ -C ₆ alkylsulfonyl, the condensed heterocyclic compound or a salt thereof according to the above [1], or their N -Oxides.

[3]
Y2 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} a C 3 -C ₆ cycloalkyl or ^{-N (R 80)} R ^81,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 60) R 61} , -C (O) OR 70, -S (O) m R ⁵⁰ represents cyano or nitro,
Y4 represents a hydrogen atom or ^{-N (R 80)} R ^81,
X ¹ represents a hydrogen atom, a halogen atom, —N (R ¹⁰ ) R ¹¹ or nitro,
X ² represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ³ represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ⁴ represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ⁶ represents a halogen atom,
R ⁶⁰ represents a hydrogen atom or a C ₁ -C ₆ alkylcarbonyl,
R ⁶¹ represents a hydrogen atom,
R ⁸⁰ represents a hydrogen atom,
R ⁸¹ represents a hydrogen atom,
m represents the integer of 0 or 1, the fused heterocyclic compound according to the above [2], a salt thereof, or an N-oxide thereof.

[4]
Y2 represents a hydrogen atom, a halogen atom or a halo _(C 1 _{~C 6)} alkyl,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 _{~C 6)} alkyl, -S and _(O) ^{m R 50} or cyano,
Y4 represents a hydrogen atom,
X ¹ represents a hydrogen atom or —N (R ¹⁰ ) R ¹¹ ,
R ¹⁰ represents C ₁ -C ₆ alkyl,
R ⁵⁰ represents the condensed heterocyclic compound or a salt thereof or the N-oxide thereof according to the above [3], wherein C ⁵⁰ represents C ₁ -C ₆ alkyl.

[5]
Y3 represents a hydrogen atom, a halogen atom or a halo _(C 1 _{~C 6)} alkyl,
X ⁴ represents halo (C ₁ -C ₆ ) alkyl;
n is the condensed heterocyclic compound or a salt thereof or the N-oxide thereof according to the above [4], wherein n represents an integer of 0 or 2.

[6]
The pest control agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of said [1]-[5] as an active ingredient.

[7]
An agrochemical containing one or more selected from the condensed heterocyclic compound according to any one of [1] to [5] above and a salt thereof as an active ingredient.

[8]
Control of internal or ectoparasites of mammals or birds containing, as an active ingredient, one or more selected from the fused heterocyclic compounds according to any one of [1] to [5] above and salts thereof Agent.

[9]
The control agent according to [8] above, wherein the ectoparasite is a flea or ticks.

[10]
An insecticide or acaricide containing, as an active ingredient, one or more selected from the condensed heterocyclic compound according to any one of [1] to [5] above and a salt thereof.

[11]
A seed treatment agent containing one or more selected from the condensed heterocyclic compound according to any one of [1] to [5] above and a salt thereof as an active ingredient.

[12]
The seed treatment agent according to [11] above, wherein the seed treatment is performed by dipping treatment.

[13]
The soil treatment agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of said [1]-[5] as an active ingredient.

[14]
The soil treatment agent according to [13], wherein the soil treatment is performed by soil irrigation treatment.

  The compound of the present invention has excellent insecticidal / miticidal activity against many agricultural pests, spider mites, mammals or birds, or against insects that have acquired resistance to existing insecticides. Even against this, it exhibits a sufficient control effect. Furthermore, it has little adverse effect on mammals, fish and beneficial insects, has low persistence, and has a light environmental impact. Therefore, the present invention can provide a useful novel pest control agent.

  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.

  Further, the compounds included in the present invention include optically active substances resulting from the presence of one or more asymmetric carbon atoms or asymmetric sulfur atoms, but the present invention includes all optically active substances or racemic compounds. Includes the body.

  In addition, the compounds included in the present invention may have tautomers depending on the type of substituent, but the present invention includes all tautomers or a mixture of tautomers included in an arbitrary ratio. Is included.

  Among the compounds included in the present invention, those that can be converted into a salt according to a conventional method are, for example, hydrohalic acid salts such as hydrofluoric acid, hydrochloric acid, hydrobromic acid, hydroiodic acid, Salts of inorganic acids such as nitric acid, sulfuric acid, phosphoric acid, chloric acid, perchloric acid, salts of sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, 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 and other carboxylic acid salts, glutamic acid, Salts of amino acids such as aspartic acid, alkali metal salts such as lithium, sodium and potassium, alkalis such as calcium, barium and magnesium Earth metal salts, aluminum salts, tetramethylammonium salts, tetrabutylammonium salts, may be quaternary ammonium salts such as benzyltrimethylammonium salts.

  In the compound of the present invention, N-oxide is a compound in which a nitrogen atom constituting a ring on a heterocyclic ring is oxidized. Examples of the heterocyclic ring that can form an N-oxide include condensed rings including a pyridine ring.

  “The compound of the present invention represented by formula (1)” is also described as “the compound of the present invention (1)”, and “the compound represented by formula (1-A)” is “compound (1-A ) ". The other compounds are similarly described.

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

  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.

In the present specification, the expression “C _a -C _b alkyl” represents a linear or branched hydrocarbon group having a carbon number of _a to _b , such as a methyl group, an ethyl group, or n-propyl. Specific examples include a group, 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. Selected within a range of each specified number of carbon atoms.

In the present specification, the expression “halo (C _a -C _b ) alkyl” refers to a straight chain composed of _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom, or This represents a branched hydrocarbon group, and when substituted with 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, 1-fluoroethyl 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, 2-bromo-2,2-difluoroethyl group, 1,1,2,2-tetrafluoroethyl group, 2-chloro-1,1,2-trifluoroethyl group, 2-chloro-1 , 1,2,2-tetrafluoroethyl group, pentafluoroethyl group, 2,2-difluoropropyl group, 3,3,3- Lifluoropropyl group, 3-bromo-3,3-difluoropropyl group, 2,2,3,3-tetrafluoropropyl group, 2,2,3,3,3-pentafluoropropyl group, 1,1,2 , 3,3,3-hexafluoropropyl group, heptafluoropropyl group, 2,2,2-trifluoro-1- (methyl) ethyl group, 2,2,2-trifluoro-1- (trifluoromethyl) Ethyl group, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethyl group, 2,2,3,4,4,4-hexafluorobutyl 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 designated number of carbon atoms.

The expression “C _a -C _b alkenyl” is a linear or branched chain having a carbon number of _a to _b and an unsaturated carbonization having one or more double bonds in the molecule. Represents hydrogen, 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- A dimethyl-2-propenyl group etc. are mentioned as a specific example, and it selects in the range of each designated number of carbon atoms.

The expression “halo (C _a -C _b ) alkenyl” is a linear or branched chain having a carbon number of _a to _b in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon having 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.

The expression “C _a -C _b alkynyl” refers to an unsaturated hydrocarbon having a linear or branched chain of _a to _b carbon atoms and having one or more triple bonds in the molecule. Specific examples include ethynyl group, propargyl group, 2-butynyl group, 3-butynyl group, 1-pentynyl group, 1-hexynyl group, 4,4,4-trifluoro-2-butynyl group and the like. , Each selected range of carbon atoms.

The expression “halo (C _a -C _b ) alkynyl” is a linear or branched chain comprising _a to _b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom And an unsaturated hydrocarbon having 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 expression “C _a -C _b alkoxy” 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, i- Specific examples include propyloxy group, n-butyloxy group, i-butyloxy group, s-butyloxy group, tert-butyloxy group, 2-ethylhexyloxy group, etc., and each is selected within the range of the designated number of carbon atoms. The

The expression “halo (C _a -C _b ) alkoxy” represents a haloalkyl-O— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethoxy group, trifluoromethoxy group, chlorodifluoro Methoxy group, bromodifluoromethoxy group, 2-fluoroethoxy group, 2-chloroethoxy group, 2,2,2-trifluoroethoxy group, 1,1,2,2, -tetrafluoroethoxy group, 2-chloro-1 Specific examples include 1,2,2-trifluoroethoxy group, 1,1,2,3,3,3-hexafluoropropyloxy group and the like, and each is selected within the range of the designated number of carbon atoms.

The notation “C _a -C _b alkylsulfonyl” represents an alkyl-SO ₂ -group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylsulfonyl group, ethylsulfonyl group, n-propylsulfonyl. Group, i-propylsulfonyl group, n-butylsulfonyl group, i-butylsulfonyl group, s-butylsulfonyl group, tert-butylsulfonyl group and the like are mentioned as specific examples, and each selected within the range of the designated number of carbon atoms. Is done.

The expression “C _a -C _b alkylcarbonyl” represents an alkyl-C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, an acetyl group, a propionyl group, a butyryl group, Specific examples include isobutyryl group, valeryl group, isovaleryl group, 2-methylbutanoyl group, pivaloyl group, hexanoyl group, heptanoyl group and the like, and each is selected in the range of the designated number of carbon atoms.

The expression “halo (C _a -C _b ) alkylcarbonyl” represents a haloalkyl-C (O) — group as defined above consisting of _a to _b carbon atoms, for example, a fluoroacetyl group, a chloroacetyl group, Group, difluoroacetyl group, dichloroacetyl group, trifluoroacetyl group, chlorodifluoroacetyl group, bromodifluoroacetyl group, trichloroacetyl group, pentafluoropropionyl group, heptafluorobutanoyl group, 3-chloro-2,2, -dimethyl Specific examples include a propanoyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The expression “C _a -C _b alkoxycarbonyl” represents an alkyl-OC (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as a methoxycarbonyl group, an ethoxycarbonyl group, n- Specific examples include propyloxycarbonyl group, i-propyloxycarbonyl group, n-butoxycarbonyl group, i-butoxycarbonyl group, s-butoxycarbonyl group, tert-butoxycarbonyl group, 2-ethylhexyloxycarbonyl group and the like. Selected within a range of each specified number of carbon atoms.

The notation “C _a -C _b alkoxycarbonyl (C _d -C _e ) alkyl” is attached to a carbon atom by C _a -C _b alkoxycarbonyl which is the above-mentioned meaning consisting of _a to _b carbon atoms. It represents an alkyl group having the above-mentioned meaning consisting of de to e carbon atoms, optionally substituted with hydrogen atoms, such as 2-methoxycarbonylethyl group, 2-ethoxycarbonylethyl group, 2- (2- Specific examples include an octyloxycarbonyl) ethyl group and the like, and each is selected within the range of the designated number of carbon atoms.

The expression “halo (C _a -C _b ) alkoxycarbonyl” represents a haloalkyl-OC (O) — group as defined above consisting of _a to _b carbon atoms, such as a chloromethoxycarbonyl group, 2 Specific examples include -chloroethoxycarbonyl group, 2,2-difluoroethoxycarbonyl group, 2,2,2-trifluoroethoxycarbonyl group, 2,2,2-trichloroethoxycarbonyl group and the like. It is selected in the range of the number of atoms.

The expression “C _a -C _b cycloalkyl” represents a cyclic hydrocarbon composed of _a to _b carbon atoms, and may form 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 cyclopropyl group, 1-methylcyclopropyl group, 2-methylcyclopropyl group, 2,2-dimethylcyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, etc. Selected in a range of numbers.

The expression “halo (C _a -C _b ) cycloalkyl” represents a cyclic hydrocarbon composed of _a to _b carbon atoms in which a hydrogen atom bonded to a carbon atom is optionally substituted with a halogen atom. A monocyclic or complex ring structure from 3 to 6-membered ring can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the substitution with a halogen atom may be a ring structure part, a side chain part, They may be both, and when they are substituted by two or more halogen atoms, the halogen atoms may be the same as or different from each other. For example, 2,2-difluorocyclopropyl group, 2,2-dichlorocyclopropyl group, 2,2-dibromocyclopropyl group, 2,2-difluoro-1-methylcyclopropyl group, 2,2-dichloro-1-methyl Specific examples include cyclopropyl group, 2,2-dibromo-1-methylcyclopropyl group, 2,2,3,3-tetrafluorocyclobutyl group, and the like, and each is selected within the range of the designated number of carbon atoms. The

The expression “C _a -C _b cycloalkenyl” represents a cyclic unsaturated hydrocarbon having 1 to 2 carbon atoms and having 1 or 2 or more double bonds. Monocyclic or complex ring structures up to 6-membered rings can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. Specific examples include 1-cyclopenten-1-yl group, 2-cyclopenten-1-yl group, 1-cyclohexen-1-yl group, 2-cyclohexen-1-yl group, and the like. Selected in a range of numbers.

The notation “halo (C _a -C _b ) cycloalkenyl” is cyclic, consisting of _a to _b carbon atoms, in which a hydrogen atom bonded to a carbon atom is optionally substituted by a halogen atom, It represents an unsaturated hydrocarbon group having two or more double bonds, and can form a monocyclic or complex ring structure having 3 to 6 members. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms, and the double bond may be either endo- or exo-. In addition, the substitution by a halogen atom may be a ring structure part, a side chain part or both of them, and when substituted by two or more halogen atoms, those halogen atoms May be the same as or different from each other. For example, 2-fluoro-1-cyclopentenyl group, 2-chloro-1-cyclopentenyl group, 3-chloro-2-cyclopentenyl group, 2-fluoro-1-cyclohexenyl group and the like are listed as specific examples. Selected within the specified number of carbon atoms.

  Specific examples of the compound of the present invention represented by the formula (1) are shown in Tables 1 and 2. In the table, "Me" is a methyl group, "Et" is an ethyl group, "n-Pr" is a normal propyl group, "c-Pr" is a cyclopropyl group, and "Ac" The notation represents an acetyl group.

  [Table 1]

―――――――――――――――――――――――――――
n Y2 Y3 Y4 R ² X ¹ X ² X ³
―――――――――――――――――――――――――――
0 CF ₃ HH Me HH CF ₃
2 CF ₃ HH Me HH CF ₃
2 H CF ₃ HHH CF ₃ H
2 H CF ₃ H n-Pr H CF ₃ H
0 CF ₃ HH Me NH ₂ H CF ₃
1 CF ₃ HH Me NH ₂ H CF ₃
2 CF ₃ HH Me NH ₂ H CF ₃
0 IHH Me NH ₂ H CF ₃
1 IHH Me NH ₂ H CF ₃
2 IHH Me NH ₂ H CF ₃
0 Br HH Me NH ₂ H CF ₃
1 Br HH Me NH ₂ H CF ₃
2 Br HH Me NH ₂ H CF ₃
0 Cl HH Me NH ₂ H CF ₃
1 Cl HH Me NH ₂ H CF ₃
2 Cl HH Me NH ₂ H CF ₃
0 c-Pr HH Me NH ₂ H CF ₃
1 c-Pr HH Me NH ₂ H CF ₃
2 c-Pr HH Me NH ₂ H CF ₃
0 NH ₂ HH Me NH ₂ H CF ₃
1 NH ₂ HH Me NH ₂ H CF ₃
2 NH ₂ HH Me NH ₂ H CF ₃
0 H CF ₃ H Me NH ₂ H CF ₃
1 H CF ₃ H Me NH ₂ H CF ₃
2 H CF ₃ H Me NH ₂ H CF ₃
0 HIH Me NH ₂ H CF ₃
1 HIH Me NH ₂ H CF ₃
2 HIH Me NH ₂ H CF ₃
0 H Br H Me NH ₂ H CF ₃
1 H Br H Me NH ₂ H CF ₃
2 H Br H Me NH ₂ H CF ₃
0 H Cl H Me NH ₂ H CF ₃
1 H Cl H Me NH ₂ H CF ₃
2 H Cl H Me NH ₂ H CF ₃
0 H c-Pr H Me NH ₂ H CF ₃
1 H c-Pr H Me NH ₂ H CF ₃
2 H c-Pr H Me NH ₂ H CF ₃
0 H NH ₂ H Me NH ₂ H CF ₃
1 H NH ₂ H Me NH ₂ H CF ₃
2 H NH ₂ H Me NH ₂ H CF ₃
0 H NHAc H Me NH ₂ H CF ₃
1 H NHAc H Me NH ₂ H CF ₃
2 H NHAc H Me NH ₂ H CF ₃
0 H NO ₂ H Me NH ₂ H CF ₃
1 H NO ₂ H Me NH ₂ H CF ₃
2 H NO ₂ H Me NH ₂ H CF ₃
0 HC (O) OH H Me NH ₂ H CF ₃
1 HC (O) OH H Me NH ₂ H CF ₃
2 HC (O) OH H Me NH ₂ H CF ₃
0 HC (O) OEt H Me NH ₂ H CF ₃
1 HC (O) OEt H Me NH ₂ H CF ₃
2 HC (O) OEt H Me NH ₂ H CF ₃
0 H CN H Me NH ₂ H CF ₃
1 H CN H Me NH ₂ H CF ₃
2 H CN H Me NH ₂ H CF ₃
0 HH NH ₂ Me NH ₂ H CF ₃
1 HH NH ₂ Me NH ₂ H CF ₃
2 HH NH ₂ Me NH ₂ H CF ₃
0 HHH Me NH ₂ H CF ₃
1 HHH Me NH ₂ H CF ₃
2 HHH Me NH ₂ H CF ₃
0 CF ₃ HH Me NO ₂ H CF ₃
1 CF ₃ HH Me NO ₂ H CF ₃
2 CF ₃ HH Me NO ₂ H CF ₃
0 IHH Me NO ₂ H CF ₃
1 IHH Me NO ₂ H CF ₃
2 IHH Me NO ₂ H CF ₃
0 Br HH Me NO ₂ H CF ₃
1 Br HH Me NO ₂ H CF ₃
2 Br HH Me NO ₂ H CF ₃
0 Cl HH Me NO ₂ H CF ₃
1 Cl HH Me NO ₂ H CF ₃
2 Cl HH Me NO ₂ H CF ₃
0 c-Pr HH Me NO ₂ H CF ₃
1 c-Pr HH Me NO ₂ H CF ₃
2 c-Pr HH Me NO ₂ H CF ₃
0 NH ₂ HH Me NO ₂ H CF ₃
1 NH ₂ HH Me NO ₂ H CF ₃
2 NH ₂ HH Me NO ₂ H CF ₃
0 H CF ₃ H Me NO ₂ H CF ₃
1 H CF ₃ H Me NO ₂ H CF ₃
2 H CF ₃ H Me NO ₂ H CF ₃
0 HIH Me NO ₂ H CF ₃
1 HIH Me NO ₂ H CF ₃
2 HIH Me NO ₂ H CF ₃
0 H Br H Me NO ₂ H CF ₃
1 H Br H Me NO ₂ H CF ₃
2 H Br H Me NO ₂ H CF ₃
0 H Cl H Me NO ₂ H CF ₃
1 H Cl H Me NO ₂ H CF ₃
2 H Cl H Me NO ₂ H CF ₃
0 H c-Pr H Me NO ₂ H CF ₃
1 H c-Pr H Me NO ₂ H CF ₃
2 H c-Pr H Me NO ₂ H CF ₃
0 H NH ₂ H Me NO ₂ H CF ₃
1 H NH ₂ H Me NO ₂ H CF ₃
2 H NH ₂ H Me NO ₂ H CF ₃
0 H NHAc H Me NO ₂ H CF ₃
1 H NHAc H Me NO ₂ H CF ₃
2 H NHAc H Me NO ₂ H CF ₃
0 H NO ₂ H Me NO ₂ H CF ₃
1 H NO ₂ H Me NO ₂ H CF ₃
2 H NO ₂ H Me NO ₂ H CF ₃
0 HC (O) OH H Me NO ₂ H CF ₃
1 HC (O) OH H Me NO ₂ H CF ₃
2 HC (O) OH H Me NO ₂ H CF ₃
0 HC (O) OEt H Me NO ₂ H CF ₃
1 HC (O) OEt H Me NO ₂ H CF ₃
2 HC (O) OEt H Me NO ₂ H CF ₃
0 H CN H Me NO ₂ H CF ₃
1 H CN H Me NO ₂ H CF ₃
2 H CN H Me NO ₂ H CF ₃
0 HH NH ₂ Me NO ₂ H CF ₃
1 HH NH ₂ Me NO ₂ H CF ₃
2 HH NH ₂ Me NO ₂ H CF ₃
0 HHH Me NO ₂ H CF ₃
1 HHH Me NO ₂ H CF ₃
2 HHH Me NO ₂ H CF ₃
0 CF ₃ HH Me Cl H CF ₃
1 CF ₃ HH Me Cl H CF ₃
2 CF ₃ HH Me Cl H CF ₃
0 IHH Me Cl H CF ₃
1 IHH Me Cl H CF ₃
2 IHH Me Cl H CF ₃
0 Br HH Me Cl H CF ₃
1 Br HH Me Cl H CF ₃
2 Br HH Me Cl H CF ₃
0 Cl HH Me Cl H CF ₃
1 Cl HH Me Cl H CF ₃
2 Cl HH Me Cl H CF ₃
0 c-Pr HH Me Cl H CF ₃
1 c-Pr HH Me Cl H CF ₃
2 c-Pr HH Me Cl H CF ₃
0 NH ₂ HH Me Cl H CF ₃
1 NH ₂ HH Me Cl H CF ₃
2 NH ₂ HH Me Cl H CF ₃
0 H CF ₃ H Me Cl H CF ₃
1 H CF ₃ H Me Cl H CF ₃
2 H CF ₃ H Me Cl H CF ₃
0 HIH Me Cl H CF ₃
1 HIH Me Cl H CF ₃
2 HIH Me Cl H CF ₃
0 H Br H Me Cl H CF ₃
1 H Br H Me Cl H CF ₃
2 H Br H Me Cl H CF ₃
0 H Cl H Me Cl H CF ₃
1 H Cl H Me Cl H CF ₃
2 H Cl H Me Cl H CF ₃
0 H c-Pr H Me Cl H CF ₃
1 H c-Pr H Me Cl H CF ₃
2 H c-Pr H Me Cl H CF ₃
0 H NH ₂ H Me Cl H CF ₃
1 H NH ₂ H Me Cl H CF ₃
2 H NH ₂ H Me Cl H CF ₃
0 H NHAc H Me Cl H CF ₃
1 H NHAc H Me Cl H CF ₃
2 H NHAc H Me Cl H CF ₃
0 H NO ₂ H Me Cl H CF ₃
1 H NO ₂ H Me Cl H CF ₃
2 H NO ₂ H Me Cl H CF ₃
0 HC (O) OH H Me Cl H CF ₃
1 HC (O) OH H Me Cl H CF ₃
2 HC (O) OH H Me Cl H CF ₃
0 HC (O) OEt H Me Cl H CF ₃
1 HC (O) OEt H Me Cl H CF ₃
2 HC (O) OEt H Me Cl H CF ₃
0 H CN H Me Cl H CF ₃
1 H CN H Me Cl H CF ₃
2 H CN H Me Cl H CF ₃
0 HH NH ₂ Me Cl H CF ₃
1 HH NH ₂ Me Cl H CF ₃
2 HH NH ₂ Me Cl H CF ₃
0 HHH Me Cl H CF ₃
1 HHH Me Cl H CF ₃
2 HHH Me Cl H CF ₃
―――――――――――――――――――――――――――
[Table 2]

―――――――――――――――――― ――――――――――――――――――
n Y2 Y3 Y4 X ¹ X ⁴ n Y2 Y3 Y4 X ¹ X ⁴
―――――――――――――――――― ――――――――――――――――――
0 CF ₃ HH Cl CF ₃ 0 CF ₃ HH NHMe CF ₃
1 CF ₃ HH Cl CF ₃ 1 CF ₃ HH NHMe CF ₃
2 CF ₃ HH Cl CF ₃ 2 CF ₃ HH NHMe CF ₃
0 IHH Cl CF ₃ 0 IHH NHMe CF ₃
1 IHH Cl CF ₃ 1 IHH NHMe CF ₃
2 IHH Cl CF ₃ 2 IHH NHMe CF ₃
0 Br HH Cl CF ₃ 0 Br HH NHMe CF ₃
1 Br HH Cl CF ₃ 1 Br HH NHMe CF ₃
2 Br HH Cl CF ₃ 2 Br HH NHMe CF ₃
0 Cl HH Cl CF ₃ 0 Cl HH NHMe CF ₃
1 Cl HH Cl CF ₃ 1 Cl HH NHMe CF ₃
2 Cl HH Cl CF ₃ 2 Cl HH NHMe CF ₃
0 c-Pr HH Cl CF ₃ 0 c-Pr HH NHMe CF ₃
1 c-Pr HH Cl CF ₃ 1 c-Pr HH NHMe CF ₃
2 c-Pr HH Cl CF ₃ 2 c-Pr HH NHMe CF ₃
0 NH ₂ HH Cl CF ₃ 0 NH ₂ HH NHMe CF ₃
1 NH ₂ HH Cl CF ₃ 1 NH ₂ HH NHMe CF ₃
2 NH ₂ HH Cl CF ₃ 2 NH ₂ HH NHMe CF ₃
0 H CF ₃ H Cl CF ₃ 0 H CF ₃ H NHMe CF ₃
1 H CF ₃ H Cl CF ₃ 1 H CF ₃ H NHMe CF ₃
2 H CF ₃ H Cl CF ₃ 2 H CF ₃ H NHMe CF ₃
0 HIH Cl CF ₃ 0 HIH NHMe CF ₃
1 HIH Cl CF ₃ 1 HIH NHMe CF ₃
2 HIH Cl CF ₃ 2 HIH NHMe CF ₃
0 H Br H Cl CF ₃ 0 H Br H NHMe CF ₃
1 H Br H Cl CF ₃ 1 H Br H NHMe CF ₃
2 H Br H Cl CF ₃ 2 H Br H NHMe CF ₃
0 H Cl H Cl CF ₃ 0 H Cl H NHMe CF ₃
1 H Cl H Cl CF ₃ 1 H Cl H NHMe CF ₃
2 H Cl H Cl CF ₃ 2 H Cl H NHMe CF ₃
0 H c-Pr H Cl CF ₃ 0 H c-Pr H NHMe CF ₃
1 H c-Pr H Cl CF ₃ 1 H c-Pr H NHMe CF ₃
2 H c-Pr H Cl CF ₃ 2 H c-Pr H NHMe CF ₃
0 H NH ₂ H Cl CF ₃ 0 H NH ₂ H NHMe CF ₃
1 H NH ₂ H Cl CF ₃ 1 H NH ₂ H NHMe CF ₃
2 H NH ₂ H Cl CF ₃ 2 H NH ₂ H NHMe CF ₃
0 H NHAc H Cl CF ₃ 0 H NHAc H NHMe CF ₃
1 H NHAc H Cl CF ₃ 1 H NHAc H NHMe CF ₃
2 H NHAc H Cl CF ₃ 2 H NHAc H NHMe CF ₃
0 H NO ₂ H Cl CF ₃ 0 H NO ₂ H NHMe CF ₃
1 H NO ₂ H Cl CF ₃ 1 H NO ₂ H NHMe CF ₃
2 H NO ₂ H Cl CF ₃ 2 H NO ₂ H NHMe CF ₃
0 HC (O) OH H Cl CF ₃ 0 HC (O) OH H NHMe CF ₃
1 HC (O) OH H Cl CF ₃ 1 HC (O) OH H NHMe CF ₃
2 HC (O) OH H Cl CF ₃ 2 HC (O) OH H NHMe CF ₃
0 HC (O) OEt H Cl CF ₃ 0 HC (O) OEt H NHMe CF ₃
1 HC (O) OEt H Cl CF ₃ 1 HC (O) OEt H NHMe CF ₃
2 HC (O) OEt H Cl CF ₃ 2 HC (O) OEt H NHMe CF ₃
0 H CN H Cl CF ₃ 0 H CN H NHMe CF ₃
1 H CN H Cl CF ₃ 1 H CN H NHMe CF ₃
2 H CN H Cl CF ₃ 2 H CN H NHMe CF ₃
0 HH NH ₂ Cl CF ₃ 0 HH NH ₂ NHMe CF ₃
1 HH NH ₂ Cl CF ₃ 1 HH NH ₂ NHMe CF ₃
2 HH NH ₂ Cl CF ₃ 2 HH NH ₂ NHMe CF ₃
0 HHH Cl CF ₃ 0 HHH NHMe CF ₃
1 HHH Cl CF ₃ 1 HHH NHMe CF ₃
2 HHH Cl CF ₃ 2 HHH NHMe CF ₃
―――――――――――――――――― ――――――――――――――――――
Next, the manufacturing method of this invention compound represented by the said Formula (1) is demonstrated below. The compound of the present invention can be produced, for example, by the following production methods 1 to 4.

[Production Method 1]
Among the compounds of the present invention represented by the formula (1), a compound represented by the formula (1-A) wherein n is an integer of 1 or 2 [hereinafter abbreviated as compound (1-A). ] Is, for example, a compound represented by the formula (1-B) in which n is an integer of 0 among the compounds of the present invention [hereinafter abbreviated as compound (1-B). And an oxidizing agent.

(In the formula, G, R ¹ , R ² , Y ² , Y 3 and Y 4 represent the same meaning as described above, and m represents an integer of 1 or 2.)
Compound (1-A) can be produced by reacting compound (1-B) with an oxidizing agent in a solvent or without a solvent, optionally in the presence of a catalyst.

  When using a solvent, the solvent used may be inert to the reaction, such as water, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Ethers, aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N′-dimethylimidazolidinone, and sulfoxides such as dimethyl sulfoxide , Lower fats such as acetic acid Acids or mixed solvents thereof.

  Examples of the oxidizing agent include peracids such as metachloroperbenzoic acid and peracetic acid, hydrogen peroxide, and oxone (OXONE, registered trademark of EI Dupont; containing potassium peroxosulfate). The equivalent of the oxidizing agent can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of compound (1-B), and preferably in the range of 1 to 20 equivalents.

  The reaction can be carried out in the presence of a catalyst. Examples of the catalyst that can be used include sodium tungstate. As an equivalent of a catalyst, it can use in 0.005 to 20 equivalent with respect to 1 equivalent of compound (1-B), and the range of 0.1 to 5 equivalent is preferable.

  The reaction temperature can be set at any temperature from −80 ° C. to the reflux temperature of the reaction mixture, and the range of 0 ° C. to the reflux temperature of the reaction mixture is preferred.

  The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours, and preferably in the range of 1 hour to 48 hours.

[Production Method 2]
Among the compounds of the present invention represented by the formula (1), a compound represented by the formula (1-D) [hereinafter abbreviated as compound (1-D). ] Is a compound represented by the formula (1-C) among the compounds of the present invention [hereinafter abbreviated as compound (1-C). ] And a compound represented by formula (50) [hereinafter abbreviated as compound (50). ] Can be made to react.

[Wherein, G, R ¹ , Y 2, Y 3, Y 4 and n represent the same meaning as described above, n represents an integer of 0, 1 or 2, R ² represents C ₁ -C ₆ alkyl, and X ¹ Is a halogen atom, C ₁ -C ₄ alkyl sulfonate (eg methanesulfonyloxy etc.), C ₁ -C ₄ haloalkyl sulfonate (eg trifluoromethanesulfonyloxy etc.) or aryl sulfonate (eg benzenesulfonyloxy, p-toluenesulfonyl etc.) Represents a leaving group such as oxy. ]
Compound (1-D) can be produced by reacting compound (1-C) and compound (50) in a solvent or without a solvent, and optionally in the presence of a base.

  As an equivalent of the compound (50) to be used, it can be used in the range of 0.5-50 equivalent with respect to 1 equivalent of compound (1-C), and the range of 1-20 equivalent is preferable.

  Some of the compounds (50) are known compounds, and some of them are commercially available.

  When using a solvent, the solvent used may be inert to the reaction, such as water, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Ethers, aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N′-dimethylimidazolidinone, and sulfoxides such as dimethyl sulfoxide , Pyridine, quino Nitrogen-containing aromatic compounds or a mixture of these solvents, such as emissions and the like.

  The reaction can be performed in the presence of a base. Examples of the base that can be used include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2. ] Organic bases such as octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) And inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of the compound (1-C), and preferably in the range of 1 to 20 equivalents.

  The reaction temperature can be set at any temperature from −80 ° C. to the reflux temperature of the reaction mixture, and the range of 0 ° C. to the reflux temperature of the reaction mixture is preferred.

  The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours, and preferably in the range of 1 hour to 48 hours.

[Production Method 3]
The compound of the present invention represented by the formula (1) is, for example, a compound represented by the formula (2) [hereinafter abbreviated as compound (2). ] And a compound represented by formula (51) [hereinafter abbreviated as compound (51). ] Can be made to react.

(Wherein R ¹ , R ² , Y ² , Y 3, Y 4, G and n represent the same meaning as described above.)
Compound (1) can be produced by reacting compound (2) and compound (51) in a solvent or without a solvent, optionally in the presence of a base.

  The equivalent of the compound (51) to be used can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of the compound (2), and preferably in the range of 1 to 20 equivalents.

  Some of the compounds (51) are known compounds, and some of them are commercially available.

  When using a solvent, the solvent used may be inert to the reaction, such as water, lower alcohols such as methanol and ethanol, diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2-dimethoxyethane and the like. Ethers, aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene, and toluene, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, and halogenated hydrocarbons such as dichloromethane, chloroform, and 1,2-dichloroethane Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N′-dimethylimidazolidinone, and sulfoxides such as dimethyl sulfoxide , Pyridine, quino Nitrogen-containing aromatic compounds or a mixture of these solvents, such as emissions and the like.

  The reaction can be performed in the presence of a base. Examples of the base that can be used include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2. ] Organic bases such as octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN) And inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to the compound (2), and preferably in the range of 1 to 20 equivalents.

  The reaction temperature can be set at any temperature from −80 ° C. to the reflux temperature of the reaction mixture, and the range of 0 ° C. to the reflux temperature of the reaction mixture is preferred.

  The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours, and preferably in the range of 1 hour to 48 hours.

[Production Method 4]
The compound of the present invention represented by the formula (1) can be produced, for example, by reacting the compound (3) with the compound (51).

(Wherein R ¹ , R ² , Y ² , Y 3, Y 4, G and n represent the same meaning as described above.)
Compound (1) can be produced by reacting compound (3) and compound (51) in a solvent or without a solvent, optionally in the presence of a base and a condensing agent.

  As an equivalent of the compound (51) to be used, it can be used by 0.5-50 equivalent with respect to 1 equivalent of compound (3), and 1-20 equivalent is preferable. Some of the compounds (51) are known compounds, and some of them are commercially available.

  When a solvent is used, the solvent used may be inert to the reaction. For example, lower alcohols such as methanol and ethanol, ethers such as diethyl ether, tetrahydrofuran, 1,4-dioxane, and 1,2-dimethoxyethane , Aromatic hydrocarbons such as benzene, chlorobenzene, bromobenzene, xylene and toluene, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, acetonitrile , Nitriles such as propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone, N, N′-dimethylimidazolidinone, sulfoxides such as dimethyl sulfoxide or the like Mixed solvent And the like.

  When a base and a condensing agent are used, examples of bases that can be used include pyridine, 2,6-lutidine, 4-dimethylaminopyridine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4 -Diazabicyclo [2.2.2] octane (DABCO), 1,8-diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene Organic bases such as (DBN), and inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like. As an equivalent of a base, it can be used in 0.1-100 equivalent with respect to 1 equivalent of compound (3), and 1-20 equivalent is preferable.

  Examples of the condensing agent that can be used include 1-ethyl- (3-dimethylaminopropyl) carbodiimide, 4- (4,6-dimethoxy-1,3,5-triangin-2-yl) -4-methylmorpholine. Examples thereof include nium chloride, acetic anhydride, pivalic anhydride, and 2-methyl-6-nitrobenzoic anhydride. As an equivalent of a condensing agent, it can be used by 0.1-100 equivalent with respect to 1 equivalent of compound (3), and 1-20 equivalent is preferable.

  The reaction temperature can be set at any temperature from −80 ° C. to the reflux temperature of the reaction mixture, and the range of 0 ° C. to the reflux temperature of the reaction mixture is preferred.

  The reaction time varies depending on the concentration of the reaction substrate and the reaction temperature, but can usually be arbitrarily set in the range of 5 minutes to 100 hours, and preferably 1 to 48 hours.

  Of the compounds (2) used in production method 3, a compound represented by formula (2-A) wherein n is an integer of 1 or 2 [hereinafter abbreviated as compound (2-A). And compound (3-A) in which n is an integer of 1 or 2 and compound (3-B) in which n is an integer of 0 among compounds (3) used in production method 4 are the following reactions: It can manufacture according to the manufacturing route shown by a formula.

  [Reaction Formula 1]

(Wherein R ¹ , Y 2, Y 3, Y 4 and m represent the same meaning as described above, L ¹ represents a halogen atom such as a chlorine atom, a bromine atom or an iodine atom, and R ^a represents C _{1 to} C ₆ alkyl. Represents.)
[Manufacturing process 1]
Compound represented by formula (6-1) [hereinafter abbreviated as compound (6-1) ] In accordance with a known method known in the literature, for example, the method described in International Publication No. 2013/018899, etc., to give a compound represented by the formula (5-1) [hereinafter, Abbreviated as compound (5-1). Can be manufactured. Some of the compounds (6-1) are known compounds, and some of them are commercially available.

[Manufacturing process 2]
Compound (5-1) is represented by formula (52) according to a known method known in the literature, for example, the method described in Organic Letters 2007, Vol. 9, page 3687, etc. [ Hereafter, it abbreviates as a compound (52). ] Is reacted with a compound represented by formula (4-1) [hereinafter abbreviated as compound (4-1). Can be manufactured. Some of the compounds (52) are known compounds, and some of them are commercially available.

[Manufacturing process 1-2]
Compound (4-1) can be obtained by a known method, for example, a method according to Organic Letters 2014, Vol. 16, page 2978, etc. Can be produced in one step from compound (6-1) by reacting in the presence of a halogenating agent.

[Manufacturing process 3]
According to a known method known in the literature for compound (4-1), for example, the method described in Bioorganic & Medicinal Chemistry Letters 2012, Vol. 22, p. 1870, etc. By performing a hydrolysis reaction, the compound represented by the formula (3-B) [hereinafter abbreviated as compound (3-B). Can be manufactured.

[Manufacturing process 4]
The compound (3-B) is reacted with an oxidant according to the method described in Production Method 1 to give a compound represented by the formula (3-A) [hereinafter abbreviated as compound (3-A). Can be manufactured.

[Manufacturing process 5]
Compound (2-A) is produced by reacting compound (3-A) with a halogenating agent according to a known method known in the literature, for example, the method described in International Publication No. 2011/041713. be able to.

  Among the compounds (2) used in production method 3, a compound represented by formula (2-B) wherein n is an integer of 0 [hereinafter abbreviated as compound (2-B). ] Can be produced according to the production method shown in Reaction Scheme 2 below.

  [Reaction Formula 2]

(In the formula, R ¹ , Y 2, Y 3 and Y 4 represent the same meaning as described above.)
The compound (2-B) can be produced by reacting the compound (3-B) with a chlorinating agent according to the method described in Production Process 5 of Reaction Scheme 1.

  Compound (6-1) used in Reaction Scheme 1 can be produced by reacting compound (7-1) with compound (53).

  [Reaction Formula 3]

(In the formula, R ¹ , Y 2, Y 3, Y 4, X ¹ and R ^a represent the same meaning as described above.)
The compound (7-1) is reacted with the compound (53) according to a known method, for example, the method described in International Publication No. 2013/087772, International Publication No. 2012/096929, etc., to give the compound (6- 1) can be manufactured.

  Compound (3-B) used in Reaction Scheme 1 can be produced according to the production route represented by the following reaction formula.

  [Reaction Formula 4]

(In the formula, R ¹ , Y 2, Y 3, Y 4, X ¹ and R ^a represent the same meaning as described above.)
[Manufacturing process 1]
Compound (6-1) is prepared by a known method, for example, sodium thiocyanate according to the method described in Organic Process Research & Development 2008, Vol. 12, page 1060, etc. Compound (8-1) can be produced by reacting with potassium thionocyanate or ammonium thiocyanate.

[Manufacturing process 2]
Compound (8-1) is reacted with Compound (54) according to a known method, for example, the method described in Pest Management Science 2002, 58, 1175, etc. (3-B) can be manufactured.

  In the production methods 1 to 4 and the reactions of reaction formulas 1 to 4, the reaction mixture after completion of the reaction is directly concentrated or dissolved in an organic solvent, washed and then concentrated in water or poured into ice water, and concentrated after extraction with an organic solvent. By performing the treatment, the target compound of the present invention can be obtained. Moreover, when the necessity for purification arises, it can be separated and purified by any purification method such as recrystallization, column chromatograph, thin layer chromatograph, liquid chromatographic fractionation and the like.

  Specific examples of the production intermediate of the compound of the present invention represented by the formula (1) are shown in Tables 3 and 4.

  [Table 3]

―――――――――――― ―――――――――――― ――――――――――――――
n Y2 Y3 Y4 Z1 n Y2 Y3 Y4 Z1 n Y2 Y3 Y4 Z1
―――――――――――― ―――――――――――― ――――――――――――――
0 CF ₃ HH OEt 0 CF ₃ HH OH 0 CF ₃ HH Cl
1 CF ₃ HH OEt 1 CF ₃ HH OH 1 CF ₃ HH Cl
2 CF ₃ HH OEt 2 CF ₃ HH OH 2 CF ₃ HH Cl
0 IHH OEt 0 IHH OH 0 IHH Cl
1 IHH OEt 1 IHH OH 1 IHH Cl
2 IHH OEt 2 IHH OH 2 IHH Cl
0 Br HH OEt 0 Br HH OH 0 Br HH Cl
1 Br HH OEt 1 Br HH OH 1 Br HH Cl
2 Br HH OEt 2 Br HH OH 2 Br HH Cl
0 Cl HH OEt 0 Cl HH OH 0 Cl HH Cl
1 Cl HH OEt 1 Cl HH OH 1 Cl HH Cl
2 Cl HH OEt 2 Cl HH OH 2 Cl HH Cl
0 c-Pr HH OEt 0 c-Pr HH OH 0 c-Pr HH Cl
1 c-Pr HH OEt 1 c-Pr HH OH 1 c-Pr HH Cl
2 c-Pr HH OEt 2 c-Pr HH OH 2 c-Pr HH Cl
0 NH ₂ HH OEt 0 NH ₂ HH OH 0 NH ₂ HH Cl
1 NH ₂ HH OEt 1 NH ₂ HH OH 1 NH ₂ HH Cl
2 NH ₂ HH OEt 2 NH ₂ HH OH 2 NH ₂ HH Cl
0 H CF ₃ H OEt 0 H CF ₃ H OH 0 H CF ₃ H Cl
1 H CF ₃ H OEt 1 H CF ₃ H OH 1 H CF ₃ H Cl
2 H CF ₃ H OEt 2 H CF ₃ H OH 2 H CF ₃ H Cl
0 HIH OEt 0 HIH OH 0 HIH Cl
1 HIH OEt 1 HIH OH 1 HIH Cl
2 HIH OEt 2 HIH OH 2 HIH Cl
0 H Br H OEt 0 H Br H OH 0 H Br H Cl
1 H Br H OEt 1 H Br H OH 1 H Br H Cl
2 H Br H OEt 2 H Br H OH 2 H Br H Cl
0 H Cl H OEt 0 H Cl H OH 0 H Cl H Cl
1 H Cl H OEt 1 H Cl H OH 1 H Cl H Cl
2 H Cl H OEt 2 H Cl H OH 2 H Cl H Cl
0 H c-Pr H OEt 0 H c-Pr H OH 0 H c-Pr H Cl
1 H c-Pr H OEt 1 H c-Pr H OH 1 H c-Pr H Cl
2 H c-Pr H OEt 2 H c-Pr H OH 2 H c-Pr H Cl
0 H NH ₂ H OEt 0 H NH ₂ H OH 0 H NH ₂ H Cl
1 H NH ₂ H OEt 1 H NH ₂ H OH 1 H NH ₂ H Cl
2 H NH ₂ H OEt 2 H NH ₂ H OH 2 H NH ₂ H Cl
0 H NHAc H OEt 0 H NHAc H OH 0 H NHAc H Cl
1 H NHAc H OEt 1 H NHAc H OH 1 H NHAc H Cl
2 H NHAc H OEt 2 H NHAc H OH 2 H NHAc H Cl
0 H NO ₂ H OEt 0 H NO ₂ H OH 0 H NO ₂ H Cl
1 H NO ₂ H OEt 1 H NO ₂ H OH 1 H NO ₂ H Cl
2 H NO ₂ H OEt 2 H NO ₂ H OH 2 H NO ₂ H Cl
0 HC (O) OH H OEt 0 HC (O) OH H OH 0 HC (O) OH H Cl
1 HC (O) OH H OEt 1 HC (O) OH H OH 1 HC (O) OH H Cl
2 HC (O) OH H OEt 2 HC (O) OH H OH 2 HC (O) OH H Cl
0 HC (O) OEt H OEt 0 HC (O) OEt H OH 0 HC (O) OEt H Cl
1 HC (O) OEt H OEt 1 HC (O) OEt H OH 1 HC (O) OEt H Cl
2 HC (O) OEt H OEt 2 HC (O) OEt H OH 2 HC (O) OEt H Cl
0 H CN H OEt 0 H CN H OH 0 H CN H Cl
1 H CN H OEt 1 H CN H OH 1 H CN H Cl
2 H CN H OEt 2 H CN H OH 2 H CN H Cl
0 HH NH ₂ OEt 0 HH NH ₂ OH 0 HH NH ₂ Cl
1 HH NH ₂ OEt 1 HH NH ₂ OH 1 HH NH ₂ Cl
2 HH NH ₂ OEt 2 HH NH ₂ OH 2 HH NH ₂ Cl
0 HHH OEt 0 HHH OH 0 HHH Cl
1 HHH OEt 1 HHH OH 1 HHH Cl
2 HHH OEt 2 HHH OH 2 HHH Cl
―――――――――――― ―――――――――――― ―――――――――――
[Table 4]

――――――――――――――――― ―――――――――――――――――
Y2 Y3 Y4 Z1 Z2 Y2 Y3 Y4 Z1 Z2
――――――――――――――――― ―――――――――――――――――
CF ₃ HH OEt H CF ₃ HH OEt Br
IHH OEt HIHH OEt Br
Br HH OEt H Br HH OEt Br
Cl HH OEt H Cl HH OEt Br
c-Pr HH OEt H c-Pr HH OEt Br
NH ₂ HH OEt H NH ₂ HH OEt Br
H CF ₃ H OEt HH CF ₃ H OEt Br
HIH OEt HHIH OEt Br
H Br H OEt HH Br H OEt Br
H Cl H OEt HH Cl H OEt Br
H c-Pr H OEt HH c-Pr H OEt Br
H NH ₂ H OEt HH NH ₂ H OEt Br
H NHAc H OEt HH NHAc H OEt Br
H NO ₂ H OEt HH NO ₂ H OEt Br
HC (O) OH H OEt HHC (O) OH H OEt Br
HC (O) OEt H OEt HHC (O) OEt H OEt Br
H CN H OEt HH CN H OEt Br
HH NH ₂ OEt HHH NH ₂ OEt Br
HHH OEt HHHH OEt Br
CF ₃ HH OH H CF ₃ HH OH Br
IHH OH HIHH OH Br
Br HH OH H Br HH OH Br
Cl HH OH H Cl HH OH Br
c-Pr HH OH H c-Pr HH OH Br
NH ₂ HH OH H NH ₂ HH OH Br
H CF ₃ H OH HH CF ₃ H OH Br
HIH OH HHIH OH Br
H Br H OH HH Br H OH Br
H Cl H OH HH Cl H OH Br
H c-Pr H OH HH c-Pr H OH Br
H NH ₂ H OH HH NH ₂ H OH Br
H NHAc H OH HH NHAc H OH Br
H NO ₂ H OH HH NO ₂ H OH Br
HC (O) OH H OH HHC (O) OH H OH Br
HC (O) OEt H OH HHC (O) OEt H OH Br
H CN H OH HH CN H OH Br
HH NH ₂ OH HHH NH ₂ OH Br
HHH OH HHHH OH Br
CF ₃ HH Cl H CF ₃ HH Cl Br
IHH Cl HIHH Cl Br
Br HH Cl H Br HH Cl Br
Cl HH Cl H Cl HH Cl Br
c-Pr HH Cl H c-Pr HH Cl Br
NH ₂ HH Cl H NH ₂ HH Cl Br
H CF ₃ H Cl HH CF ₃ H Cl Br
HIH Cl HHIH Cl Br
H Br H Cl HH Br H Cl Br
H Cl H Cl HH Cl H Cl Br
H c-Pr H Cl HH c-Pr H Cl Br
H NH ₂ H Cl HH NH ₂ H Cl Br
H NHAc H Cl HH NHAc H Cl Br
H NO ₂ H Cl HH NO ₂ H Cl Br
HC (O) OH H Cl HHC (O) OH H Cl Br
HC (O) OEt H Cl HHC (O) OEt H Cl Br
H CN H Cl HH CN H Cl Br
HH NH ₂ Cl HHH NH ₂ Cl Br
HHH Cl HHHH Cl Br
CF ₃ HH OEt Cl CF ₃ HH OEt I
IHH OEt Cl IHH OEt I
Br HH OEt Cl Br HH OEt I
Cl HH OEt Cl Cl HH OEt I
c-Pr HH OEt Cl c-Pr HH OEt I
NH ₂ HH OEt Cl NH ₂ HH Oet I
H CF ₃ H OEt Cl H CF ₃ H OEt I
HIH OEt Cl HIH OEt I
H Br H OEt Cl H Br H OEt I
H Cl H OEt Cl H Cl H OEt I
H c-Pr H OEt Cl H c-Pr H OEt I
H NH ₂ H OEt Cl H NH ₂ H OEt I
H NHAc H OEt Cl H NHAc H OEt I
H NO ₂ H OEt Cl H NO ₂ H OEt I
HC (O) OH H OEt Cl HC (O) OH H OEt I
HC (O) OEt H OEt Cl HC (O) OEt H OEt I
H CN H OEt Cl H CN H OEt I
HH NH ₂ OEt Cl HH NH ₂ OEt I
HHH OEt Cl HHH OEt I
CF ₃ HH OH Cl CF ₃ HH OH I
IHH OH Cl IHH OH I
Br HH OH Cl Br HH OH I
Cl HH OH Cl Cl HH OH I
c-Pr HH OH Cl c-Pr HH OH I
NH ₂ HH OH Cl NH ₂ HH OH I
H CF ₃ H OH Cl H CF ₃ H OH I
HIH OH Cl HIH OH I
H Br H OH Cl H Br H OH I
H Cl H OH Cl H Cl H OH I
H c-Pr H OH Cl H c-Pr H OH I
H NH ₂ H OH Cl H NH ₂ H OH I
H NHAc H OH Cl H NHAc H OH I
H NO ₂ H OH Cl H NO ₂ H OH I
HC (O) OH H OH Cl HC (O) OH H OH I
HC (O) OEt H OH Cl HC (O) OEt H OH I
H CN H OH Cl H CN H OH I
HH NH ₂ OH Cl HH NH ₂ OH I
HHH OH Cl HHH OH I
CF ₃ HH Cl Cl CF ₃ HH Cl I
IHH Cl Cl IHH Cl I
Br HH Cl Cl Br HH Cl I
Cl HH Cl Cl Cl HH Cl I
c-Pr HH Cl Cl c-Pr HH Cl I
NH ₂ HH Cl Cl NH ₂ HH Cl I
H CF ₃ H Cl Cl H CF ₃ H Cl I
HIH Cl Cl HIH Cl I
H Br H Cl Cl H Br H Cl I
H Cl H Cl Cl H Cl H Cl I
H c-Pr H Cl Cl H c-Pr H Cl I
H NH ₂ H Cl Cl H NH ₂ H Cl I
H NHAc H Cl Cl H NHAc H Cl I
H NO ₂ H Cl Cl H NO ₂ H Cl I
HC (O) OH H Cl Cl HC (O) OH H Cl I
HC (O) OEt H Cl Cl HC (O) OEt H Cl I
H CN H Cl Cl H CN H Cl I
HH NH ₂ Cl Cl HH NH ₂ Cl I
HHH Cl Cl HHH Cl I
――――――――――――――――― ―――――――――――――――――
The pest control agent in the present invention is the field of agriculture and horticulture or the field of livestock and hygiene (internal parasites / external parasites for domestic animals and pets, hygiene pests and unpleasant pests for domestic and commercial use) It means a pest control agent for harmful arthropods such as The agrochemical in the present invention means an insecticide / acaricide, nematicide, herbicide, fungicide, etc. in the field of agriculture and horticulture.

  Specific examples of insects, mites, crustaceans, molluscs and nematodes that can be controlled using the compounds of the present invention include the following organisms, but the present invention is not limited to these. Is not to be done.

  Adoxophyes honmai, Adoxophyes orana fascita, Archips breviplicanus, Archips fuscocupreanus, Grapholita molesta, Chamani nan Leguminivora glycinivorella, Matsumuraeses phaseoli, Pandemis heparana, Bucculatrix pyrivorella, Lyonetia clerkella, Lyonetia prunifal malp ringoniella), citrus leafworm (Phyllocnistis citrella), green moth (Acrolepiopsis sapporensis), yamanoimokoga (Acrolepiopsis suzukiella), konaga (Plutella xylostella), oyster leaf moth (Stathmopoda masinissa), Hemogram (Helcystogramma triannulella), Cotton beetle (Pectinophora gossypiella), Peachinosigaiga (Carposina sasakii), Codlinga (Cydla pomonella), Green moth (Chilo suppressalis), Cnaphalocrocis medinalis, Hemagogai indica), Etiella zinckenella, Glyphodes pyloalis, Hellula undalis, Ostrinia furnacalis, Austinia scapulalinia, biloba tris, European tribe Parapediasia teterrella, Parnara guttata, Pieris brassicae, Pieris rapae crucivora, Ascotis selenaria, Soybean looper (Pseudoplusia includens), Chadokuga (Euproctis pseudoconspersa), Japanese gypsy moth (Lymantria dispar), Japanese white squirrel (Orgyia thyellina), American white starfish (Hyphantria cunea), Kuwagomadara hitori (Lemyra imparilis), Akebiko ty ), Agrotis ipsilon, Agrotis segetum, Autographa nigrisigna, Ctenoplusia agnata, Helicoverpa armigera, Helicoverpa assultaH, coverball worm, coverball worm Bad worm (Heliothis virescens), Mamestra brassicae, Mythimna separata, Naranga aenescens, Southern army worm (Spodoptera eridania), Spodoptera exigua, Falla Mewworm (Spodoptera frugiperda), Cotton leaf worm (Spodoptera littoralis), Spodoptera litura, Spodoptera depravata, Nettle quail (Trichoplusia ni), Grapeberry moss (Endopiza viteana), Tomato horn Lepidopterous insects such as tobacco hornworm (Manduca sexta).

  Thrips thrips (Frankliniella intonsa), Thrips thrips (Frankliniella occidentalis), Black thrips (Trips thrips) Moths in total.

  Spotted beetle (Dolycoris baccarum), sea turtle (Eurydema rugosum), bark beetle (Eysarcoris aeneus), bark beetle (Eysarcoris lewisi), bark beetle (Eysarcoris ventralis), subtilus , Nezara antennata, Nezara viridula, Piezodorus hybneri, Plautia crossota, Scotinophora lurida, tiger p Stink bug (Leptocorisa chinensis), Hoso-heli beetle (Riptortus clavatus), Red-headed beetle (Rhopalus maculatus), Cavelerius saccharivorus, Red-footed beetle (Togo hemipterus), Red-billed bug (Togo hemipterus) cus cingulatus, Stephanitis pyrioides, Black beetle turtle (Halticus insularis), Turned plant bug (Lygus lineolaris), Nugget beetle turtle (Stenodema sibiricum), Akazika damselfly (Stenotus rubrovittatus), Mine hawk beetle Trigonotylus caelestialium), Arboridia apicalis, Balclutha saltuella, Epiacanthus stramineus, Potato leaf hopper (Empoasca fabae), Empoasca nipp (Empoasca onukii), green bean leaf (Empoasca sakaii), yellow leaf butterfly (Macrosteles striifrons), black leafhopper (Nephotettix cincticeps), cotton free hopper (Psuedatomoscelis seriatus), Himetolluna x a), white planthopper (Nilaparvata lugens), white planthopper (Sogatella furcifera), citrus lice (Diaphorina citri), pear lice (Psylla pyrisuga), citrus white lice (Aleurocanthus spiniferus), silver leaf white genta (Boli gentia) Japanese whitefly (Dialeurodes citri), Whitefly (Trialeurodes vaporariorum), Grape aphid (Viteus vitifolii), Cotton aphid (Aphis gossypii), Snowy aphid (Aphis spiraecola), Peach aphid (Myzus persicae) , Drosicha corpulenta, Icerya purchasi, Phenacoccus solani, Planococcus citri, Planococcus citri, Planococci occus kraunhiae), stag beetle (Pseudococcus comstocki), horned beetle (Ceroplastes ceriferus), ruby weevil (Ceroplastes rubens), red beetle (Aonidiella aurantii), pear beetle (Comstockaspis perniciosa), tea scale (Comstockaspis perniciosa), scale Pseudaonidia paeoniae), Pseudaulacaspis pentagona, Pseudaulacaspis prunicola, Pepperula scales (Unaspis euonymi), Pteridae scales (Unaspis yanonensis), Insect lecti

  Douganebubui (Anomala cuprea), Japanese common squirrel (Anomala rufocuprea), Coreo hanamuri (Gametis jucunda), Nagachakogane (Heptophylla picea), Japanese beetle (Popillia japonica), Colorado potato beetle (Leptinotarsa decemlineata) White-footed beetle (Melanotus tamsuyensis), Tobacco beetle (Lasioderma serricorne), Himetaketakekisui (Epuraea domina), Common beetle (Epilachna varivestis), Nyungyahoshi-tento (Epilachna vigintioctopunctata), Tenebromometomu-to Tribolium castaneum, Anoplophora malasiaca, Monochamus alternatus, Psacothea hilaris, Xylotrechus pyrrhoderus, Azuki beetle (Callosobruchus chinensis), cucumber beetle (Aulacophora femoralis), beetle beetle (Chaetocnema concinna), southern corn root worm (Diabrotica undecimpunctata), western corn root worm (Diabrotica virgifera), northern corn root worm (Diabrotica barberi), rice plant oryzae, Phyllotreta striolata, Psylliodes angusticollis, Rhynchites heros, Cylas formicarius, Anthonomus grandis, cezo, ce postfasciatus), alfalfa weevil (Hypera postica), rice weevil (Lissorhoptrus oryzophilus), horned weevil (Otiorhynchus sulcatus), granary weevil (Sitophilus granarius) ), Sitophilus zeamais, Sphenophorus venatus vestitus, and Coleoptera (Paederus fuscipes).

  Soybean flies (Asphondylia yushimai), mud wings (Sitodiplosis mosellana), sand flies (Bactrocera cucurbitae), citrus fruit flies (Bactrocera dorsalis), citrus fruit ross (Ceratitis capitata), rice larvae rel Leafhopper (Agromyza oryzae), Leafworm (Chromatomyia horticola), Eggplant leaffly (Liriomyza bryoniae), Leafhopper fly (Liriomyza chinensis), Tomato leaffly (Liriomyza sativae), Beanworm fly (Liriomyza trifolia) (Pegomya cunicularia), Apple Maggot (Rhagoletis pomonella), Hessian Fly (Mayetiola destructor), Housefly (Musca domestica), Stomoxys calcitrans, Sheep Flies (Melophagus ovinu) s), bullflies (Hypoderma bovis), bullflies (Hypoderma lineatum), sheep flies (Oestrus ovis), tsetse flies (Glossina palpalis, Glossina morsitans), bark fly (Prosimulium yezoensis), bullfly (Tabanus trigonco), moth butterfly Diptera such as Leptoconops nipponensis, Culex pipiens pallens, Aedes aegypti, Aedes albopictus, Anopheles hyracanus sinesis.

  Bumblebee (Apethymus kuri), Athalia rosae, Bumblebee (Arge pagana), Bumblebee (Neodiprion sertifer), Bumblebee (Dryocosmus kuriphilus), Gunciari (Eciton burchelli, Eciton schmitus) Hymenoptera insects such as mandarina, bulldog ant (Myrmecia spp.), fire ant (Solenopsis spp.), pharaoh ant (Monomorium pharaonis).

  Direct insects such as Teleogryllus emma, Gryllotalpa orientalis, Locusta migratoria, Oxya yezoensis, and Schistocerca gregaria.

  Coleoptera insects such as Onychiurus folsomi, Onychiurus sibiricus and Bourletiella hortensis.

  Reticulate insects such as the black cockroach (Periplaneta fuliginosa), the cockroach (Periplaneta japonica) and the German cockroach (Blattella germanica).

  Termite insects such as termites (Coptotermes formosanus), Yamato termites (Reticulitermes speratus), and Thai termites (Odontotermes formosanus).

  Fleas such as cat fleas (Ctenocephalides felis), dog fleas (Ctenocephalides canis), chicken fleas (Echidnophaga gallinacea), human fleas (Pulex irritans), keops rat fleas (Xenopsylla cheopis).

  Insects such as chicken lice (Menacanthus stramineus) and bovine lice (Bovicola bovis).

  Lice insects such as cattle lice (Haematopinus eurysternus), pig lice (Haematopinus suis), cattle white lice (Linognathus vituli), solenopotes capillatus and the like.

  Dust mites such as cyclamen dust mites (Phytonemus pallidus), chano dust mites (Polyphagotarsonemus latus), and mites (Tarsonemus bilobatus).

  Spider mites such as cabbage mite (Penthaleus erythrocephalus) and wheat mite (Penthaleus major).

  Spider mites such as rice spider mite (Oligonychus shinkajii), citrus spider mite (Panonychus citri), swan spider mite (Panonychus mori), apple spider mite (Panonychus ulmi), Kanzawa spider mite (Tetranychus kanzawai), spider mite (Tetranychus urticae), etc.

  Chinese cabbage mite (Acaphylla theavagrans), Tulip rust mite (Aceria tulipae), Tomato rust mite (Aculops lycopersici), Citrus radix (Aculops pelekassi), Apple rust mite (Aculus schlechtendali), Green rust mite (Eriophyes chitrastrostrum) ) Etc.

  Acarids such as Robin tick (Rhizoglyphus robini), Tyrophagus putrescentiae, Tyrophagus similis.

  Spider mites such as honeybees (Varroa jacobsoni).

  Tick tick (Boophilus microplus), Rhipicephalus sanguineus, Tick tick (Haemaphysalis longicornis), Tick tick (Haemaphysalis flava), Tick tick (Haemaphysalis campanulata), Tick tick (Ixo tus tick (Ixo tus tick) Tick such as Amblyomma spp.), Dermacentor spp.

  Mesostigmata ticks such as red mite (Dermanyssus gallinae), house dust mite Tropical rat mite (Ornithonyssus bacoti), avian mite Northern fowl mite (Ornithonyssus sylviarum).

  Crawling ticks, such as the crayfish tick (Cheyletiella yasguri) and the cat crawfish tick (Cheyletiella blakei).

  Acne mites, such as the Inode mite (Demodex canis) and the Caterpillar mite (Demodex cati).

  Cucumber mites such as sheep cucumber mites (Psoroptes ovis).

  Spider mites, such as Sarcoptes scabiei, cattle spider mite (Notoedres cati), chicken spider mite (Knemidocoptes spp.).

  Crustaceans such as Armadillidium vulgare.

  Gastropods such as Pomacea canaliculata, African mussel (Achatina fulica), Slug (Meghimatium bilineatum), Chinese scallop (Limax Valentiana), Uskawamai (Acusta despecta sieboldiana), Mishamai mai (Euhadra peliomphala).

  Southern nematode nematode (Pratylenchus coffeae), Kitane equestrian nematode (Pratylenchus penetrans), Klemine easter nematode (Pratylenchus vulnus), potato cyst nematode (Globodera rostochiensis), soybean cyst nematode (Heterodera hemopus) Nematodes such as root-knot nematodes (Meloidogyne incognita), rice-spotted nematodes (Aphelenchoides besseyi), and pine wood nematodes (Bursaphelenchus xylophilus).

  Wild flies or Haematobia irritans, Abu or Tabanus spp. , Flies or Stomoxys calcitrans, blackfish or Simulium spp. , Mekurabu or Chrysops spp. , Lice flies or Melophagus ovinus, and tsetse flies or Glossina spp. Adult flies such as.

  Sheep flies (Oestrus ovis and Cuterebra spp.), Black flies or Phaenicia spp. , Flyfly or Cochliomyia hominivorax, cowfly or Hypoderma spp. Parasitic flies such as horse fleeceworm and Gastrophilus.

  Culex spp. Anopheles spp. And Aedes spp. Mosquitoes etc.

  Specific examples of endoparasites such as livestock, poultry, and pet animals that can be controlled using the compounds of the present invention include the following endoparasites, but the present invention is not limited to these. It is not something.

  Haemonchus, Trichostrongylus, Ostertagia, Nematodirus, Couperia, Ascaris, Bunostomum, Esphagotome Genus (Oesophagostomum), Chabertia, Trichuris, Strongylus, Trichonema, Dictyocaulus, Capillaria, Heterakis ), Toxocara, Ascaridia, Oxyuris, Ancylostoma, Uncinaria, Toxacaris, Parascaris and other nematodes .

  Filariidae nematodes such as Wuchereria, Bruga, Onchocerca, Dirofilaria, and Loa.

  Dracunculidae nematodes, such as the genus Deacunculus.

  Dogworms (Dipylidium caninum), cats (Taenia taeniaeformis), rodents (Taenia solium), striped tapeworms (Taenia saginata), contracted tapeworms (Hymenolepis diminuta), Beneden tapeworms (Moniezia benedeni), Tapeworms such as Diphyllobothrium latum, Diphyllobothrium erinacei, Echinococcus granulosus, Echinococcus multilocularis.

  Fasciola hepatica (F. gigantica), Westermann lung fluke (Paragonimus westermani), hypertrophied fluke (Fasciolopsic buski), pancreatic fluke (Eurytrema pancreaticum, E. coelomaticum), liver fluke (Clonorchis sinensis), Japanese schistosomiasis (Schistosoma) japonicum), Schistosoma haematobium, Schistosoma mansoni, etc.

  Eimeria tenella, Eimeria acervulina, Eimeria brunetti, Eimeria maxima, Eimeria necatrix, Eimeria bovis, Eimeria bovis Eimeria spp., Such as Eimeria ovinoidalis.

  Trypanosoma cruzi, Leishmania spp., Plasmodium spp., Babesis spp., Trichomonadidae spp., Histomanas spp., Giardia (Giardia spp.), Toxoplasma spp., Entamoeba histolytica, Theileria spp.

  Furthermore, the compound of the present invention is also effective against pests having developed resistance against existing insecticides such as organophosphorus compounds, carbamate compounds, pyrethroid compounds and the like.

  That is, the compound of the present invention is composed of the order of slime (Coleoptera), reticulate (Roaches), straight (Plicata), termites, common moths (Thrips), hemimorphs (stink bugs and leafhoppers). Eyes), Lepidoptera (Lepidoptera), Coleoptera (Coleoptera), Hymenoptera (Hymenoptera), Diptera (Flyidae), Isoleoptera (Flea), Liceidae, and other insects, ticks In addition, pests belonging to gastropods, nematodes and the like can be effectively controlled at low concentrations.

  On the other hand, the compound of the present invention has very little adverse effect on mammals, fish, crustaceans and beneficial insects (useful insects such as honeybees and bumblebees, natural enemies such as honeybees, wasps, mistletoe flies, stink bugs, and tick mites) and is extremely useful. It has various features.

  When using the compound of the present invention, it is usually mixed with an appropriate solid carrier or liquid carrier, and further, if desired, a surfactant, penetrant, spreading agent, thickener, antifreeze agent, binder, anti-caking agent. Agent, disintegrating agent, antifoaming agent, antiseptic, anti-degradation agent, etc. added, soluble concentrate, emulsion (emulsifiable concentrate), wettable powder, water soluble powder, granule Water dispersible granule, water soluble granule, suspension concentrate, concentrated emulsion, suspoemulsion, microemulsion, dustable It can be put to practical use as a preparation of any dosage form such as powder, granule tablet, and emulsifiable gel. In addition, from the viewpoint of labor saving and safety improvement, the preparations of any of the above dosage forms can be provided by being enclosed in a water-soluble package such as a water-soluble capsule or a water-soluble film bag.

  Examples of the solid support include quartz, calcite, gypsum, dolomite, chalk, kaolinite, pyrophyllite, sericite, halosite, metahalosite, kibushi clay, glazed clay, porcelain stone, dikelite, Natural minerals such as allophane, shirasu, giraffe, talc, bentonite, activated clay, acid clay, pumice, attapulgite, zeolite, diatomaceous earth, etc .; natural minerals such as calcined clay, perlite, shirasu balloon, vermiculite, attapalgus clay, calcined diatomaceous earth Quality baked goods; inorganic salts such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium hydrogen carbonate, ammonium sulfate, sodium sulfate, magnesium sulfate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, potassium chloride; glucose, fructose, sucrose , Sugars such as lactose; starch, powder Polysaccharides such as cellulose and dextrin; Organic substances such as urea, urea derivatives, benzoic acid, benzoic acid salts; plants such as wood flour, cork flour, corn cobs, walnut shells, tobacco stems; fly ash, white carbon ( For example, hydrous synthetic silica, anhydrous synthetic silica, hydrous synthetic silicate, etc.), fertilizer;

Examples of liquid carriers include aromatic hydrocarbons such as xylene, alkyl (C ₉ or C ₁₀ etc.) benzene, phenyl xylyl ethane, alkyl (C ₁ or C ₃ etc.) naphthalene; machine oil, normal paraffin, isoparaffin Aliphatic hydrocarbons such as naphthene, aromatic hydrocarbons such as kerosene and aliphatic hydrocarbons; alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol, benzyl alcohol; ethylene glycol, propylene glycol, diethylene glycol, hexylene Polyhydric alcohols such as glycol, polyethylene glycol, polypropylene glycol; propyl cellosolve, butyl cellosolve, phenyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl Ethers such as ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, propylene glycol monophenyl ether; ketones such as acetophenone, cyclohexanone, and γ-butyrolactone; fatty acid methyl esters, succinic acid dialkyl esters, glutamic acid dialkyl esters, adipic acid dialkyl esters , Esters such as dialkyl phthalates; acid amides such as N-alkyl (C ₁ , C ₈ or C ₁₂ ) pyrrolidone; fats and oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil, castor oil; dimethyl And sulfoxide, water; and the like.

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

  Examples of the surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl (mono or di) phenyl ether, polyoxyethylene (mono, di or tri) styryl phenyl ether, polyoxyethylene polyoxypropylene block copolymer, polyoxyethylene Oxyethylene fatty acid (mono or di) ester, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, acetylene glycol, acetylene alcohol, ethylene oxide adduct of acetylene glycol, ethylene oxide adduct of acetylene alcohol, Nonionic surfactants such as alkyl glycosides; alkyl sulfate salts, alkylbenzene sulfonates, lignin sulfonates, alkyls Succinate, naphthalenesulfonate, alkylnaphthalenesulfonate, salt of formalin condensate of naphthalenesulfonic acid, salt of formalin condensate of alkylnaphthalenesulfonic acid, polyoxyethylene alkyl ether sulfate or phosphate ester salt, polyoxyethylene (Mono or di) alkyl phenyl ether sulfate or phosphate ester salt, polyoxyethylene (mono, di or tri) styryl phenyl ether sulfate or phosphate ester salt, polycarboxylate (eg, polyacrylate, polymaleate, malee) Copolymer of acid and olefin), anionic surfactant such as polystyrene sulfonate; cationic surfactant such as alkylamine salt and alkyl quaternary ammonium salt; amphoteric surfactant such as amino acid type and betaine type Agent; silicone Surfactants, fluorine-based surfactants; and the like.

  Although content of these surfactants is not specifically limited, The range of 0.05-20 mass parts is desirable normally with respect to 100 mass parts of preparations of this invention. These surfactants may be used alone or in combination of two or more.

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

  On the other hand, when using the compound of the present invention for the control of the ectoparasites of mammals and birds as domestic animals and pets, an effective amount of the compound of the present invention is administered orally together with a pharmaceutical additive; Parenteral administration such as internal, subcutaneous, intravenous, intraperitoneal, etc .; transdermal administration such as immersion, spraying, bathing, washing, pouring-on and spotting-on, dusting; It can be administered by nasal administration or the like. The compounds of the present invention can also be administered by molded products using strips, plates, bands, collars, ear marks, limb bands, labeling devices and the like.

  In administration, the compound of the present invention can be in any dosage form suitable for the administration route.

  When exterminating ectoparasites or endoparasites using the compound of the present invention, the preferred dosage of the compound of the present invention represented by the formula (1), which is the active ingredient, is the type of the target parasite to be controlled and the subject to be administered. Although it depends on the species of animal or administration method, it is generally 0.01-100 mg / kg, preferably 0.01-50 mg / kg, based on the body weight of the subject animal to be administered. In particular, the dose to the dog may vary depending on the type or age of the target dog or the ectoparasite to be controlled, but is usually 1 to 5000 mg / kg per kg of the living weight of the target dog, preferably 1-100 mg / kg.

  When exterminating ectoparasites or endoparasites by administration of the compound of the present invention, the administration interval depends on the type of target parasite to be controlled, the type of target animal to be administered or the administration method, etc. It can be arbitrarily set in a range from daily to once a year. It is preferably once a week to once every 6 months, more preferably daily (24 hours), monthly, once a month, once every two months, or once every three months.

  In addition, when the compound of the present invention is used for controlling ectoparasites in dogs, the compound of the present invention is orally administered to the dog, for example, at a timing just before 30 minutes after the start of food or 120 minutes after the end of the diet. Can be mentioned. Here, 30 minutes before the start of the diet and 120 minutes after the end of the diet are based on the act of eating the food given to the dog for the purpose of nutrition intake. For example, when the dog's diet time is 20 minutes, the prescribed time is a total of 170 minutes from 30 minutes before the start of the diet to 120 minutes after the end of the diet, based on the meal act. This includes the case where the diet is interrupted once during the diet, and the diet is resumed after oral administration of the compound of the present invention. In addition, in this specification, a diet means the act which an animal eats.

  In general, the number of daily diets for dogs varies depending on the breed, age and custom, but usually 3-4 times a day for dogs younger than 2 years, 2 to 3 times a day for dogs less than 1 year from the second half of life, It is considered to be twice a day for adult dogs of about 1 to 5 years old and about 2 to 3 times a day for elderly dogs over 6 years old. In the present invention, diet means an act of feeding for the purpose of ingesting nutrition, and does not include an act of feeding so-called dogs and food for the purpose of training.

  Arbitrary dosage forms to be prepared include powders, granules, wettable powders, pellets, tablets, large pills, capsules, solid preparations such as molded products containing active compounds; injection solutions, oral solutions, skin Liquid preparations such as liquids used above or in body cavities; Solution preparations such as Pour-on, Spot-on, flowable and emulsion; Semi-solid preparations such as ointments and gels And so on.

  Examples of the dosage form for oral administration of the compound of the present invention include tablets (Tablets), solid dosage forms (Chewables), capsules (Capsules), pills (Pills), large pills (Boluses), and granules (Granules). ), Solid preparations such as powders; semi-solid preparations such as pastes and gels; liquid preparations such as drinks; and the like.

  The dosage form for transdermal administration includes, for example, solid preparations such as powders (Cream), ointments (Salve and Ointment), pastes (Pastes), gels (Gels) Semi-solid preparations such as; sprays (Spray), aerosols (Aerosols), solutions (Solutions and Emulsions), suspensions (Suspensions), liquid preparations such as lotions (Lotions); and the like.

  Furthermore, examples of the dosage form for administration by injection include liquid preparations such as solutions (Solutions and Emulsions) and suspensions (Suspensions). Examples of dosage forms for nasal administration include And liquid preparations such as aerosols (Aerosols).

  In addition, as a dosage form in the case of spraying treatment in an animal breeding environment such as a barn, for example, solid preparations such as wettable powders, powders (Dusts), granules (Emulsions); emulsions (Emulsions) And liquid preparations such as flowable concentrates (Suspension concentrates).

  In addition, the formulation used for the parasite control agent of this invention is not limited only to these dosage forms.

  The solid preparation can be administered orally as it is, or diluted with water and used by transdermal administration or spraying in an animal breeding environment such as a barn.

  The solid preparation used for oral administration comprises a compound represented by formula (1) or a salt thereof, one or more excipients and binders suitable for oral administration, and if necessary, a lubricant. It can be prepared by mixing with a physiologically acceptable additive such as an agent, a disintegrant, a dye, and a pigment and molding the mixture into a desired shape.

  Examples of the excipient and binder include sugars or sugar derivatives such as lactose, sucrose, mannitol, and sorbitol; starches such as corn starch, wheat starch, rice starch, and potato starch; methylcellulose, carboxymethylcellulose, hydroxyethylcellulose, hydroxy Examples thereof include cellulose or cellulose derivatives such as propylcellulose and hydroxypropylmethylcellulose; proteins or protein derivatives such as zein and gelatin; synthetic polymer compounds such as honey, gum arabic glue, polyvinyl alcohol, and polyvinylpyrrolidone.

  Examples of the lubricant include magnesium stearate, and examples of the disintegrant include cellulose, agar, alginic acid, cross-linked polyvinyl pyrrolidinone, and carbonate.

  Furthermore, among solid preparations used for oral administration, especially in the case of solid preparations such as chewable agents, additives that give taste, texture, and taste preferred by the animals to be administered can also be used. The carriers and additives used in the solid preparation of the control agent composition are not limited to these.

  Liquid preparations should be administered as they are, transdermally or by injection, or mixed with feed, orally administered, diluted with water, transdermally administered, and sprayed into animal breeding environments such as barns. Can do.

  Injection solutions can be administered intravenously, intramuscularly and subcutaneously. Injection solutions can be prepared by dissolving the active compound in a suitable solvent and adding additives such as solubilizers, acids, bases, buffer salts, antioxidants, protective agents, etc., if necessary.

  Suitable solvents include water, ethanol, butanol, benzyl alcohol, glycerin, propylene glycol, polyethylene glycol, N-methylpyrrolidone and mixtures thereof, physiologically acceptable vegetable oils, synthetic oils suitable for injection, and the like.

  Examples of the solubilizer include polyvinyl pyrrolidone, polyoxyethylated castor oil, polyoxyethylated sorbitan ester, and the like.

  Examples of the protective agent include benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid ester, n-butanol and the like.

  Oral solutions can be administered directly or diluted. It can be prepared in the same manner as an injectable solution.

  Flowable agents, emulsions and the like can be administered directly or diluted, transdermally, or by environmental treatment.

  Solutions used on the skin can be administered by dripping, spreading, rubbing, spraying, spraying or applying by dipping (immersion, bathing or washing). These solutions can be prepared in the same manner as injection solutions.

  Pour-on and spot-on agents can be dripped or sprayed onto a limited area of the skin, so that the active compound is immersed in the skin and acts systemically. it can.

  Drops and drop preparations can be prepared by dissolving, suspending or emulsifying the active ingredient in suitable skin-compatible solvents or solvent mixtures. If necessary, auxiliary agents such as surfactants, colorants, absorption promoting substances, antioxidants, light stabilizers, and adhesives may be added.

  Suitable solvents include water, alkanol, glycol, polyethylene glycol, polypropylene glycol, glycerin, benzyl alcohol, phenylethanol, phenoxyethanol, ethyl acetate, butyl acetate, benzyl benzoate, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, acetone, Methyl ethyl ketone, aromatic and / or aliphatic hydrocarbons, vegetable or synthetic oil, DMF (N, N-dimethylformamide), liquid paraffin, light liquid paraffin, silicone, dimethylacetamide, N-methylpyrrolidone or 2,2-dimethyl- 4-oxy-methylene-1,3-dioxolane is mentioned.

  Absorption promoting substances include DMSO (dimethyl sulfoxide), isopropyl myristate, dipropylene glycol pelargonate, silicone oil, aliphatic esters, triglycerides or fatty alcohols.

  Antioxidants include sulfite, metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole or tocopherol.

  The emulsion can be administered orally, transdermally or as an injection. An emulsion is prepared by dissolving an active ingredient in a hydrophobic phase or a hydrophilic phase, and adding this to a suitable emulsifier, if necessary, a colorant, an absorption promoting substance, a protective agent, an antioxidant, a light-shielding agent, a thickening substance. It can be prepared by homogenizing with other phase solvents together with other auxiliary agents.

  As hydrophobic phase (oil), paraffin oil, silicone oil, sesame oil, almond oil, castor oil, synthetic triglyceride, ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol pelargonate, branched chain Of a short fatty acid having a chain length and a saturated fatty acid having a chain length of C16 to C18, isopropyl myristate, isopropyl palmitate, capryl / caprate of a saturated fatty alcohol having a chain length of C12 to C18, isopropyl stearate, oleyl oleate Decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid ester, dibutyl phthalate, diisopropyl adipate, isotridecyl alcohol, 2-octyldodecanol, cetyl stearyl alcohol, oleyl alcohol, etc. It is.

  Examples of the hydrophilic phase include water, propylene glycol, glycerin, sorbitol and the like.

  Emulsifiers include nonionic interfaces such as polyoxyethylated castor oil, polyoxyethylated sorbitan monoolefin acid, sorbitan monostearate, glyceryl monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether, etc. Activators; amphoteric surfactants such as disodium N-lauryl-β-iminodipropionate and lecithin; anions such as sodium lauryl sulfate, fatty alcohol sulfate ether, monoethanolamine salt of mono / dialkyl polyglycol orthophosphate Surfactants; cationic surfactants such as cetyltrimethylammonium chloride; and the like.

  Other adjuvants include carboxymethyl cellulose, methyl cellulose, polyacrylate, alginate, gelatin, gum arabic, polyvinyl pyrrolidone, polyvinyl alcohol, methyl vinyl ether, maleic anhydride copolymer, polyethylene glycol, wax, colloidal silica and the like. It is done.

  Semi-solid preparations can be administered by application on the skin or spreading or introduction into body cavities. Gels can be prepared by adding sufficient thickener to a solution prepared as described above for injectable solutions to produce a clear material having an ointment-like consistency.

  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, “parts” means parts by mass.

[Wettable powder]
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.

〔emulsion〕
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.

[Suspension]
Compounds 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.

(Granule wettable powder)
Compound of the present invention 0.1 to 90 parts Solid carrier 0 to 98.9 parts Surfactant 1 to 20 parts Others 0 to 10 parts Others include, for example, binders and decomposition inhibitors.

[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.

[Granule]
Compound of the present invention 0.01 to 80 parts Solid carrier 10 to 99.99 parts Others 0 to 10 parts Others include, for example, binders, decomposition inhibitors and the like.

[Dust]
Compound of the present invention 0.01 to 30 parts Solid support 65 to 99.99 parts Others 0 to 5 parts Other examples include a drift inhibitor and a decomposition inhibitor.

  Next, although the formulation example which uses this invention compound as an active ingredient is shown more concretely, this invention is not limited to these.

  In the following formulation examples, “parts” means parts by mass.

[Formulation Example 1] Wetting Agent Compound No. 1-002a 20 parts Pyrophyllite 74 parts Solpol 5039 4 parts (trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.)
Carplex # 80D 2 parts (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
The above is uniformly mixed and ground to obtain a wettable powder.

[Formulation Example 2] Emulsion Compound No. 1-002a 5 parts xylene 75 parts N-methylpyrrolidone 15 parts Solpol 2680 5 parts (trade name, mixture of nonionic surfactant and anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.)
The above is uniformly mixed to obtain an emulsion.

[Formulation Example 3] Suspending Agent Compound No. 1-002a 25 parts Agrisol S-710 10 parts (trade name, nonionic surfactant: manufactured by Kao Corporation)
Lnox 1000C 0.5 part (trade name, anionic surfactant: manufactured by Toho Chemical Industry Co., Ltd.)
Xanthan gum 0.2 parts Water 64.3 parts After uniformly mixing the above, wet pulverize to make a suspension.

[Formulation Example 4] Granule wettable powder of the present compound No. 1-002a 75 parts Hytenol NE-15 5 parts (trade name, anionic surfactant: manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
Vanillex N 10 parts (trade name, anionic surfactant: manufactured by Nippon Paper Industries Co., Ltd.)
Carplex # 80D 10 parts (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to obtain a granulated wettable powder.

[Formulation Example 5] Granules of the present compound No. 1-002a 5 parts Bentonite 50 parts Talc 45 parts After uniformly mixing and pulverizing the above, a small amount of water is added, stirred and mixed, granulated with an extrusion granulator, and dried to form granules.

[Composition Example 6] Powder This invention compound No. 1-002a 3 parts Carplex # 80D 0.5 part (trade name, synthetic hydrous silicic acid: manufactured by Shionogi & Co.)
Kaolinite 95 parts Diisopropyl phosphate 1.5 parts or more uniformly mixed and pulverized to obtain a powder.

  In use, the above preparation is diluted 1 to 10,000 times with water or sprayed directly without dilution.

[Formulation 7] wettable powder preparation Compound No. 1-002a 25 parts sodium diisobutyl naphthalenesulfonate 1 part calcium n-dodecylbenzenesulfonate 10 parts alkylaryl polyglycol ether 12 parts sodium salt of naphthalenesulfonic acid formalin condensate 3 parts emulsion type silicone 1 part silicon dioxide 3 parts kaolin 45 Part [Formulation Example 8] Water-soluble thickener preparation 1-002a 20 parts polyoxyethylene lauryl ether 3 parts sodium dioctylsulfosuccinate 3.5 parts dimethyl sulfoxide 37 parts 2-propanol 36.5 parts [Formulation Example 9] Spraying solution 1-002a 2 parts dimethyl sulfoxide 10 parts 2-propanol 35 parts acetone 53 parts [Formulation Example 10] Solution for transdermal administration Compound No. of the present invention 1-002a 5 parts Hexylene glycol 50 parts Isopropanol 45 parts [Formulation Example 11] Solution for transdermal administration Compound No. of the present invention 1-002a 5 parts propylene glycol monomethyl ether 50 parts dipropylene glycol 45 parts [Formulation Example 12] Solution for transdermal administration (dropping) The present compound No. 1 1-002a 2 parts light liquid paraffin 98 parts [Formulation Example 13] Solution for transdermal administration (dropping) The present compound No. 1 1-002a 2 parts light liquid paraffin 58 parts olive oil 30 parts ODO-H 9 parts Shin-Etsu silicone 1 part In addition, when the compound of the present invention is used as an agrochemical, other types of herbicides are used at the time of formulation or spraying as necessary. You may mix and apply with an agent, various insecticides, an acaricide, a nematicide, a fungicide, a plant growth regulator, a synergist, a fertilizer, a soil conditioner, etc.

  In particular, by applying a mixture with other agricultural chemicals or plant hormones, it is possible to reduce the cost by reducing the amount of applied medicine, to expand the insecticidal spectrum due to the synergistic action of the mixed drugs, and to achieve a higher pest control effect. At this time, a combination with a plurality of known agricultural chemicals is also possible.

  Examples of the type of agricultural chemical used in combination with the compound of the present invention include compounds described in The Pesticide Manual 15th edition, 2009, and the like. Specific examples of the general names are as follows, but are not necessarily limited to these.

  Bactericides: acibenzolar-S-methyl, acylaminobenzamide, acypetacs, aldimorph, ametoctradin, aminopyrifen, amisulbrom, Amobam, ampropyfos, anilazine, azaconazole, azithiram, azoxystrobin, barium polysulfide, benalaxyl, benalaxyl-M (Benalaxyl-M), benodanil, benomyl, benquinox, bentaluron, benthiavalicarb-isopropyl, benthiazole, benzacryl zamacril), benzamorf, benzovindiflupyr, bethoxazine, binapacryl, biphenyl, bitertanol, blasticidin-S (blasticidin-S), bixaphene ( bixafen, bordeaux mixture, boscalid, bromuconazole, bupirimate, buthiobate, calcium polysulfide, calcium polysulfide, captaphor (Captafol), captan, carpropamid, carbamorph, carbendazim, carboxin, carvone, cheshunt mixture, chinomethionat Chlobenthiazone, chloraniformethane, chloranil, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chloroquinox, Chlozolinate, climbazole, clotrimazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate ( copper naphthenate, copper oleate, basic copper oxychloride, copper sulfate, copper sulfate, basic, copper zinc chromate, cupraneb (Cufraneb), coumoxystrobin, cuprobum (cupro) bam), cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazol, cyprodinil, propromil (Cyprofuram), dazomet, debacarb, decafentin, dehydroacetic acid, diclobentiazox, dichlofluanid, dichlone, dichloro Fen (dichlorophen), dichlozoline, diclobutrazol, diclocymet, diclomedine, dicloran, etc.

  Bactericides (continued): dietofencarb, difenoconazole, diflumetorim, dimethirimol, dimethomorph, dimoxystrobin, diiconazole-diniconazole-diniconazole-M M), dinobuton, dinocap, dinocap-4, dinocap-6, dinocton, dinosulfon, dinoterbon, diphenylamine ), Dipymetitrone, dipyrithione, ditalimfos, dithianon, dodemorph-acetate, dodine, drazoxolon, edifenphos, nesifenphos Robin (enestrobin), enoxastrobin, epoxiconazole, etaconazole, ethaboxam, etem, etirimol, ethoxyquin, etridiazole, famoxadone (Famoxadone), fenarimol, fenbuconazole, fenamidone, fenaminosulf, fenaminoinstrobin, fenapanil, fendazosulam, fendazosulam, fenfuram, fenfuram Fenhexamid, fenitropan, fenoxanil, fenpiclonil, fenpicoxamid, fenpropidin, fenpyrazamine fenpyrazamine, fenpropimorph, fentin, ferbam, ferimzone, fluazinam, fludioxonil, flufenoxystrobin, fluindapyr, fluindapyr flumetover, flumorph, fluopicolide, fluopyram, fluorimide, fluotrimazole, fluoxastrobin, fluquinconazole, flusilazole, Flusulfamide, flutianil, flutolanil, flutriafol, fluxapyroxad, folpet, fosetyl-alumini Fosetyl-aluminium, fthalide, fuberidazole, furaxaxyl, furametpyr, furcarbanil, furconazole, furconazole, fluconazole-cis, flumeciclos ( furmecyclox, furphanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexaconazole, hexylthiofos, hydroxyquinoline 8-hydroxyquinoline sulfate, hymexazol, imazalil, imibenconazole, iminoctadine-albesilate, iminocta Acetate (iminoctadine-triacetate), impylfluxam (inpyrfluxam), ipconazole, ipfentrifluconazole, iprobenfos, iprodione, iprovalicarb (is), isetamid, isetamid Isoflucypram, isoprothiolane, isopyrazam, isothianil, isovaledione and the like.

  Bactericides (continued): kasugamycin, kresoxim-methyl, laminarin, mancopper, mancozeb, mandestrobin, mandipropamid, mannepropamid maneb, mebenil, mecarbinzid, mefentrifluconazole, mepanipyrim, meptyldinocap, mepronil, metalaxyl, metalaxyl-M (metalaxyl-M) M), metam, metazoxolon, metconazole, methasulfocarb, metfuroxam, methyl isothiocyanate, metiram, metinominostrone obin, metrafenone, metsulfovax, milneb, microbutanil, microzoline, nabam, natamycin, nickel bis (dimethyldithiocarbamate) (Dimethyldithiocarbamate), nitrostyrene, nitrothal-isopropyl, nuarimol, OCH, octhilinone, offurace, orysastrobin, oxathapi Proline (oxathiapiprolin), oxadixyl, oxine copper, oxycarboxin, oxpoconazole fumarate, pepozoate, penconazole nazole), penflufen, penencycuron, penthiopyrad, orthophenylphenol, phosdiphen, phosdiphen, picarbutrazox, picoxystrobin, piperaline ( piperalin, polycarbamate, polyoxins, polyoxin-D (polyoxorim), potassium azide, potassium hydrogen carbonate, proquinazid, probenazole, prochloraz ( prochloraz, procymidone, propamocarb hydrochloride, propiconazole, propineb, prothiocarb, prothioconazole, pidiflume Pydiflumetofen, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyraziflumid, pyrazophos, pyribencarb-methyl ), Pyridinitril, Pyrifenox, Pyrimethanil, Pyriminostrobin, Pyrimorph, Pyriofenone, Pyroxoxazole, Pyroxilone, roxychlor ), Pyroxyfur, quinomethionate, quinofumelin, quinoxyfen, quintozene, quinacetol-sulfate, ki Zamido (quinazamid), Kinkonazoru (quinconazole), Rabenzazoru (Rabenzazole) and Bacillus subtilis (Bacillus subtilis, Strain: D747, FZB24, GBO3, HAI0404, MBI600, QST713, Y1336, or the like).

  Bactericides (continued): sedaxane, sodium azide, sodium hydrogen carbonate, sodium hypochlorite, sulfur, spiroxamine, salicylanilide (Salycylanilide), silthiofam, simeconazole, tebuconazole, tebufloquin, tecnazene, tecoram, tetraconazole, thiabendazole, thiabendazole thiadifluor, thicyofen, thifluzamide, thiochlorfenphim, thiophanate, thiophanate-methyl, thioquinox, thiram, thiadi Tiadinil, tioxymid, tolclofos-methyl, tolprocarb, tolylfluanid, triadimefon, triadimenol, triamiphos, triamiphos (triamiphos) triarimol, triazoxide, triazbutil, tributyltin oxide, trichlamide, tricyclazole, triridemorph, trifloxystrobin, triflumizole , Triforine, triclopyricarb, triticonazole, validamycin, valifenalate, vinclozolin, zarylamide (z) arilamide, zinc sulfate, zineb, ziram, zoxamide, shiitake mycelium extract, shiitake fruiting body extract, NF-180 (test name), MIF-1002 (test) Name), S-2399 (test name) and AKD-5195 (test name).

  Bactericides: benzalkonium chloride, bithionol, bronopol, cresol, formaldehyde, nitrapyrin, oxolinic acid, oxyterracycline , Streptomycin and tecloftalam.

  Nematicides: aldoxycarb, benclothiaz, cadusafos, davylope (DBCP), dichlofenthion, dsp (DSP), etoprophos, fenamiphos, fensulfothion (Fensulfothion), fluazaindolizine, fluenesulfone, fosthiazate, fosthietan, imisiafos, isamidofos, isazofos, oxamyl, oxamyl, thiaxazafen), thionazin, tioxazafen, BYI-1921 (test name) and MAI-08015 (test name).

  Acaricide: acequinocyl, acrinathrin, acynonapyr, amidoflumet, amitraz, azocyclotin, BCI-033 (study name), benzoximate, Bifenazate, bromopropylate, chinomethionat, chlorobezilate, clofentezine, cyenopyrafen, cyflumetofen, cyhexatine, olhol , Dienochlor, diflovidazin, DNOC, etoxazole, fenazaquin, fenbutatin oxide, phenothiocarb ( fenothiocarb, fenpropathrin, fenpyroximate, fluacrypyrim, fluacrypyrim, halfenprox, hexythiazox, milbemectin, propargite, piflumide (pyflubum) ), Pyrimidifen, S-1870 (test name), spirodiclofen, spyromesifen, CL900187 (test name), tebufenpyrad and NA-89 (test name).

    Insecticides: abamectin, acephate, acetamipirid, afidopyropen, afoxolaner, alanycarb, aldicarb, alesphos, amethphos, azaphos Ethyl (azinphos-ethyl), azinphos-methyl, bacillus thuringiensis, bendiocarb, benfluthrin, benfuracarb, bensultap, benzpyrimoxy Sun (benzpyrimoxan), bifenthrin, bioallethrin, bioresmethrin, bistrifluron, broflanilide, buprofezin, Tocarboxim, carbaryl, carbofuran, carbofuran, carbosulfan, cartap, chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlorfenapyr Chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin, clothianidin Cyanophos, cyantraniliprole, cyclaniliprole, cycloprothrin, cyflumetofen, cyfluthrin, Beta-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin (alpha-) cypermethrin), beta-cypermethrin, beta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, deltamethrin, diacloden, diafenthiuron ), Diazinon, dicloromezotiaz, dichlorvos, diflubenzuron, dimefluthrin, dimethylvinphos, dinotefuran, diofenol an), disulfoton, dimethoate, emamectin-benzoate, empenthrin, endosulfan, alpha-endosulfan, EPN, esfenvalerate ), Etiofencarb, ethiprole, etofenprox, etrimfos, fenitrothion, fenobucarb, phenoxycarb, fenpropathrin, fenthion ), Fenvalerate, fipronil, flonicamid, fluazuron, flubendiamide, flucycloxuron , Flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrinin, fluralaner, fluvalinate, tau Fluvalinate, tono-fluvalinate, fonophos, formetanate, formothion, furthiothiocarb, flufiprole, fluhexafon, flupyradifurone, flometoquin, flometoquin, etc. .

  Insecticides (continued): halofenozide, heptafluthrin, hexaflumuron, hydramethylnon, imidacloprid, imiprothrin, isofenphos, indoxacarb (Indoxacarb), indoxacarb-MP (indoxacarb-MP), isoprocarb (isoprocarb), isoxathion (isoxathion), kappa-bifenthrin, kappa-tefluthrin, lepimectin (lepimectin), lufenuron ( lufenuron, malathion, meperfluthrin, metaflumizone, metalaldehyde, metamidophos, methidathion, methacrifos, metalcarb b), methomyl, methoprene, methoxychlor, methoxyfenozide, methyl bromide, metofluthrin, epsilon-metofluthrin, momfluorothrin ), Epsilon-momfluorothrin, monocrotophos, muscalure, nitenpyram, novaluron, noviflumuron, omethoate, oxydemeton-methyl (oxydemeton-methyl) methyl), oxydeprofos, parathion, parathion-methyl, pentachlorophenol, permethrin, phenothrin, phenothrin Phenthoate, phoxim, phorate, phosalone, phosmet, phosphamidon, pirimicarb, pirimiphos-methyl, profenofos, profluthrin (Profluthrin), prothiofos, propaphos, protrifenbute, pymetrozine, pyraclofos, pyrethrins, pyridalyl, pyrifluquinapy, prorifenquine ), Pyrafluprole, pyriproxyfen, resmethrin, rotenone, SI-0405 (study name), sulprofos, silafluofen, spinetoram (spine) toram), spinosad, spiromesifen, spirotetramat, spiropidion, sulfoxaflor, sulfoxap, SYJ-159 (test name), tebfenozide, Teflubenzuron, tefluthorin, terbufos, tetrachlorovinphos, tetramethrin, d-T-80-phthalthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin, tetramethylfluthrin Niliprol (tetraniliprole), thiacloprid, thiocyclam, thiodicarb, thiamethoxam, thiofanox, thiometon, tolfenpyrad, Tralomethrin, transfluthrin, triazamate, trichlorfon, triazuron, triflumezopyrim, triflumuron, vamidion, MI -1209 (test name) and ME5382 (test name).

  Hereinafter, the present invention will be described in more detail by describing synthesis examples and test examples of the compounds of the present invention as examples, but the present invention is not limited thereto.

  The medium pressure preparative liquid chromatography described in the synthesis example used an intermediate pressure preparative apparatus (Yamazen Co., Ltd.); YFLC-Wprep (flow rate 18 ml / min, silica gel 40 μm column).

The chemical shift value of the proton nuclear magnetic resonance spectrum described below (hereinafter referred to as ¹ H-NMR) is 300 MHz in deuterated chloroform solvent using Me ₄ Si (tetramethylsilane) as a reference substance. (Model: JNM-ECX300 or JNM-ECP300, manufactured by JEOL). In addition, the symbol in the chemical shift value of ¹ H-NMR represents the following meaning.
s: singlet, d: doublet, dd: double doublet, t: triplet, q: quartet, m: multiplet, brs: broad singlet Synthesis Example 1: N- (2,2-difluorobenzo [d] [1,3 Synthesis of dioxole-5-yl) -3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxamide (the present compound No. 5-001a) 5-amino To a mixed solution of 83 mg of 2,2-difluoro-1,3-benzo [d] [1,3] dioxole, 391 mg of triethylamine and 1.0 ml of dichloromethane at room temperature, 3- (ethylsulfonyl) -7- (tri Fluoromethyl) imidazo [1,2-a] pyridine-2-carbonyl chloride 110 mg and dichloromethane 1.0 ml If the solution was added. After the addition was complete, the reaction mixture was stirred at room temperature for 18 hours. After completion of the reaction, 5 ml of saturated sodium bicarbonate was added to the reaction mixture, and the mixture was extracted with chloroform (5 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then 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 90:10 to 20:80 (volume ratio, the same applies hereinafter)]. 120 mg of the product was obtained as a pale yellow solid.
Melting point: 197-200 ° C
¹ H-NMR (CDCl ₃ ): δ9.55 (d, J = 7.5Hz, 1H), 9.35 (s, 1H), 8.05 (s, 1H), 7.85 (d, J = 1.8Hz, 1H), 7.30 -7.20 (m, 2H), 7.05 (d, J = 8.7Hz, 1H), 3.96 (q, J = 7.2Hz, 2H), 1.37 (t, J = 7.2Hz, 3H).
Synthesis Example 2: N- (2,2-difluorobenzo [d] [1,3] dioxol-5-yl) -3- (ethylsulfonyl) -N-methyl-7- (trifluoromethyl) imidazo [1, 2-a] Synthesis of pyridine-2-carboxamide (Compound No. 5-002a of the present invention) In a mixed solution of 60% by weight sodium hydride (dispersed in mineral oil) 10 mg and THF 0.5 ml, the above Synthesis Example 1 was performed at room temperature. N- (2,2-difluorobenzo [d] [1,3] dioxol-5-yl) -3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2 -A] A solution of 108 mg of pyridine-2-carboxamide in 1.2 ml of THF was added. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. After completion of stirring, 35 mg of methyl iodide was added to the reaction mixture at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. After completion of the reaction, 5 ml of water was added to the reaction mixture and extracted with ethyl acetate (5 ml × 3). The obtained organic layer was dehydrated and dried in the order of saturated saline and then anhydrous sodium sulfate, and then 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 from 95: 5 to 30:70) to obtain 42 mg of the desired product as a colorless oil. .
¹ H-NMR (CDCl ₃ ): δ9.03 (d, J = 7.2Hz, 1H), 7.86 (s, 1H), 7.25-7.05 (m, 3H), 6.86 (d, J = 8.4Hz, 1H) , 3.60 (q, J = 7.5Hz, 2H), 3.49 (s, 3H), 1.36 (t, J = 7.5Hz, 3H).
Synthesis Example 3: 3- (Ethylthio) -N-methyl-7- (trifluoromethyl) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2 -A] Synthesis of pyridine-2-carboxamide (the present compound No. 4-001b) 3- (Ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid 300 mg and dichloromethane To 4 ml of the mixed solution, 377 mg of oxalyl chloride and 20 mg of N, N-dimethylformamide were sequentially added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the solvent was distilled off from the reaction mixture under reduced pressure to obtain 3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carbonyl chloride. . 3- (Ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carbonyl chloride dissolved in 3 ml of dichloromethane was converted to 2-methylamino-5- (trifluoromethyl) -1, To a mixed solution of 208 mg of 3,4-thiadiazole and 3 ml of pyridine, it was added under ice cooling. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. To the obtained residue, 5 ml of water was added and extracted with ethyl acetate (5 ml × 3). The obtained organic layer was washed with 5 ml of 1 mol / L hydrochloric acid, dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The resulting residue was purified by alumina column chromatography eluting with n-hexane-ethyl acetate (95: 5 to 30:70 gradient). Further, the obtained solid was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient of 95: 5 to 30:70) to obtain 525 mg of the desired product as a pale yellow solid.
Melting point: 84-86 ° C
¹ H-NMR (CDCl ₃ ): δ8.70 (d, J = 7.5Hz, 1H), 8.03 (s, 1H), 7.23 (d, J = 7.5Hz, 1H), 4.04 (s, 3H), 2.98 (q, J = 7.5Hz, 2H), 1.23 (t, J = 7.5Hz, 3H).
Synthesis Example 4: 3- (Ethylsulfinyl) -N-methyl-7- (trifluoromethyl) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1, 2-a] Synthesis of pyridine-2-carboxamide (Compound No. 4-001c of the present invention) 3- (ethylthio) -N-methyl-7- (trifluoromethyl)-synthesized by the method described in Synthesis Example 3 above To a mixed solution of N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide and 3 ml of chloroform under ice-cooling. 35 mg of 65% by mass metachloroperbenzoic acid (manufactured by Tokyo Chemical Industry Co., Ltd .: containing about 30% by mass of water; the same applies hereinafter) was added. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. After completion of the reaction, 5 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (5 ml × 3). The obtained organic layer was washed with 5 ml of 1 mol / L sodium hydroxide aqueous solution, dehydrated and dried over anhydrous sodium sulfate, and then 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 95: 5 to 5:95) to obtain 75 mg of the desired product as a pale yellow solid.
Melting point: 153-154 ° C
¹ H-NMR (CDCl ₃ ): δ9.56 (d, J = 7.2Hz, 1H), 8.09 (s, 1H), 7.19 (d, J = 7.2Hz, 1H), 4.43 (s, 3H), 3.60 -3.30 (m, 2H), 1.50 (t, J = 7.5Hz, 3H).
Synthesis Example 5: 3- (Ethylsulfonyl) -N-methyl-7- (trifluoromethyl) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1, 2-a] Synthesis of pyridine-2-carboxamide (Compound No. 4-001a of the present invention) 3- (ethylthio) -N-methyl-7- (trifluoromethyl)-synthesized by the method described in Synthesis Example 3 above To a mixed solution of 150 mg of N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide and 3 ml of chloroform under ice cooling. 193 mg of 65 wt% metachloroperbenzoic acid (containing about 30 wt% water) was added. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After completion of the reaction, 5 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (5 ml × 3). The obtained organic layer was washed with 5 ml of 1 mol / L sodium hydroxide aqueous solution, dehydrated and dried over anhydrous sodium sulfate, and then 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 95: 5 to 5:95) to obtain 183 mg of the desired product as a pale yellow oil. . ¹ H-NMR (CDCl ₃ ): δ 9.16 (d, J = 7.5Hz, 1H), 8.15 (s, 1H), 7.38 (d, J = 7.5Hz, 1H), 3.87 (s, 3H), 3.57 (q, J = 7.5Hz, 2H), 1.42 (t, J = 7.5Hz, 3H).
Synthesis Example 6: 3- (Ethylthio) -7-iodo-N-methyl-N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine Synthesis of 2-carboxamide (Compound No. 4-002c of the present invention) 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid 624 mg, 1,2-dichloroethane 10 ml and tetrahydrofuran 1 ml To this mixed solution, 765 mg of 4-dimethylaminopyridine and 741 mg of 2-methyl-6-nitrobenzoic anhydride were sequentially added at room temperature. After completion of the addition, the mixture was stirred at room temperature for 20 minutes. 344 mg of N-methyl-5- (trifluoromethyl) -1,3,4-thiadiazol-2-amine was added to the reaction mixture, and the mixture was stirred at room temperature for 21 hours. After completion of the reaction, 10 ml of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with chloroform (10 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 100: 0 to 50:50 gradient) to obtain 554 mg of the desired product as a pale yellow solid.
¹ H-NMR (CDCl ₃ ): δ 8.32 (d, J = 7.5Hz, 1H), 8.13 (s, 1H), 7.35-7.25 (m, 1H), 4.03 (s, 3H), 2.94 (q, J = 7.2Hz, 2H), 1.27 (t, J = 7.2Hz, 3H).
Melting point: 184-186 ° C
Synthesis Example 7: 7-Cyano-3- (ethylthio) -N-methyl-N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine- Synthesis of 2-carboxamide (Compound No. 4-003c of the present invention) 3- (ethylthio) -7-iodo-N-methyl-N- [5- (trifluoromethyl)-synthesized by the method described in Synthesis Example 6 To a mixed solution of 350 mg of 1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide, 120 mg of zinc cyanide and 3.4 ml of N-methyl-2-pyrrolidone, tetrakis (tri 79 mg of enylphosphine) palladium (0) was added. After replacing the inside of the reaction vessel with nitrogen gas, the mixture was stirred at 120 ° C. for 2 hours. After completion of the reaction, 0.2 ml of 28% by mass aqueous ammonia was added to the reaction mixture, followed by extraction with chloroform (10 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 50:50) to obtain 109 mg of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ8.67 (d, J = 7.2Hz, 1H), 8.15-8.10 (m, 1H), 7.25-7.15 (m, 1H), 4.03 (s, 3H), 2.99 ( q, J = 7.5Hz, 2H), 1.23 (t, J = 7.5Hz, 3H).
Melting point: 194-195 ° C
Synthesis Example 8 7-Cyano-3- (ethylsulfonyl) -N-methyl-N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] Synthesis of pyridine-2-carboxamide (the present compound No. 4-003a) 7-Cyano-3- (ethylthio) -N-methyl-N- [5- (trifluoromethyl) synthesized by the method described in Synthesis Example 7 ) -1,3,4-thiadiazol-2yl] imidazo [1,2-a] pyridine-2-carboxamide in a mixed solution of 82 mg and 2 ml of chloroform was added 111 mg of 65% by mass metachloroperbenzoic acid under ice-cooling. did. After the addition was complete, the reaction mixture was stirred at room temperature for 3 hours. After completion of the reaction, 5 ml of a saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (5 ml × 3). The obtained organic layer was washed with 5 ml of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated 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 (gradient of n-hexane: ethyl acetate = 100: 0-50: 50) to obtain 34 mg of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ 9.15-9.10 (m, 1H), 8.25-8.20 (m, 1H), 7.40-7.30 (m, 1H), 3.87 (s, 3H), 3.57 (q, J = 7.5Hz, 2H), 1.41 (t, J = 7.5Hz, 3H).
Melting point: 161-165 ° C
Synthesis Example 9: 3- (Ethylsulfonyl) -7-iodo-N-methyl-N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] Synthesis of Pyridine-2-carboxamide (Compound No. 4-002a of the Present Invention) 3- (Ethylthio) -7-iodo-N-methyl-N- [5- (trifluoromethyl) synthesized by the method described in Synthesis Example 6 ) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide 91 mg and chloroform 2 mass 99 ml were added 99% 65% metachloroperbenzoic acid at 0 ° C. did. The reaction mixture was stirred at room temperature for 14 hours. To the reaction mixture was added 5 ml of a saturated aqueous sodium thiosulfate solution, and the mixture was extracted with chloroform (5 ml × 3). The obtained organic layer was washed with 5 ml of a saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated 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 (n-hexane: ethyl acetate = 100: 0 to 50:50 gradient) to obtain 89 mg of the desired product as a pale yellow solid.
¹ H-NMR (CDCl ₃ ): δ8.75-8.70 (m, 1H), 8.25 (s, 1H), 7.50-7.40 (m, 1H), 3.85 (s, 3H), 3.51 (q, J = 7.5 Hz, 2H), 1.39 (t, J = 7.5Hz, 3H).
Melting point: 185-188 ° C
Synthesis Example 10: 3- (Ethylsulfonyl) -N-methyl-7- (methylthio) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2- a] Synthesis of pyridine-2-carboxamide (Compound No. 4-004a of the present invention) Step 1: 2-ethylhexyl 3-[(3- [ethylsulfonyl] -2- (methyl [5- (trifluoromethyl) -1 , 3,4-thiadiazol-2-yl] carbamoyl) imidazo [1,2-a] pyridin-7-yl) thio] propanoate 3- (ethylsulfonyl) -7 synthesized by the method described in Synthesis Example 9 90 mg of iodo-N-methyl-N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide; To a mixed solution of 1 ml of 1,4-dioxane, 85 μl of diisopropylethylamine, 10 mg of 4,5-bis (diphenylphosphino) -9,9-dimethylxanthene, 10 mg of tris (dibenzylideneacetone) dipalladium (0) at room temperature. And 54 mg of 2-ethylhexyl 3-mercaptopropanoate were added sequentially. The inside of the reaction vessel was replaced with nitrogen gas, and then stirred for 2 hours under heating and reflux. 5 ml of water was added to the reaction mixture, and the mixture was extracted with chloroform (5 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 95: 5 to 60:40 gradient) to obtain the desired product (95 mg) as a yellow oil.
¹ H-NMR (CDCl ₃ ): δ8.80-8.75 (m, 1H), 7.55-7.45 (m, 1H), 7.05-7.00 (m, 1H), 4.10-4.00 (m, 2H), 3.86 (s , 3H), 3.50 (q, J = 7.2Hz, 2H), 3.35 (t, J = 7.2Hz, 2H), 2.79 (t, J = 7.2Hz, 2H), 1.45-1.20 (m, 12H), 0.95 -0.85 (m, 6H).
Step 2: 3- (Ethylsulfonyl) -N-methyl-7- (methylthio) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a ] Synthesis of pyridine-2-carboxamide (Compound No. 4-004a of the present invention) 2-ethylhexyl 3-[(3- [ethylsulfonyl] -2- (methyl [5- (tri Fluoromethyl) -1,3,4-thiadiazol-2-yl] carbamoyl) imidazo [1,2-a] pyridin-7-yl) thio] propanoate in a mixed solution of 179 mg and tetrahydrofuran 2.8 ml at room temperature , 8-diazabicyclo [5.4.0] -7-undecene 129 mg was added. The reaction mixture was stirred for 4 hours. To the reaction mixture, 139 mg of methyl trifluoromethanesulfonate was added and stirred at room temperature for 1.5 hours. After completion of the reaction, 5 ml of a saturated aqueous ammonium chloride solution was added to the reaction mixture, and the mixture was extracted with chloroform (5 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (n-hexane: ethyl acetate = 95: 5 to 50:50 gradient) to obtain 40 mg of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ8.75-8.70 (m, 1H), 7.40-7.35 (m, 1H), 7.05-6.95 (m, 1H), 3.86 (s, 3H), 3.49 (q, J = 7.5Hz, 2H), 2.60 (s, 3H), 1.39 (t, J = 7.5Hz, 3H).
Synthesis Example 11 3- (Ethylsulfonyl) -N-methyl-7- (methylsulfinyl) -N- [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2 -A] Synthesis of pyridine-2-carboxamide (Compound No. 4-005a of the present invention) 3- (ethylsulfonyl) -N-methyl-7- (methylthio) -N- synthesized by the method described in Synthesis Example 10 above 30 weights at room temperature in a mixed solution of 40 mg of [5- (trifluoromethyl) -1,3,4-thiadiazol-2-yl] imidazo [1,2-a] pyridine-2-carboxamide and 0.3 ml of acetic acid 10% aqueous hydrogen peroxide was added. The reaction mixture was stirred at room temperature for 19 hours. The reaction mixture was purified by medium pressure preparative liquid chromatography eluting with n-hexane-ethyl acetate (gradient of 100: 0 to 0: 100) to obtain 26 mg of the desired product as a white solid.
Melting point: 174-177 ° C
¹ H-NMR (CDCl ₃ ): δ9.15 (d, J = 7.5Hz, 1H), 8.18 (s, 1H), 7.40-7.30 (m, 1H), 3.87 (s, 3H), 3.56 (q, J = 7.5Hz, 2H), 2.87 (s, 3H), 1.42 (t, J = 7.5Hz, 3H).
Below, the synthesis example of the synthetic intermediate of this invention compound is described.

Intermediate Synthesis Example 1: Synthesis of 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid Step 1: 3-iodo-7- (trifluoromethyl) imidazo Synthesis of ethyl [1,2-a] pyridine-2-carboxylate of 3.73 g of ethyl 7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylate and 20 ml of N, N-dimethylformamide. To the mixed solution, 6.5 g of N-iodosuccinimide was added at room temperature. After completion of the addition, the reaction mixture was stirred at 80 ° C. for 5 hours. After completion of the reaction, water was added to the reaction mixture, and the precipitated solid was separated by filtration. The obtained solid was dissolved in 20 ml of chloroform, and washed with a saturated aqueous sodium thiosulfate solution and then with saturated sodium hydrogen carbonate. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 5.08 g of the desired product as a pale yellow solid.
Melting point: 183-185 ° C
¹ H-NMR (CDCl ₃ ): δ8.40 (d, J = 7.2Hz, 1H), 7.99 (s, 1H), 7.17 (dd, J = 7.2, 1.7Hz, 1H), 4.53 (q, J = 7.2Hz, 2H), 1.50 (t, J = 7.2Hz, 3H).
Step 2: Synthesis of ethyl 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylate 3-Iodo-7- (trifluoromethyl) imidazo [1,2- a] To a mixed solution of 5.73 g of ethyl pyridine-2-carboxylate and 40 ml of 1,4-dioxane at room temperature, 5.79 g of diisopropylethylamine, 4,5-bis (diphenylphosphino) -9,9-dimethyl 862 mg of xanthene, 682 mg of tris (dibenzylideneacetone) dipalladium (zero valent), and 1.85 g of ethanethiol were sequentially added. After completion of the addition, the inside of the reaction vessel was replaced with nitrogen gas, and then stirred for 2 hours under heating and reflux. After completion of the reaction, the reaction mixture was filtered using celite, and the celite was washed with 30 ml of chloroform. The obtained filtrate and washing solution were combined 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 100: 0 to 50:50) to obtain 5.58 g of the objective product as a brown solid. It was.
Melting point: 50-52 ° C
¹ H-NMR (CDCl ₃ ): δ 8.67 (d, J = 7.4Hz, 1H), 8.02-8.00 (m, 1H), 7.15 (dd, J = 7.4, 1.8Hz, 1H), 4.52 (q, J = 7.0Hz, 2H), 2.98 (q, J = 7.5Hz, 2H), 1.48 (t, J = 7.0Hz, 3H), 1.20 (t, J = 7.5Hz, 3H).
Step 3: Synthesis of 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2 -A] To a mixed solution of 5.58 g of ethyl pyridine-2-carboxylate, 60 ml of ethanol and 30 ml of tetrahydrofuran, 10 ml of a 3 mol / L aqueous sodium hydroxide solution was added at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 5 hours. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. A 1 mol / L hydrochloric acid aqueous solution was added to the obtained residue to adjust the pH of the aqueous layer to 2, followed by extraction with ethyl acetate (20 ml × 2). The obtained organic layer was dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 3.40 g of the desired product as a yellow solid.
Melting point: 163-171 ° C
¹ H-NMR (CDCl ₃ ): δ 8.69 (d, J = 7.2Hz, 1H), 8.19 (s, 1H), 7.22 (dd, J = 7.2, 1.4Hz, 1H), 3.06 (q, J = (7.4Hz, 2H), 1.23 (t, J = 7.4Hz, 3H) (CO ₂ H proton signal could not be observed).
Intermediate Synthesis Example 2: Synthesis of 3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carbonyl chloride Step 1: 3- (ethylsulfonyl) -7- (tri Synthesis of fluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid 5.00 g of 3- (ethylthio) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxylic acid and To a mixed solution of 43 ml of acetic acid, 4.88 g of 30% by weight hydrogen peroxide and 10 mg of sodium tungsten (VI) dihydrate were sequentially added at room temperature. After completion of the addition, the reaction mixture was stirred at 50 ° C. for 6 hours. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. The precipitated solid was washed with 30 ml of hexane and filtered off by filtration to obtain 4.39 g of the desired product as a pale yellow solid.
¹ H-NMR (CDCl ₃ ): δ9.41 (d, J = 7.2Hz, 1H), 8.08 (s, 1H), 7.30-7.20 (m, 1H), 3.78 (q, J = 7.2Hz, 2H) , 1.34 (t, J = 7.2Hz, 3H) (The proton signal of CO ₂ H could not be observed).
Step 2: Synthesis of 3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1,2-a] pyridine-2-carbonyl chloride 3- (ethylsulfonyl) -7- (trifluoromethyl) imidazo [1 , 2-a] To a mixed solution of 4.39 g of pyridine-2-carboxylic acid and 13.6 ml of dichloromethane, 2.3 ml of oxalyl chloride and 1 drop of N, N-dimethylformamide were sequentially added at room temperature. After the addition was complete, the reaction mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. The precipitated solid was washed with 30 ml of hexane and filtered off by filtration to obtain 4.52 g of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ9.39 (d, J = 7.5Hz, 1H), 8.20 (brs, 1H), 7.40-7.30 (m, 1H), 3.64 (q, J = 7.5Hz, 2H) , 1.38 (t, J = 7.5Hz, 3H).
Intermediate Synthesis Example 3: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid Step 1: 7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid Synthesis of ethyl acid To a mixed solution of 19.0 g of 2-amino-4-iodopyridine and 100 ml of ethanol, 9.4 g of sodium bicarbonate and 22.0 g of ethyl bromopyruvate were sequentially added at room temperature. The reaction mixture was stirred for 2 hours under heating to reflux. After completion of the reaction, the solvent was distilled off under reduced pressure. 100 ml of water and 100 ml of diisopropyl ether were added to the obtained residue, and the precipitated solid was removed by filtration. 100 ml of ethanol was added to the obtained solid, and the solvent was distilled off under reduced pressure. 100 ml of toluene was added to the obtained residue, and the solvent was distilled off under reduced pressure to obtain 23.4 g of the desired product as an orange solid.
¹ H-NMR (CDCl ₃ ): δ8.15-8.05 (m, 2H), 7.90-7.85 (m, 1H), 7.10-7.05 (m, 1H), 4.45 (q, J = 7.2Hz, 2H), 1.43 (t, J = 7.2Hz, 3H).
Step 2: Synthesis of ethyl 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylate To a mixed solution of 3.38 g of N-chlorosuccinimide and 31 ml of 1,2-dichloroethane, -20 At 28 ° C., 2.28 ml of ethanethiol was added. The reaction mixture was stirred at room temperature for 4 hours. To the reaction mixture, 1.00 g of ethyl 7-iodoimidazo [1,2-a] pyridine-2-carboxylate was added at room temperature. The reaction mixture was stirred for 6 hours under heating to reflux. To the reaction mixture, a solution of 3.38 g of N-chlorosuccinimide prepared in a separate container and 2.28 ml of ethanethiol in 31 ml of 1,2-dichloroethane was added at room temperature. The reaction mixture was stirred for 5 hours under heating to reflux. After completion of the reaction, 100 ml of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture, and the mixture was extracted with chloroform (100 ml × 2). The obtained organic layer was dehydrated 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 (gradient of n-hexane-ethyl acetate = 98: 2-90: 10) to obtain 880 mg of the desired product as a brown solid.
¹ H-NMR (CDCl ₃ ): δ 8.29 (d, J = 6.6Hz, 1H), 8.10 (d, J = 0.9Hz, 1H), 7.21 (dd, J = 7.2, 1.5Hz, 1H), 4.49 (q, J = 7.2Hz, 2H), 2.93 (q, J = 7.2Hz, 2H), 1.47 (t, J = 7.5Hz, 3H), 1.18 (t, J = 7.5Hz, 3H).
Step 3: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid To a mixed solution of 880 mg of ethyl acid and 9 ml of tetrahydrofuran, 3 ml of 0.6 mol / L lithium hydroxide aqueous solution was added at 0 ° C. The reaction mixture was stirred at room temperature for 3 hours. After completion of the reaction, the solvent of the reaction mixture was distilled off under reduced pressure. 10 ml of water was added to the obtained residue, and the aqueous layer was washed with 10 ml of diethyl ether. 2 mol / L hydrochloric acid was added to the obtained aqueous layer to adjust the pH of the aqueous layer to 2, followed by extraction with chloroform (10 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 654 mg of the desired product as a yellow solid.
Melting point: 175-178 ° C
Intermediate Synthesis Example 4: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid Step 1: 7-iodo-3-thiocyanatoimidazo [1,2-a Synthesis of ethyl pyridine-2-carboxylate 7-iodoimidazo [1,1] synthesized in the mixed solution of 184 mg of potassium thiocyanate and 3 ml of acetonitrile at 0 ° C. by the method of Step 1 of Intermediate Synthesis Example 3 2-a] 300 mg of ethyl pyridine-2-carboxylate was added sequentially. The reaction mixture was stirred at room temperature for 1 hour. The reaction mixture was stirred at 60 ° C. for 2 hours. After completion of the reaction, 5 ml of a 10% by mass aqueous sodium hydrogen sulfite solution and 10 ml of chloroform were sequentially added to the reaction mixture. The reaction mixture was filtered using celite, and the celite was washed with chloroform. The obtained filtrate and washings were combined and extracted with 10 ml of chloroform. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane-ethyl acetate = 100: 5 to 50:50) to obtain 161 mg of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ 8.30-8.25 (m, 1H), 8.17 (d, J = 6.9Hz, 1H), 7.47 (dd, J = 6.9, 1.5Hz, 1H), 4.54 (q, J = 6.9Hz, 2H), 1.49 (t, J = 6.9Hz, 3H).
Step 2: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid 7-iodo-3-thiocyanatoimidazo [1,2-a obtained in Step 1 ] To a mixed solution of 106 mg of ethyl pyridine-2-carboxylate and 2 ml of ethanol, 193 mg of an ethanol solution of 21% by mass sodium ethoxide (manufactured by Sigma-Aldrich) was added at room temperature. The reaction mixture was stirred at 60 ° C. for 30 minutes. To the reaction mixture, 109 mg of an ethanol solution of 21% by mass sodium ethoxide and 109 mg of iodoethane were sequentially added at room temperature. The reaction mixture was stirred at room temperature for 30 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure. To the obtained residue, 10 ml of a 1.0 mol / L aqueous sodium hydroxide solution was added, and the aqueous layer was washed with 10 ml of chloroform. Concentrated hydrochloric acid was added to the obtained aqueous layer to adjust the pH of the aqueous layer to 3, followed by extraction with 10 ml of chloroform. The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 33 mg of the desired product as a light brown solid.
¹ H-NMR (CDCl ₃ ): δ8.50-8.20 (m, 2H), 7.30-7.20 (m, 1H), 3.00 (q, J = 7.2Hz, 2H), 1.18 (t, J = 7.2Hz, 3H) (Proton signal of CO ₂ H could not be observed).
Intermediate Synthesis Example 5: Synthesis of ethyl 7-cyano-3- (ethylthio) imidazo [1,2-a] pyridine-2-carboxylate Step 1: Ethyl 3- (ethylthio) -2- (methoxyimino) propionate Synthesis of ethyl 3-bromo-2- (methoxyimino) propionate (5.5 g) and N, N-dimethylformamide (20 ml) at 0 ° C., ethyl mercaptan (2.2 ml) and potassium carbonate (4.1 g) were sequentially added. did. The reaction mixture was stirred at room temperature for 2 hours. After completion of the reaction, 100 ml of water was added to the reaction mixture and extracted with diethyl ether (100 ml × 2). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 5.6 g of the desired product as a yellow oil.
¹ H-NMR (CDCl ₃ ): δ4.35 (q, J = 7.2Hz, 2H), 4.06 (s, 3H), 3.58 (s, 2H), 2.54 (q, J = 7.5Hz, 2H), 1.36 (t, J = 7.2Hz, 3H), 1.26 (t, J = 7.5Hz, 3H).
Step 2: Synthesis of ethyl 3- (ethylsulfinyl) -2- (methoxyimino) propionate Mixing of 2.0 g of ethyl 3- (ethylthio) -2- (methoxyimino) propionate obtained in Step 1 and 20 ml of chloroform To the solution, 2.6 g of 65% by mass metachloroperbenzoic acid was added at 0 ° C. The reaction mixture was stirred at 0 ° C. for 30 minutes. After completion of the reaction, 15 ml of a 10% by weight saturated aqueous sodium thiosulfate solution was added to the reaction mixture, followed by extraction with chloroform (20 ml × 3). The obtained organic layer was washed with 100 ml of saturated aqueous sodium hydrogen carbonate solution. The organic layer was dehydrated 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 (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 1.7 g of the desired product as a pale yellow oil. .
¹ H-NMR (CDCl ₃ ): δ 4.37 (q, J = 7.2Hz, 2H), 4.15 (s, 3H), 4.10-4.00 (m, 2H), 2.85-2.65 (m, 2H), 1.45- 1.30 (m, 6H).
Separately from the desired product, 351 mg of ethyl 3- (ethylsulfonyl) -2- (methoxyimino) propionate was obtained as a pale yellow solid.
¹ H-NMR (CDCl ₃ ): δ 4.39 (s, 2H), 4.38 (q, J = 7.5Hz, 2H), 3.06 (s, 3H), 3.06 (q, J = 7.5Hz, 2H), 1.42 (t, J = 7.5Hz, 3H), 1.38 (t, J = 7.5Hz, 3H).
Step 3: Synthesis of ethyl 3-chloro-3- (ethylthio) -2- (methoxyimino) propionate 200 mg of ethyl 3- (ethylsulfinyl) -2- (methoxyimino) propionate obtained in Step 2 and 3 ml of dichloromethane 108 mg of thionyl chloride was added to the mixed solution at 0 ° C. The reaction mixture was stirred at room temperature for 10 minutes. After completion of the reaction, the solvent was distilled off under reduced pressure to obtain 250 mg of the desired product as a light brown oil.
¹ H-NMR (CDCl ₃ ): δ6.31 (s, 1H), 4.38 (q, J = 7.2Hz, 2H), 4.16 (s, 3H), 2.82 (q, J = 7.5Hz, 2H), 1.38 (t, J = 7.2Hz, 3H), 1.35 (t, J = 7.5Hz, 3H).
Step 4: Synthesis of ethyl 7-cyano-3- (ethylthio) imidazo [1,2-a] pyridine-2-carboxylate 3-Chloro-3- (ethylthio) -2- (methoxyimino obtained in Step 3 ) 94 mg of 4-cyanopyridine was added to a mixed solvent of 250 mg of ethyl propionate and 2 ml of acetonitrile at room temperature. The reaction mixture was stirred for 2 hours under heating to reflux. 116 mg of N, N-diisopropylethylamine was added to the reaction mixture, and the mixture was stirred for 1 hour with heating under reflux. After completion of the reaction, 5 ml of 1 mol / L hydrochloric acid was added to the reaction mixture, followed by extraction with chloroform (5 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure. The obtained residue was purified by medium pressure preparative liquid chromatography (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 50 mg of the desired product as a pale yellow oil.
¹ H-NMR (CDCl ₃ ): δ 8.66 (dd, J = 7.2, 0.9Hz, 1H), 8.15-8.10 (m, 1H), 7.12 (dd, J = 7.2, 1.7Hz, 1H), 4.52 ( q, J = 7.2Hz, 2H), 3.00 (q, J = 7.4Hz, 2H), 1.48 (t, J = 7.2Hz, 3H), 1.20 (q, J = 7.4Hz, 3H).
The compounds of the present invention and synthetic intermediates can be synthesized according to the above production method and synthesis examples. Examples of the condensed heterocyclic compounds produced in the same manner as in Synthesis Examples 1 to 11 and Intermediate Synthesis Examples 1 to 5 are shown in Tables 5 to 10, but are included in the present invention. The heterocyclic compound is not limited to these.

  In the table, "Me" is a methyl group, "Et" is an ethyl group, "n-Pr" is a normal propyl group, "c-Pr" is a cyclopropyl group, and "Ac" The notation represents an acetyl group. The notation “*” represents that the compound is an oily or resinous compound having no melting point.

  [Table 5]

――――――――――――――――――――――――――――――――
No. n Y2 Y3 R ² X ² X ³ X ⁴ mp (℃)
――――――――――――――――――――――――――――――――
1-001a 2 H CF ₃ HH CF ₃ H 213-215
1-002a 2 H CF ₃ Me H CF ₃ H *
1-003a 2 H CF ₃ H CF ₃ H CF ₃ 205-208
1-004a 2 H CF ₃ Me CF ₃ H CF ₃ *
――――――――――――――――――――――――――――――――
[Table 6]

――――――――――――――――――――――――――――――――――――
No. n Y2 Y3 Y4 R ² X ¹ X ² X ³ mp (℃)
――――――――――――――――――――――――――――――――――――
2-001b 0 CF ₃ HH Me HH CF ₃ *
2-001a 2 CF ₃ HH Me HH CF ₃ 168-170
2-002a 2 H CF ₃ HHH CF ₃ H 194-199
2-003a 2 H CF ₃ H n-Pr H CF ₃ H *
――――――――――――――――――――――――――――――――――――
[Table 7]

――――――――――――――――――――――――――――――
No. n Y2 Y3 R ² X ³ mp (℃)
――――――――――――――――――――――――――――――
3-001a 2 H CF ₃ Me CF ₃ 224-226
――――――――――――――――――――――――――――――
[Table 8]

――――――――――――――――――――――――――――――
No. n Y2 Y3 R ² X ³ mp (℃)
――――――――――――――――――――――――――――――
4-001b 0 H CF ₃ Me CF ₃ 84-86
4-001c 1 H CF ₃ Me CF ₃ 153-154
4-001a 2 H CF ₃ Me CF ₃ *
4-002c 0 HI Me CF ₃ 184-186
4-002a 2 HI Me CF ₃ 185-188
4-003c 0 H CN Me CF ₃ 194-195
4-003a 2 H CN Me CF ₃ 161-165
4-004a 2 H SMe Me CF ₃ *
4-005a 2 HS (O) Me Me CF ₃ 174-177
――――――――――――――――――――――――――――――
[Table 9]

――――――――――――――――――――――――――――――
No. n Y2 Y3 R ² X ⁶ mp (℃)
――――――――――――――――――――――――――――――
5-001a 2 H CF ₃ HF 197-200
5-002a 2 H CF ₃ Me F *
――――――――――――――――――――――――――――――
[Table 10]

――――――――――――――――――――――――――――――
No. n Y2 Y3 Y4 X ¹ X ⁴ mp (℃)
――――――――――――――――――――――――――――――
5-021c 0 IHH NHMe CF ₃ 90-92
5-026c 0 H CF ₃ H NHMe CF ₃ 135-140
5-027c 0 HIH NHMe CF ₃ *
――――――――――――――――――――――――――――――
Examples of synthetic intermediates of the compounds of the present invention are shown below [Table 11]

―――――――――――――――――――――――――――
No. n Y2 Y3 Y4 Z1 mp (℃)
―――――――――――――――――――――――――――
i1-001c 0 CF ₃ HH OEt 76-78
i1-002c 0 IHH OEt 110-112
i1-002a 2 IHH OEt 202-204
i1-004c 0 Cl HH OEt 63-64
i1-007c 0 H CF ₃ H OEt 50-52
i1-007a 2 H CF ₃ H OEt 129-131
i1-008a 2 HIH OEt 124-126
i1-010c 0 H Cl H OEt 70-71
i1-012c 0 H NH ₂ H OEt *
i1-012a 2 H NH ₂ H OEt *
i1-013a 2 H NHAc H OEt *
i1-014c 0 H NO ₂ H OEt 234-235
i1-017c 0 H CN H OEt *
i1-020c 0 CF ₃ HH OH 200-201
i1-021c 0 IHH OH 214-215
i1-021a 2 IHH OH 164-166
i1-022c 0 Br HH OH 170-173
i1-023c 0 Cl HH OH 178-180
i1-026c 0 H CF ₃ H OH 163-171
i1-026a 2 H CF ₃ H OH 158-160
i1-027c 0 HIH OH 175-178
i1-027a 2 HIH OH 148-150
i1-028c 0 H Br H OH 150-152
i1-029c 0 H Cl H OH 210-212
i1-031a 2 H NH ₂ H OH *
―――――――――――――――――――――――――――
[Table 12]

―――――――――――――――――――――――――――――
No. Y2 Y3 Y4 Z1 Z2 mp (℃)
―――――――――――――――――――――――――――――
i2-001 CF ₃ HH OEt H 84-88
i2-003 Br HH OEt H 103-104
i2-007 H CF ₃ H OEt H 180-182
i2-009 H Br H OEt H 154-157
i2-010 H Cl H OEt H 170-174
i2-020 CF ₃ HH OH H 245-250
i2-065 HIH OEt Cl 149-151
i2-115 CF ₃ HH OEt Br 114-116
i2-175 Cl HH OEt I 168-169
i2-178 H CF ₃ H OEt I 183-185
i2-181 H Cl H OEt I 160-162
i2-190 HHH OEt I 133-135
―――――――――――――――――――――――――――――
Of the compounds of the present invention and synthetic intermediates shown in Tables 5 to 12, ¹ H-NMR data of compounds having no melting point are shown in Table 13. In addition, No.i1-031a was measured in a heavy water solvent, and other than that was measured in deuterated chloroform.

[Table 13]
―――――――――――――――――――――――――――――――――――――
No. ¹ H NMR (CDCl ₃ , Me ₄ Si, 300 MHz).
―――――――――――――――――――――――――――――――――――――
1-002a
δ9.04 (d, J = 7.2Hz, 1H), 7.82 (s, 1H), 7.55-7.40 (m, 4H), 7.25-7.10 (m, 1H), 3.62 (q, J = 7.5Hz, 2H) , 3.55 (s, 3H), 1.37 (t, J = 7.5Hz, 3H).
1-004a
δ9.02 (brs, 1H), 8.10-7.50 (m, 4H), 7.20 (brs, 1H), 3.70-3.35 (m, 5H), 1.37 (t, J = 7.8Hz, 3H).
2-001b
δ8.83 (s, 1H), 8.62 (s, 1H), 7.77 (dd, J = 8.7, 1.8Hz, 1H), 7.64 (d, J = 9.6Hz, 1H), 7.55-7.40 (m, 2H) , 3.67 (s, 3H), 2.92 (q, J = 7.2Hz, 2H), 1.24 (t, J = 7.2Hz, 3H).
2-003a
δ9.14 (d, J = 7.5Hz, 1H), 8.59 (d, J = 5.1Hz, 1H), 7.87 (brs, 1H), 7.30-7.15 (m, 3H), 4.12 (t, J = 7.2Hz , 2H), 3.64 (q, J = 6.9Hz, 2H), 1.85-1.65 (m, 2H), 1.38 (t, J = 7.2Hz, 3H), 1.00-0.85 (m, 3H).
4-001a
δ9.16 (d, J = 7.5Hz, 1H), 8.15 (s, 1H), 7.38 (d, J = 7.5Hz, 1H), 3.87 (s, 3H), 3.57 (q, J = 7.5Hz, 2H ), 1.42 (t, J = 7.5Hz, 3H) .5-002a δ9.03 (d, J = 7.2Hz, 1H), 7.86 (s, 1H), 7.25-7.05 (m, 3H), 6.86 (d , J = 8.4Hz, 1H), 3.60 (q, J = 7.5Hz, 2H), 3.49 (s, 3H), 1.36 (t, J = 7.5Hz, 3H).
5-027c
δ9.00-8.90 (brs, 1H), 8.35-8.30 (m, 2H), 8.10-8.00 (m, 1H), 7.92 (d, J = 1.8Hz, 1H), 7.30-7.20 (m, 1H), 5.30-5.20 (brs, 1H), 3.09 (d, J = 5.1Hz, 3H), 3.01 (q, J = 7.5Hz, 2H), 1.19 (t, J = 7.4Hz, 3H).
i1-012c
δ8.27 (d, J = 7.4Hz, 1H), 6.75-6.65 (m, 1H), 6.46 (dd, J = 7.4, 1.6Hz, 1H), 4.46 (q, J = 7.0Hz, 2H), 4.20 -4.05 (brs, 2H), 2.87 (q, J = 7.4Hz, 2H), 1.44 (t, J = 7.0Hz, 3H), 1.17 (t, J = 7.4Hz, 3H).
i1-012a
δ8.90 (d, J = 7.2Hz, 1H), 6.76 (s, 1H), 6.58-6.48 (m, 1H), 4.48 (q, J = 7.2Hz, 2H), 4.45 (brs, 2H), 3.65 (q, J = 7.2Hz, 2H), 1.45 (t, J = 7.2Hz, 3H), 1.33 (t, J = 7.2Hz, 3H).
i1-013a
δ9.12 (d, J = 8.1Hz, 1H), 8.06 (s, 1H), 7.63-7.58 (m, 1H), 7.34 (d, J = 8.1Hz, 1H), 4.51 (q, J = 7.2Hz , 2H), 3.70 (q, J = 7.2Hz, 2H), 2.25 (s, 3H), 1.47 (t, J = 7.2Hz, 3H), 1.34 (t, J = 7.2Hz, 3H).
i1-017c
δ8.66 (dd, J = 7.2, 0.9Hz, 1H), 8.15-8.10 (m, 1H), 7.12 (dd, J = 7.2, 1.7Hz, 1H), 4.52 (q, J = 7.2Hz, 2H) , 3.00 (q, J = 7.4Hz, 2H), 1.48 (t, J = 7.2Hz, 3H), 1.20 (q, J = 7.4Hz, 3H).
i1-031a
δ8.35 (d, J = 6.6Hz, 1H), 6.62 (d, J = 6.6Hz, 1H), 6.61 (s, H), 3.43 (q, J = 7.5Hz, 2H), 1.91 (t, J = 7.5Hz, 3H) (NH ₂ and CO ₂ H proton signals could not be observed).
―――――――――――――――――――――――――――――――――――――
Next, the usefulness of the compound of the present invention as a pest control agent will be specifically described in the following test examples, but the present invention is not limited thereto.

Test Example 1: Insecticidal test against brown planthopper A 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. Rice leaf sheaths were immersed in the chemical solution for about 10 seconds. After the dipping operation was finished, the leaf sheath of the rice treated with the chemical solution was air-dried and then placed in a test tube. In this, 5 third-instar larvae of the green planthopper (Nilaparvatta lugens) were released per test tube, covered with a sponge, and housed in a constant temperature room at 25 ° C. Six days after accommodation, the number of dead planthoppers in the test tube was examined, and the death rate was calculated from the following formula. In addition, the test was performed by 2 continuous systems.

(Calculation formula) Death rate (%) = (Number of dead insects / Number of test insects) × 100
As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
The present compound: 1-002a, 4-001a, 4-002a, 4-003a, 4-005a.

Test Example 2: Insecticidal test for goldfish 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. In the chemical solution, kanran leaves were immersed for about 10 seconds. After the dipping operation was completed, the kanran leaves treated with the chemical solution were air-dried and then placed in a petri dish. In this, 5 third-instar larvae of Pterella xylostella were released per petri dish, covered, and housed in a thermostatic chamber at 25 ° C. Six days after housing, the number of dead moths in petri dishes was examined, and the mortality rate was calculated from the same calculation formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001a, 1-002a, 1-004a, 2-001b, 2-001a, 2-002a, 2-003a, 4-001b, 4-001c, 4-001a, 4-002c, 4- 002a, 4-003a, 4-005a, 5-002a, 5-021c, 5-026c.

Test Example 3: Insecticidal test against Spodoptera litura 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. In the chemical solution, kanran leaves were immersed for about 10 seconds. After the dipping operation was completed, the kanran leaves treated with the chemical solution were air-dried and then placed in a petri dish. In this, 5 third-instar larvae of Spodoptera litura were released per petri dish, covered, and housed in a thermostatic chamber at 25 ° C. Six days after being housed, the number of dead insects of Spodoptera litura in the petri dish was examined, and the death rate was calculated from the same formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-001a, 1-002a, 1-003a, 1-004a, 2-001b, 2-001a, 2-002a, 4-001a, 4-002c, 4-002a, 5-002a.

Test Example 4: Insecticidal activity against citrus white thrips A wet filter paper was laid on a 7 cm inner diameter styrol cup, and 3 mm square green beans were placed on it, and 20 larvae of the citrus white thrips (Franklinella occentalis) per leaf were placed. Head inoculated. A 10% emulsion of the compound of the present invention (a 10% wettable powder was tested depending on the compound) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. The prepared chemical solution was sprayed by 2.5 ml per styrene cup using a rotary spray tower (2.5 mg / cm ² ). The number of dead citrus thrips ingested two days later and the damage of green beans were investigated. The mortality was calculated from the same calculation formula as in Test Example 1. The damage degree was determined as follows. 1: 0-20% damage, 2: 20-50% damage, 3: 50-70% damage, 4: 70% or more damage. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a mortality rate of 50% or more and a food damage level of 2 or more.
The compound of the present invention: 1-002a, 1-003a, 1-004a, 2-001b, 2-001a, 4-003c.

Test Example 5: Insecticidal test against peach aphid Placed wet cotton wool on a glass petri dish with an inner diameter of 3 cm, placed kanran leaves cut out on the same diameter, and released four adult mosquito aphids (Myzus persicae) Insects. One day later, a 10% emulsion of the compound of the present invention (depending on the compound, 10% wettable powder was tested) was diluted with water containing a spreading agent to prepare a chemical solution having a concentration of 500 ppm. The prepared chemical was sprayed (2.5 mg / cm ² ) in a rotary spray tower, covered, and stored in a 25 ° C. constant temperature room. Six days after housing, the number of dead peach aphids in the petri dish was examined, and the mortality rate was calculated from the same formula as in Test Example 1. In addition, the test was performed by 2 continuous systems.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
Compounds of the present invention: 1-002a, 1-004a, 2-001b, 2-001a, 4-001b, 4-001c, 4-001a, 4-002a, 4-003a, 4-005a, 5-002a.

Test Example 6: Osmotic transfer test against brown planthopper A 10% emulsion of the compound of the present invention was diluted with tap water to prepare a chemical solution having a concentration of 20 ppm, and the roots of rice cell seedlings (two leaves) were immersed. Seven days later, the rice was cut out and placed in a test tube, in which five third-instar larvae of the green planthopper (Nilaparvata lugens) were released per test tube, covered with a sponge, and housed in a thermostatic chamber at 25 ° C. Six days after the release, the number of dead planthoppers was examined, and the death rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the compounds tested, the following compounds showed a death rate of 90% or more.
The compound of the present invention: 1-001a, 1-002a, 2-001a, 4-001a, 4-002a, 4-003a, 4-005a.

Test Example 7: Effect test on mung beetle mite 3.5 mg of the compound of the present invention was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 μl of the chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm 2, acetone was volatilized to produce a thin film of the compound on the inner wall of the glass container. The inner wall of the glass container used is 35 cm2, and the amount of treatment drug is 10 μg / cm2. In the treated glass container, 5 first nymphs (mixed male and female) of Rhipicophalus sanguineus were released, capped and housed in a constant temperature room at 25 ° C. Four days after the release, the number of ticks was examined, and the death rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the compounds tested, the following compounds showed a death rate of 50% or more.
The compounds of the present invention: 1-002a, 2-002a, 4-001b, 4-003c, 4-003a, 4-005a, 5-001a, 5-002a.

Test Example 8: Effect test on cat fleas 3.5 mg of the present compound was dissolved in 3.5 ml of acetone to prepare a chemical solution having a concentration of 1000 ppm. After 350 μl of the chemical solution was applied to the bottom and side surfaces of a glass container having an inner wall surface area of 35 cm 2, acetone was volatilized to produce a thin film of the compound on the inner wall of the glass container. Since the inner wall of the used glass container is 35 cm 2, the treatment dose is 10 μg / cm 2. In the treated glass container, 5 adults (mixed male and female) of cat flea (Ctenocephalides felis) were released, covered, and housed in a thermostatic chamber at 25 ° C. Four days after releasing, the number of dead fleas was investigated, and the death rate was calculated from the same calculation formula as in Test Example 1.

As a result, among the compounds tested, the following compounds showed a death rate of 50% or more.
The compounds of the present invention: 1-002a, 1-004a, 2-001b, 4-001b, 4-001c, 4-001a, 4-003a.

  The compound in the present invention is an extremely useful compound that exhibits excellent pest control activity and has almost no adverse effect on non-target organisms such as mammals, fish and beneficial insects.

Claims (14)

Formula (1):

[Wherein, R ¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ Alkynyl, halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl Represent,
R ² is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
G represents a structure represented by G ^{1 to} G ⁶ ;

Y2 and Y4 are each independently a hydrogen atom, a halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkenyl, halo _(C 1 ~C ₆₎ alkenyl, C ₁ -C ₆ alkynyl, halo _(C 1 ~C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 -C ₆ ) Represents cycloalkenyl, —OR ⁴⁰ , —N (R ⁸⁰ ) R ⁸¹ , —C (O) OR ⁷⁰ , —S (O) _m R ⁵⁰ , cyano or nitro;
Y3 is hydrogen atom, halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl,} C 1 -C ₆ alkenyl, halo _(C 1 ~C _{6) alkenyl,} C 1 -C ₆ alkynyl, Halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl, halo (C ₃ -C ₆ ) cycloalkenyl, -OR ^{40, -N (R 60) R} 61, -C (O) oR 70, -S (O) m R 50, cyano or nitro,
X ¹ , X ² , X ³ , X ⁴ and X ⁶ are each independently a hydrogen atom, a halogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, Halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C Represents ₆ cycloalkenyl, halo (C ₃ -C ₆ ) cycloalkenyl, —OR ⁹⁰ , —N (R ¹⁰ ) R ¹¹ , —C (O) OR ⁷⁰ , —S (O) _p R ³⁰ , cyano or nitro. ,
R ¹⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ¹¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ³⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁴⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁵⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C ₆₎ cycloalkenyl or _C 1 -C ₁₀ alkoxycarbonyl _(C 1 ~C ₆₎ alkyl,
R ⁶⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ⁶¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁷⁰ represents a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C ₆ ) alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
R ⁸⁰ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo ( C ₁ -C _{6) alkynyl,} C 3 -C ₆ cycloalkyl, halo _(C 3 ~C _{6) cycloalkyl,} C 3 -C ₆ cycloalkenyl, halo _(C 3 ~C _{6) cycloalkenyl,} C 1 -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkoxycarbonyl, halo (C ₁ -C ₆ ) alkoxycarbonyl or represents _C 1 -C ₆ alkylsulfonyl,
R ⁸¹ is a hydrogen atom, C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkylcarbonyl, halo (C ₁ -C ₆ ) alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl , Halo (C ₁ -C ₆ ) alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁹⁰ is C ₁ -C ₆ alkyl, halo (C ₁ -C ₆ ) alkyl, C ₁ -C ₆ alkenyl, halo (C ₁ -C ₆ ) alkenyl, C ₁ -C ₆ alkynyl, halo (C _1- C ₆ ) represents alkynyl, C ₃ -C ₆ cycloalkyl, halo (C ₃ -C ₆ ) cycloalkyl, C ₃ -C ₆ cycloalkenyl or halo (C ₃ -C ₆ ) cycloalkenyl,
n represents an integer of 0, 1 or 2;
m represents an integer of 0, 1 or 2;
p represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides. R ¹ represents C ₁ -C ₆ alkyl;
R ² represents a hydrogen atom or C ₁ -C ₆ alkyl,
Y2 and Y4 are each independently a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 80) R 81} , -C (O) OR 70, Represents —S (O) _m R ⁵⁰ , cyano or nitro,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 60) R 61} , -C (O) OR 70, -S (O) m R ⁵⁰ represents cyano or nitro,
X ¹ , X ² , X ³ , X ⁴ and X ⁶ each independently represent a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, —N (R ¹⁰ ) R ¹¹ or nitro,
R ¹⁰ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ¹¹ represents a hydrogen atom,
R ⁵⁰ represents C ₁ -C ₆ alkyl or C ₁ -C ₁₀ alkoxycarbonyl (C ₁ -C ₆ ) alkyl;
R ⁶⁰ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁶¹ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
R ⁷⁰ represents a hydrogen atom or C ₁ -C ₆ alkyl,
R ⁸⁰ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl or C ₁ -C ₆ alkylsulfonyl,
The condensed heterocyclic compound or a salt thereof or an N-oxide thereof according to claim 1, wherein R ⁸¹ represents a hydrogen atom, C ₁ -C ₆ alkylcarbonyl, C ₁ -C ₆ alkoxycarbonyl, or C ₁ -C ₆ alkylsulfonyl. . Y2 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} a C 3 -C ₆ cycloalkyl or ^{-N (R 80)} R ^81,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 ~C _{6) alkyl,} C 3 -C ₆ ^{cycloalkyl, -N (R 60) R 61} , -C (O) OR 70, -S (O) m R ⁵⁰ represents cyano or nitro,
Y4 represents a hydrogen atom or ^{-N (R 80)} R ^81,
X ¹ represents a hydrogen atom, a halogen atom, —N (R ¹⁰ ) R ¹¹ or nitro,
X ² represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ³ represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ⁴ represents a hydrogen atom or halo (C ₁ -C ₆ ) alkyl,
X ⁶ represents a halogen atom,
R ⁶⁰ represents a hydrogen atom or a C ₁ -C ₆ alkylcarbonyl,
R ⁶¹ represents a hydrogen atom,
R ⁸⁰ represents a hydrogen atom,
R ⁸¹ represents a hydrogen atom,
The fused heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 2, wherein m represents an integer of 0 or 1. Y2 represents a hydrogen atom, a halogen atom or a halo _(C 1 _{~C 6)} alkyl,
Y3 represents a hydrogen atom, a halogen atom, halo _(C 1 _{~C 6)} alkyl, -S and _(O) ^{m R 50} or cyano,
Y4 represents a hydrogen atom,
X ¹ represents a hydrogen atom or —N (R ¹⁰ ) R ¹¹ ,
R ¹⁰ represents C ₁ -C ₆ alkyl,
The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim 3, wherein R ⁵⁰ represents C _{1 to} C ₆ alkyl. Y3 represents a hydrogen atom, a halogen atom or a halo _(C 1 _{~C 6)} alkyl,
X ⁴ represents halo (C ₁ -C ₆ ) alkyl;
5. The condensed heterocyclic compound or a salt thereof or an N-oxide thereof according to claim 4, wherein n represents 0 or an integer of 2.   The pest control agent which contains 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-5 as an active ingredient.   The agrochemical containing 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-5 as an active ingredient.   The control agent of the inside or ectoparasite of the mammal or bird which contains as an active ingredient 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-5.   The control agent according to claim 8, wherein the ectoparasite is a flea or a tick.   An insecticide or acaricide containing, as an active ingredient, one or more selected from the condensed heterocyclic compound according to any one of claims 1 to 5 and a salt thereof.   The seed treatment agent which contains the 1 type (s) or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-5 as an active ingredient.   The seed treatment agent according to claim 11, wherein the seed treatment is performed by dipping treatment.   The soil treatment agent which contains the 1 type, or 2 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-5 as an active ingredient.   The soil treatment agent according to claim 13, wherein the soil treatment is performed by a soil irrigation treatment.