JP2019182855A - Condensed heterocyclic compound and pest control agent - Google Patents

Abstract

To provide a novel pest control agent, particularly an insecticide or a miticide.SOLUTION: The present invention provides a condensed heterocyclic compound represented by formula (1) [where Ais C-Calkyl or the like, Aand Aindependently represent a nitrogen atom or the like, Ris C-Calkyl or the like, Ris a hydrogen atom or the like, Ris halo (C-C) alkyl or the like, Y6, Y7, Y8 and Y9 independently represent a hydrogen atom, G1 or the like, G1 is formula G1-1, Y1, Y2, Y3, Y4 and Y5 independently represent halo (C-C) alkyl or the like, n is an integer of 0, 1 or 2, m is an integer of 0, 1 or 2] or a salt thereof or an N-oxide thereof.SELECTED DRAWING: None

Description

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

  For example, Patent Documents 1 to 4 disclose fused heterocyclic compounds, but do not disclose any fused heterocyclic 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. 2016/129684 International Publication No. 2016/162318 International Publication No. 2017/061497 International Publication No. 2017/144341

  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 [12].
.

[1]
Formula (1):

[ ^Wherein , A ^1a represents a hydrogen atom or C ₁ -C ₆ alkyl,
A ⁴ represents a nitrogen atom or C (R ⁴ ),
A ⁵ represents a nitrogen atom or C (R ⁵ ),
R ¹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ² and R ⁵ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl,
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio, halo (C ₁ -C ₆ ) alkylsulfinyl or halo. _(C 1 ~C ₆₎ alkyl sulfonyl,
Y6, Y7, Y8 and Y9 are each independently hydrogen atom, halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 _{~C 6) alkyl,} C 1 -C ₆ alkoxy, halo _(C 1 -C _{6) alkoxy,} C 1 -C ₆ alkylthio, halo _(C 1 -C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 -C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo ( C ₁ -C ₆₎ alkylsulfonyl, represents cyano, nitro or G1, G1 represents a structure represented by G1-1,

Y1, Y2, Y3, Y4 and Y5 are independently a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl, C} 1 ~ C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkylsulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, Represents C ₁ -C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , —NHR ^{90 g} , cyano or nitro,
R ^90g is 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, C ₁ -C ₆ alkylsulfonyl or halo (C ₁ -C ₆ ) alkylsulfonyl,
n represents an integer of 0, 1 or 2;
m represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides.

[2]
A ^1a represents C ₁ -C ₆ alkyl,
A ⁴ represents C (R ⁴ ),
A ⁵ represents a nitrogen atom,
R ¹ represents C ₁ -C ₆ alkyl;
R ² and R ⁴ represent a hydrogen atom,
R ³ represents halo (C ₁ -C ₆ ) alkyl, the condensed heterocyclic compound or a salt thereof according to [1], or an N-oxide thereof.

[3]
Y6, Y7 and Y9 represent a hydrogen atom,
Y8 represents G1, Y1 and Y2 are each independently hydrogen atom or a halo _(C 1 _{~C 6)} alkyl,
Y3 represents a hydrogen atom, halo _(C 1 ~C _{6) alkyl,} a C 1 -C ₆ alkylthio or _C 1 -C ₆ alkylsulfonyl,
Y4 and Y5 represent a hydrogen atom,
n represents an integer of 2, the fused heterocyclic compound or a salt thereof according to [2], or an N-oxide thereof.

[4]
A pest control agent comprising one or more selected from the condensed heterocyclic compound according to any one of [1] to [3] and a salt thereof as an active ingredient.

[5]
An agrochemical containing one or more selected from the condensed heterocyclic compound according to any one of [1] to [3] and a salt thereof as an active ingredient.

[6]
A control agent for an internal or ectoparasite of a mammal or a bird containing one or more selected from the condensed heterocyclic compound according to any one of [1] to [3] and a salt thereof as an active ingredient.

[7]
The control agent according to [6], wherein the ectoparasite is a flea or ticks.

[8]
An insecticide or acaricide containing, as an active ingredient, one or more selected from the fused heterocyclic compound according to any one of [1] to [3] and a salt thereof.

[9]
The soil treatment agent which contains 1 or more types chosen from the condensed heterocyclic compound and its salt of any one of [1]-[3] as an active ingredient.

[10]
The soil treatment agent according to [9], wherein the soil treatment is performed by a soil irrigation treatment.

[11]
[1] A seed treatment agent containing one or more selected from the condensed heterocyclic compound according to any one of [3] and a salt thereof as an active ingredient.

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

  In this specification, the definitions and meanings of the following terms are as follows.

  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 , for example, methyl, ethyl, n-propyl, i Specific examples include -propyl, n-butyl, i-butyl, s-butyl, tert-butyl, n-pentyl, 1,1-dimethylpropyl, n-hexyl, etc., and each designated number of carbon atoms Selected.

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, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, dichloromethyl, trifluoromethyl, chlorodifluoromethyl, trichloromethyl, bromodifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2-chloroethyl, 2-bromoethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trichloroethyl, 2-bromo-2,2-difluoroethyl, 1, 1,2,2-tetrafluoroethyl, 2-chloro-1,1,2-trifluoroethyl, 2-chloro-1,1,2,2-tetrafluoroethyl, pentafluoroethyl, 2,2-difluoropropyl 3,3,3-trifluoropropyl, 3-bromo-3,3-diflu Ropropyl, 2,2,3,3-tetrafluoropropyl, 2,2,3,3,3-pentafluoropropyl, 1,1,2,3,3,3-hexafluoropropyl, heptafluoropropyl, 2, 2,2-trifluoro-1- (methyl) ethyl, 2,2,2-trifluoro-1- (trifluoromethyl) ethyl, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) Specific examples include ethyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, nonafluorobutyl, etc. In the range of the number of carbon atoms.

In the present specification, the expression “C _a -C _b cycloalkyl” represents a cyclic hydrocarbon group having a carbon number of _a to _{b, and} is a monocyclic or complex ring structure having 3 to 6 members. Can be formed. Each ring may be optionally substituted with an alkyl group within the range of the specified number of carbon atoms. For example, cyclopropyl, 1-methylcyclopropyl, 2-methylcyclopropyl, 2,2-dimethylcyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like can be mentioned as specific examples, and each is selected within the range of the designated number of carbon atoms. .

In the present specification, 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, ethoxy, n-propyloxy, i Specific examples include -propyloxy, n-butyloxy, i-butyloxy, s-butyloxy, tert-butyloxy, 2-ethylhexyloxy and the like, and each is selected within the range of the designated number of carbon atoms.

In the present specification, 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, such as difluoromethoxy, trifluoromethoxy, Chlorodifluoromethoxy, bromodifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2, -tetrafluoroethoxy, 2-chloro-1,1,2 -Trifluoroethoxy, 1,1,2,3,3,3-hexafluoropropyloxy and the like are listed as specific examples, and each is selected in the range of the designated number of carbon atoms.

In the present specification, the expression “C _a -C _b alkylthio” represents an alkyl-S— group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methylthio, ethylthio, n-propylthio, i- Specific examples include propylthio, n-butylthio, i-butylthio, s-butylthio, tert-butylthio and the like, each selected within the range of the specified number of carbon atoms.

In the present specification, the expression “halo (C _a -C _b ) alkylthio” represents a haloalkyl-S— group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as difluoromethylthio, trifluoromethylthio, Chlorodifluoromethylthio, bromodifluoromethylthio, 2,2,2-trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2-chloro-1,1,2-trifluoroethylthio, pentafluoroethyl Thio, 1,1,2,3,3,3-hexafluoropropylthio, heptafluoropropylthio, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylthio, nonafluorobutylthio and the like Specific examples are given, each selected in the range of the specified number of carbon atoms.

In the present specification, the expression “C _a -C _b alkylsulfinyl” represents an alkyl-S (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as methylsulfinyl, ethylsulfinyl, Specific examples include n-propylsulfinyl, i-propylsulfinyl, n-butylsulfinyl, i-butylsulfinyl, s-butylsulfinyl, tert-butylsulfinyl and the like, each selected within the range of the designated number of carbon atoms. .

In the present specification, the expression “halo (C _a -C _b ) alkylsulfinyl” represents a haloalkyl-S (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, difluoromethylsulfinyl. , Trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, 1,2,2,2-tetrafluoro-1- (trifluoromethyl) ethylsulfinyl, nonafluoro Specific examples include butylsulfinyl and the like, each selected within the range of the designated number of carbon atoms.

In the present specification, the expression “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, ethylsulfonyl, n- Specific examples include propylsulfonyl, i-propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, s-butylsulfonyl, tert-butylsulfonyl and the like, each selected within the range of the number of carbon atoms specified.

The expression “halo (C _a -C _b ) alkylsulfonyl” in the present specification represents a haloalkyl-SO ₂ -group having the above-mentioned meaning consisting of _a to _b carbon atoms, such as difluoromethylsulfonyl, tri Fluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, 2,2,2-trifluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2-chloro-1,1,2-trifluoro Specific examples include ethylsulfonyl and the like, and each is selected within the range of the designated number of carbon atoms.

In the present specification, 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, acetyl, propionyl, butyryl. , Isobutyryl, valeryl, isovaleryl, 2-methylbutanoyl, pivaloyl, hexanoyl, heptanoyl, and the like, are selected as specific examples, and each is selected within the range of the designated number of carbon atoms.

In the present specification, the expression “halo (C _a -C _b ) alkylcarbonyl” represents a haloalkyl-C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, fluoroacetyl Specific examples include chloroacetyl, difluoroacetyl, dichloroacetyl, trifluoroacetyl, chlorodifluoroacetyl, bromodifluoroacetyl, trichloroacetyl, pentafluoropropionyl, heptafluorobutanoyl, 3-chloro-2,2-dimethylpropanoyl, etc. Each of which is selected for each specified number of carbon atoms.

In the present specification, the expression “C _a -C _b alkoxycarbonyl” represents an alkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, methoxycarbonyl, ethoxy Specific examples include carbonyl, n-propyloxycarbonyl, i-propyloxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, s-butoxycarbonyl, tert-butoxycarbonyl, 2-ethylhexyloxycarbonyl and the like. Is selected within the range of the specified number of carbon atoms.

In the present specification, the expression “halo (C _a -C _b ) alkoxycarbonyl” represents a haloalkyl-O—C (O) — group having the above-mentioned meaning consisting of _a to _b carbon atoms, for example, Specific examples include chloromethoxycarbonyl, 2-chloroethoxycarbonyl, 2,2-difluoroethoxycarbonyl, 2,2,2, -trifluoroethoxycarbonyl, 2,2,2, -trichloroethoxycarbonyl, etc. Selected within the specified number of carbon atoms.

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 6.
[Production Method 1]
Among the compounds of the present invention represented by the formula (1), the compound (1-A) in which m is an integer of 1 or 2 is, for example, the compound (1) in which m is an integer of 0 among the compounds of the present invention. It can be produced by reacting -B) with an oxidizing agent.

(Wherein R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , Y 1, Y 2, Y 3, Y 4 and Y 5 represent the same meaning as described above, and m 1 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]
Compound (1-B) can be produced, for example, by reacting compound (1-C1) with compound (50).

(Wherein R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , Y 1, Y 2, Y 3, Y 4 and Y 5 represent the same meaning as described above, and X 1 represents a bromine atom or an iodine atom).
Compound (1-B) can be produced by reacting compound (1-C1) and compound (50) in a solvent or without solvent in the presence of a palladium catalyst, a ligand and a base.

  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 Or a mixture of these Medium, and the like.

  Examples of the palladium catalyst include bis (triphenylphosphine) palladium (II) dichloride, tetrakis (triphenylphosphine) palladium (0), bis (dibenzylideneacetone) palladium (0), tris (dibenzylideneacetone) dipalladium (0 ), [1,1′-bis (diphenylphosphino) ferrocene] palladium (II) dichloride dichloromethane adduct and the like. As an equivalent of a palladium catalyst, it can use in 0.005 to 20 equivalent with respect to 1 equivalent of compound (1-C1), and the range of 0.01 to 5 equivalent is preferable.

  Examples of the ligand include 4,5'-bis (diphenylphosphino) -9,9'-dimethylxanthene, 1,10-phenanthroline and the like. The equivalent of the ligand can be used in the range of 0.005 to 20 equivalents relative to 1 equivalent of the compound (1-C1), and preferably in the range of 0.01 to 5 equivalents.

  Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. As an equivalent of a base, it can use in 0.1-100 equivalent with respect to 1 equivalent of compound (1-C1), and the range of 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 in the range of 1 hour to 48 hours.

  As the equivalent of the substrate, compound (50) can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of compound (1-C1), and preferably in the range of 1 to 20 equivalents.

Some of the compounds (50) are known compounds, and some of them are commercially available.
[Production Method 3]
Compound (1-C1) can be produced, for example, by reacting compound (1-C2), which can be produced by reacting compound (3) with compound (51), with an oxidizing agent. .

(Wherein R ¹ , R ² , R ³ , A ^1a , A ⁴ and A ⁵ represent the same meaning as described above, X ¹ represents a bromine atom or an iodine atom, and L ¹ represents a chlorine atom, a bromine atom or an iodine atom. Represents a leaving group such as
Step 1: Compound (1-C2) can be produced by reacting Compound (3) with Compound (51) according to Production Method 6 described in International Publication No. 2016/129684.

  Some of the compound (3) is a known compound, and a part thereof can be synthesized by the method of Step 1 to Step 2 of Synthesis Example 27 of International Publication No. 2016/129684. Some of the compounds (51) are known compounds, and some of them are commercially available.

Step 2: Compound (1-C1) can be produced by oxidizing compound (1-C2) according to the method described in Production Method 1.
[Production Method 4]
Among the compounds of the present invention represented by the formula (1), the compound (1-D1) in which n represents an integer of 2 is produced, for example, by reacting the compound (20) and the compound (30-1). can do.

(In the formula, R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above.)
Compound (1-D1) is obtained by reacting compound (20) and compound (30-1) in a solvent or without a solvent in the presence of an oxidizing agent, optionally in the presence of an acid, and optionally in the presence of a sulfite. Can be manufactured.

  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.

  Examples of the oxidizing agent include oxygen and copper (II) chloride. The usage-amount of an oxidizing agent can be used in 0.1-100 equivalent with respect to 1 equivalent of a compound (20), and 1-20 equivalent is preferable.

  The reaction can be carried out in the presence of an acid. Examples of the acid include p-toluenesulfonic acid, polyphosphoric acid, acetic acid, and propionic acid. The usage-amount of an acid can be used with 0.1-1000 equivalent with respect to 1 equivalent of a compound (20), and 1-500 equivalent is preferable.

  The reaction can be carried out in the presence of sulfite. Examples of sulfites include sodium bisulfite and sodium disulfite. The usage-amount of sulfite can be used in 0.1-100 equivalent with respect to 1 equivalent of compound (20), 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 in the range of 1 hour to 48 hours.

  With respect to the equivalent of the substrate, compound (30-1) can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of compound (20), and preferably in the range of 1 to 20 equivalents.

Some of the compounds (20) are known compounds, and some of them are available as commercial products.
[Production Method 5]
Among the compounds of the present invention represented by the formula (1), the compound (1-D3) in which n represents an integer of 1 and (1-D1) in which n represents an integer of 2 are, for example, the compound (20) and The compound (1-D2), which can be produced by reacting the compound (30-2), can be produced by reacting with an oxidizing agent.

(In the formula, R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above.)
Step 1: Compound (1-D2) can be produced by reacting compound (20) with compound (30-2) according to the method described in Production Method 4.
Step 2: Compound (1-D3) and Compound (1-D1) can be produced by oxidizing compound (1-D2) according to the method described in Production Method 1.
[Production Method 6]
Compound (1-D2) can be produced, for example, by subjecting compound (2), which can be produced by reacting compound (20) and compound (40), to a dehydration cyclization reaction.

(In the formula, R ¹ , R ² , R ³ , A ^1a , A ⁴ , A ⁵ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above.)
Step 1: Compound (2) can be produced by reacting Compound (20) with Compound (40) according to Step [A] of Production Method 1 described in International Publication No. 2016/129684.

  Step 2: Compound (1-D2) can be produced by subjecting Compound (2) to a dehydration cyclization reaction according to Step [B] of Production Method 1 described in International Publication No. 2016/129684.

Compound (30-1) used in production method 4 can be produced, for example, according to the production route represented by the following reaction formulas 1 to 3.
[Reaction Formula 1]

(Wherein R ¹ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above, X 2, X 3 and X 4 represent a halogen atom, and W 1 represents a sodium atom or a potassium atom.)
Step 1: Compound (31) can be produced by reacting Compound (60) with Compound (52) according to Step 1 of Reference Example 1 described in International Publication No. 2016/129684.
Some of the compound (60) and the compound (52) are known compounds, and some of them are commercially available.
Step 2: According to Step 2 of Reference Example 1 described in International Publication No. 2016/129684, the compound (31) and a halogenating agent (for example, chlorine, bromine, iodine, N-chlorosuccinimide, N-bromosuccinimide, N -Iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, 1,3-diiodo-5,5-dimethylhydantoin, etc.) Compound (32) can be produced.
Step 3: According to the reaction conditions described in Japanese Patent Application Publication No. 2014/214118, Journal of Heterocyclic Chemistry 1992, 29, 691, etc., compound (32 ) Can be hydrolyzed in the presence of an acid (eg, hydrochloric acid, sulfuric acid, etc.) or a base (eg, calcium carbonate, sodium acetate, etc.) to produce compound (33).
Process 4: A compound (30-1) can be manufactured by making a compound (33) and a compound (53) react according to reaction conditions as described in international publication 2014/031012 grade | etc.,.
Some of the compounds (53) are known compounds, and some of them are commercially available.
[Reaction Formula 2]

(In the formula, R ¹ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above.)
Step 1: Compound (34-1) can be produced by oxidizing compound (34-2) according to the method described in Production Method 1.

Step 2: According to the reaction conditions described in Journal of Medicinal Chemistry 1998, 41, 4317, etc., compound (34-1) is reduced to reduce compound (30- 1) can be manufactured.
[Reaction Formula 3]

(In the formula, R ¹ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above.)
Step 1: Compound (30-2) can be produced by reducing compound (34-2) according to the method described in Step 2 of Reaction Scheme 2.

  Step 2: Compound (30-1) and Compound (30-3) can be produced by oxidizing compound (30-2) according to the method described in Production Method 1.

The compound (34-2) used in the reaction formula 2 and the reaction formula 3 can be produced, for example, according to the production route represented by the following reaction formula 4.
[Reaction Formula 4]

(In the formula, R ¹ , Y 6, Y 7, Y 8 and Y 9 represent the same meaning as described above, X 5 and X 6 represent a halogen atom, and R ^a represents C ₁ -C ₆ alkyl.)
Step 1: Compound (35) can be produced by reacting Compound (60) with Compound (54) according to the method described in Step 1 of Reaction Scheme 1.
Some of the compounds (54) are known compounds, and some of them are commercially available.

  Process 2: A compound (36) can be manufactured by hydrolyzing a compound (35) according to the process 4 of the reference example 1 as described in international publication 2016/129684.

  Step 3: In accordance with the method described in International Publication No. 2017/098328, etc., the compound (36) is reacted with isobutyl chloroformate to form a mixed acid anhydride, and then reacted with aqueous ammonia to give a compound (37 ) Can be manufactured.

  Step 4: The compound (38) can be produced by subjecting the compound (37) to a dehydration reaction according to the method described in International Publication No. 2013/110443.

  Step 5: Compound (39) can be produced by reacting compound (38) with a halogenating agent according to the method described in Reaction Scheme 4, Step 2.

  Process 6: According to the manufacturing method 3 of international publication 2016/129684, a compound (34-2) can be manufactured by making a compound (39) and a compound (55) react.

  Some of the compounds (55) are known compounds, and some of them are commercially available.

Compound (30-2) used in Reaction Scheme 3 can be produced, for example, according to the production route represented by Reaction Formula 5 and Reaction Formula 6 below.
[Reaction Formula 5]

(Wherein R ¹ , Y 6, Y 7, Y 8, Y 9 and X 4 represent the same meaning as described above.)
Compound (30-2) is produced by reacting Compound (33) with Compound (55) or Compound (56) according to Step [E] of Production Method 3 described in International Publication No. 2016/129684. it can.

Some of the compounds (56) are known compounds, and some of them are commercially available.
[Reaction Scheme 6]

(In the formula, R ¹ , Y 6, Y 7, Y 8, Y 9 and X 4 represent the same meaning as described above, and W 2 represents a sodium atom or a hydrogen atom.)
Step 1: Compound (41) can be produced by reacting compound (33) with a thiolating agent in a solvent or without a solvent, optionally in the presence of a base.

  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 Or a mixture of these Medium, and the like.

  Examples of the thiolating agent include sodium hydrogen sulfide and sodium sulfide. The usage-amount of a thiolizing agent can be used in 0.1-100 equivalent with respect to 1 equivalent of a compound (33), and 1-20 equivalent is preferable.

  The reaction can be performed in the presence of a base. Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of the compound (33), 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.

  Step 2: Compound (30-2) can be produced by reacting compound (41) with an alkylating agent in a solvent or without a solvent, optionally in the presence of a base.

  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 Or a mixture of these Medium, and the like.

  Examples of the alkylating agent include iodoethane, bromoethane, and diethyl sulfate. The usage-amount of an alkylating agent can be used in 0.1-100 equivalent with respect to 1 equivalent of compound (41), and 1-20 equivalent is preferable.

  The reaction can be performed in the presence of a base. Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of the compound (41), 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.
Compound (40) used in production method 6 can be produced, for example, according to the production route represented by the following reaction formula 7.
[Reaction Scheme 7]

(In the formula, R ¹ , Y 6, Y 7, Y 8, Y 9 and R ^a represent the same meaning as described above.)
Step 1: Compound (42) can be produced by reacting compound (35) with 2-ethylhexyl 3-mercaptopropionate in the presence of a halogenating agent in a solvent or without solvent.

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, toluene, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, Nitriles such as acetonitrile and propionitrile, amides such as N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone and N, N′-dimethylimidazolidinone, sulfoxides such as dimethyl sulfoxide, or These mixed solvents Etc.
Examples of the halogenating agent include chlorine, bromine, iodine, iodine monochloride, N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo. Examples include -5,5-dimethylhydantoin and 1,3-diiodo-5,5-dimethylhydantoin. The usage-amount of a halogenating agent can be used in 0.1-100 equivalent with respect to 1 equivalent of compound (35), 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 in the range of 1 hour to 48 hours.
As an equivalent of the substrate, 2-ethylhexyl 3-mercaptopropionate can be used in the range of 0.5 to 50 equivalents relative to 1 equivalent of compound (35), and preferably in the range of 1 to 20 equivalents.
Step 2: Compound (43) can be produced by reacting compound (42) with an alkylating agent in a solvent or without a solvent in the presence of a base.

  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 Or a mixture of these Medium, and the like.

  Examples of the alkylating agent include iodoethane, bromoethane, and diethyl sulfate. The usage-amount of an alkylating agent can be used in 0.1-100 equivalent with respect to 1 equivalent of compound (42), and 1-20 equivalent is preferable.

  Examples of the base include pyridine, 2,6-lutidine, triethylamine, diisopropylethylamine, tributylamine, 4- (dimethylamino) pyridine, 1,4-diazabicyclo [2.2.2] octane (DABCO), 1,8- Organic bases such as diazabicyclo [5.4.0] -7-undecene (DBU) or 1,5-diazabicyclo [4.3.0] -5-nonene (DBN), sodium hydroxide, potassium hydroxide, hydrogen Inorganic bases such as sodium hydride, sodium hydrogen carbonate, potassium carbonate, cesium carbonate and the like can be mentioned. The equivalent of the base can be used in the range of 0.1 to 100 equivalents relative to 1 equivalent of the compound (42), 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.
Step 3: Compound (40) can be produced by hydrolyzing Compound (43) according to the method described in Step 2 of Reaction Scheme 4.

  In the reactions of Production Method 1 to Production Method 6 and Reaction Equation 1 to Reaction Equation 7, 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. The target compound of the present invention can be obtained by ordinary post-treatment. 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.

  Examples of the condensed heterocyclic compound represented by the formula (1) included in the present invention that can be produced using the above method include compounds shown in Tables 1 to 15 below. However, the compounds shown in Tables 1 to 15 below are for illustrative purposes, and the compounds included in the present invention are not limited to these.

  In the table, “Me” represents methyl, and “Et” represents ethyl.

  [Table 1]

Continuation of [Table 1] Continuation of [Table 1] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 2]

Continuation of [Table 2] Continuation of [Table 2] ――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 3]

Continuation of [Table 3] Continuation of [Table 3] ――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 4]

Continuation of [Table 4] Continuation of [Table 4] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 5]

Continuation of [Table 5] Continuation of [Table 5] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 6]

Continuation of [Table 6] Continuation of [Table 6] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 7]

Continuation of [Table 7] Continuation of [Table 7] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 8]

Continuation of [Table 8] Continuation of [Table 8] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 9]

Continuation of [Table 9] Continuation of [Table 9] ――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 10]

Continuation of [Table 10] Continuation of [Table 10] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 11]

Continuation of [Table 11] Continuation of [Table 11] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――

[Table 12]

Continuation of [Table 12] Continuation of [Table 12] ―――――――― ――――――――― ―――――――――
Y1 Y2 Y3 Y1 Y2 Y3 Y1 Y2 Y3
――――――――――――――――――――――――――――
HHHH Cl HHH Cl
Cl HHH Me HHH Me
Me HHH CF ₃ HHH CF ₃
CF ₃ HHH OMe HHH OMe
OMe HHH OCF ₃ HHH OCF ₃
OCF ₃ HHH SMe HHH SMe
SMe HHH SO ₂ Me HHH SO ₂ Me
SO ₂ Me HHH NO ₂ HHH NO ₂
NO ₂ HHH CN HHH CN
CN HH ――――――――― ―――――――――
――――――――
[Table 13]

Continuation of [Table 13] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 13] Continuation of [Table 13] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 14]

Continuation of [Table 14] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 14] Continuation of [Table 14] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 15]

Continuation of [Table 15] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 15] Continuation of [Table 15] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
Specific examples of production intermediates of the condensed heterocyclic compound represented by the formula (1) included in the present invention that can be produced by using the above method are shown in Tables 16 to 21. In the table, “Me” represents methyl, and “Et” represents ethyl.

  [Table 16]

Continuation of [Table 16] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 16] Continuation of [Table 16] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 17]

Continuation of [Table 17] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 17] Continuation of [Table 17] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 18]

Continuation of [Table 18] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 18] Continuation of [Table 18] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 19]

Continuation of [Table 19] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 19] Continuation of [Table 19] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
[Table 20]

Continuation of [Table 20] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 20] Continuation of [Table 20] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――

[Table 21]

Continuation of [Table 21] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HHHHHHFH
FHHHHH Cl H
Cl HHHHH Br H
Br HHHHHIH
IHHHHH Me H
Me HHHHH CF ₃ H
CF ₃ HHHHH SMe H
HFHHHH SOMe H
H Cl HHHH SO ₂ Me H
H Br HHHH OMe H
HIHHHH OCF ₃ H
H Me HHHH NO ₂ H
H CF ₃ HHHH CN H
H SMe HHHHHF
H SOMe HHHHH Cl
H SO ₂ Me HHHHH Br
H OMe HHHHHI
H OCF ₃ HHHHH Me
H NO ₂ HHHHH CF ₃
H CN HH ――――――――――――
――――――――――――
Continuation of [Table 21] Continuation of [Table 21] ―――――――――――― ――――――――――――
Y6 Y7 Y8 Y9 Y6 Y7 Y8 Y9
―――――――――――― ――――――――――――
HFHFHFFH
H Cl H Cl H Cl Cl H
H Br H Br H Br Br H
HIHIHIIH
HFH Cl HF Cl H
HFH Br HF Br H
HFHIHFIH
H Cl HFH Cl FH
H Cl H Br H Cl Br H
H Cl HIH Cl IH
H Br HFH Br FH
H Br H Cl H Br Cl H
H Br HIH Br IH
HIHFHIFH
HIH Cl HI Cl H
HIH Br HI Br H
HFH CN HF CN H
H Cl H CN H Cl CN H
H Br H CN H Br CN H
HIH CN HI CN H
H CF ₃ HFH CF ₃ FH
H CF ₃ H Cl H CF ₃ Cl H
H CF ₃ H Br H CF ₃ Br H
H CF ₃ HIH CF ₃ IH
H CF ₃ H CN H CF ₃ CN H
―――――――――――― ――――――――――――
The pest control agent in the present invention refers to the field of agriculture and horticulture or the field of livestock and hygiene (endoparasites / external parasites for mammals or birds as domestic animals and pets, hygiene pests and unpleasant pests for household and commercial use) It means a pest control agent for harmful arthropods such as The agrochemical in the present invention means an insecticide / acaricide, a nematicide, a herbicide, a fungicide and the like 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.

  Adachiphyes honmai, Adoxophyes orana fasciata, Archips breviplicanus, Archips fuscocupreanus, Grapholita molesta, Hoa magoni, Hoa Leguminivora glycinivorella, Matsumuraeses phaseoli, Pandemis heparana, Bucculatrix pyrivorella, Lyonetia clerkella, Lyonetia prunifal malp ringoniella), citrus leaflet (Phyllocnistis citrella), green scallop (Acrolepiopsis sapporensis), yamanoimokoga (Acrolepiopsis suzukiella), scallop (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, Greater white butterfly (Pieris brassicae), Great white butterfly (Pieris rapae crucivora), Ascitis 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), Fly Hessian (Mayetiola destructor), Housefly (Musca domestica), Fly (Stomoxys calcitrans), Flyfly (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 (Boophilus microplus), Thip tick (Haemaphysaliscampanulata), Tick tick (Haemaphysaliscampanulata), Tick tick (Ixo tus tick) spp.), ticks such as 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 products; inorganic salts such as magnesium carbonate, calcium carbonate, sodium carbonate, sodium bicarbonate, 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; mixtures of aromatic and aliphatic hydrocarbons such as kerosene; alcohols such as ethanol, isopropanol, cyclohexanol, phenoxyethanol, and 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 (C1, C8 or C12) pyrrolidone; fats and oils such as soybean oil, linseed oil, rapeseed oil, coconut oil, cottonseed oil, castor oil; 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 surfactant 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 ectoparasites or ectoparasites are controlled 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 a 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 giving a so-called canine dog or 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.

  In addition, as a dosage form for transdermal administration, for example, solid preparations such as powders (Cream), creams (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, particularly 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.

  The liquid preparation should be administered as it is, transdermally or by injection, or mixed with feed, orally administered, diluted with water, transdermally administered, sprayed into animal breeding environments such as barns, etc. 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-butylyl 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.

  As an emulsifier, 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. 1-001a 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. 1-001a 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 Industries)
The above is uniformly mixed to obtain an emulsion.

[Formulation Example 3] Suspending Agent Compound No. 1-001a 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. 1-001a 75 parts Hightenol 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. 1-001a 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. 1-001a 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. 1-001a 25 parts sodium diisobutylnaphthalenesulfonate 1 part calcium n-dodecylbenzenesulfonate 10 parts alkylaryl polyglycol ether 12 parts sodium salt of formalin condensate naphthalenesulfonate 3 parts emulsion type silicone 1 part silicon dioxide 3 parts kaolin 45 Part [Formulation Example 8] Water-soluble thickener preparation 1-001a 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 1-001a 2 parts dimethyl sulfoxide 10 parts 2-propanol 35 parts acetone 53 parts [Formulation Example 10] Solution for transdermal administration Compound No. 1-001a 5 parts Hexylene glycol 50 parts Isopropanol 45 parts [Formulation Example 11] Solution for transdermal administration Compound No. of the present invention 1-001a 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 1-001a 2 parts light liquid paraffin 98 parts [Formulation Example 13] Solution for transdermal administration (dropping) The present compound No. 1 1-001a 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 herbicidal substances are formulated or sprayed 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, benzamacryl acril), benzamorf, benzovindiflupyr, bethoxazine, binapacryl, biphenyl, bitertanol, blasticidin-S (blasticidin-S), bixafen ( bixafen, bordeaux mixture, boscalid, bromuconazole, bupirimate, buthiobate, calcium polysulfide, calcium polysulfide, captaphor (Captafol), captan, carpropamid, carbamorph, carbendazim, carboxin, carvone, cheshunt mixture, chinomethionat, Robbenthiazone, chloraniformethane, chloranil, chlorfenazol, chloroneb, chloropicrin, chlorothalonil, chloroquinox, clozoline ( chlozolinate, climbazole, clotrimazole, copper acetate, copper carbonate, basic, copper hydroxide, copper naphthenate ), Copper oleate, copper oxychloride, copper sulfate, copper sulfate, basic, copper zinc chromate, cufraneb ), Coumoxystrobin, cuprobam ), Cyazofamid, cyclafuramid, cycloheximide, cyflufenamid, cymoxanil, cypendazole, cyproconazol, cyprodinil, proflam cyprofuram, dazomet, debacarb, decafentin, dehydroacetic acid, diclobentiazox, dichlofluanid, dichlone, dichlorophen (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, drazoxolone, edifenphos, nesifonphos 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, florylpicoxamid, fluazinam, fludioxonil, flufenoxystrobin ), Fluindapyr, flumetover, flumorph, fluopicolide, fluopyram, fluorimide, fluotrimazole, fluoxastrobin, fluopimide ), Fluquinconazole, flusilazole, flusulfamide, flutianil, flutolanil, flutriafol, fluxafol Loxad (fluxapyroxad), folpet, fosetyl-aluminium, fthalide, fuberidazole, furalaxyl, furametpyr, furamepanyl, furcarbanil, fluconazole Fluconazole-cis, furmecyclox, furphanate, glyodin, griseofulvin, guazatine, halacrinate, hexachlorobenzene, hexaconazole (Hexaconazole), hexylthiofos, hydroxyquinoline sulfate, hymexazol, imazalil, imibenconazole Iminoctadine-albesilate, iminoctadine-triacetate, inpyrfluxam, ipconazole, ipfentrifluconazole, ipflufenoquine, ipflufenoquin (Iprobenfos), iprodione, iprovalicarb, isofetamid, isoflucypram, isoprothiolane, isopyrazam, isothianil, isovaledione, etc.

  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, methyl tetraprole, methyl tetraprole metiram), mettominostrobin, metrafenone, metsulfovax, milneb, microbutanil, microzoline, nabam, natamycin, nickel bis ( Dimethyldithiocarbamate (nickel bis (dimethyldithiocarbamate)), nitrostyrene, nitrothal-isopropyl, nuarimol, ocariin (OCH), octhilinone, offurace, orisatrobin (Orysastrobin), oxathiapiproline, oxadixyl, 8-hydroxyquinoline copper, oxycarboxin, oxpoconazole fumarate, pefrazoe Pefurzoate, penconazole, penflufen, penencycuron, penthiopyrad, orthophenylphenol, phosdiphen, picarbutrazox, picoxy Stroxybin, piperalin, polycarbamate, polyoxins, polyoxin-D (polyoxorim), potassium azide, potassium hydrogen carbonate, proquinazid , Probenazole, prochloraz, procymidone, propamocarb hydrochloride, propiconazole, propineb, prothiocarb, prothiocarb Prothioconazole, pyridiflumetofen, pyracarbolid, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyrapropoyne, pyradiflumide, pyraziflumid Pyrazophos, pyribencarb-methyl, pyridachlometyl, pyridiinitril, pyrifenox, pyrimethanil, pyriminostrobin, pyrimorph ), Pyriofenone, pyrisoxazole, pyroquilon, pyroxychlor, pyroxyfur, quinomethionate, quinofumelin, Quinoxyfen, quintozene, quinacetol-sulfate, quinazamid, quinconazole, rabenzazole and Bacillus subtilis, Strain: D747, FZB24, GBO , MBI600, QST713, Y1336, etc.).

  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, oxytetracycline , 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, benspyrimoxane (Benzpyrimoxan), bifenthrin, bioallethrin, bioresmethrin, bistrifluron, broflanilide, buprofezin, buprofezin Carboxy (butocarboxim), carbaryl, carbofuran, carbofuran, carbosulfan, cartap, chlorantraniliprole, chlorethxyfos, chlorfenapyr, chlor Chlorfenvinphos, chlorfluazuron, chlormephos, chloroprallethrin, chlorpyrifos, chlorpyrifos-methyl, chromafenozide, clothianidin , Cyanophos, cyantraniliprole, cyclaniliprole, cycloprothrin, cyflumetofen, cyfluthrin, Ter-cyfluthrin, cyhalodiamide, cyhalothrin, gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin (alpha) -cypermethrin), beta-cypermethrin, zeta-cypermethrin, cyphenothrin, cyromazine, deltamethrin, diacloden, diafenthiuron ( diafenthiuron, diazinon, dichlorolorzozotiaz, dichlorvos, diflubenzuron, dimefluthrin, dimethylvinphos, dinotefuran, diofenolan , Disulfoton, dimethoate, emamectin-benzoate, empenthrin, endosulfan, alpha-endosulfan, EP-N, EPN, esfenvalerate, Ethiofencarb, ethiprole, etofenprox, etrimfos, fenitrothion, fenobucarb, phenoxycarb, fenpropathrin, fenthion, fenthion Fenvalerate, fipronil, flonicamid, fluazuron, flubendiamide, flucycloxuron Flucythrinate, flufenerim, flufenoxuron, flufenprox, flumethrin, flupyrinin, fluralaner, fluvalinate, tau-fulvali Such as tau-fluvalinate, fonophos, formetanate, formothion, furathiocarb, flufiprole, fluhexafon, flupyradifurone, 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, oxazosulfyl ), Oxydemeton-methyl, oxydeprofos, parathion, parathion-methyl, pentachlorophenol, permethrin, fe Phenothrin, phenthoate, phoxim, phorate, foalone, phosmet, phosphamidon, pirimicarb, pirimiphos-methyl, profenofos (Profenofos), profluthrin, prothiofos, propaphos, protrifenbute, pymetrozine, pyraclofos, pyrethrins, pyridalyl, pyrifilyl ), Pyriprole, pyrafluprole, pyriproxyfen, resmethrin, rotenone, SI-0405 (study name), sulprofos, silafluofe (Silafluofen), spinetoram (spinetoram), spinosad (spinosad), spiromesifen (spiromesifen), spirotetramat (spirotetraion) (spiropidion), sulfoxaflor (sulfoxaflor), sulfotep (sulfotep), SYJ-159 (test name) , Tebfenozide, teflubenzuron, tefluthorin, terbufos, tetrachlorantraniliprole, tetrachlorvinphos, tetramethrin, d-T-80- Phthathrin (d-tetramethrin), tetramethylfluthrin, tetraniliprole, thiacloprid, thiocyclam, thiodicarb, thiamethoxam ), Thiofanox, thiometon, tolfenpyrad, tralomethrin, transfluthrin, triazamate, trichlorfon, triazuron, triflumezopyrim ( triflumezopyrim), triflumuron, tyclopyrazoflor, vamidothion, fluxametamide, MIE-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).
In addition, the proton nuclear magnetic resonance spectrum described below (hereinafter referred to as ¹ H-NMR) was measured at 300 MHz (JNM-ECX300 or JNM-ECP300, manufactured by JEOL). Heavy chloroform or heavy dimethyl sulfoxide was used as a measurement solvent. When deuterated chloroform was used as a solvent, tetramethylsilane was used as a reference substance.

The symbol in the chemical shift value of ¹ H-NMR represents the following meaning.
s: singlet, brs: broad singlet, d: doublet, dd: double doublet, t: triplet, q: quartet, m: multiplet Synthesis Example 1: 2- {3- (ethylsulfonyl) -7-[(2- (Trifluoromethyl) phenyl) thio] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine (invention) Compound No. 1-001b) and 2- {3- (ethylsulfonyl) -7-[(2- (trifluoromethyl) phenyl) sulfonyl] imidazo [1,2-a] pyridin-2-yl} -3- Synthesis step 1: 2- {3- (ethyls) of methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine (the present compound No. 1-001a) (Lufonyl) -7-[(2- (trifluoromethyl) phenyl) thio] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6- (trifluoromethyl) -3H-imidazo [4 , 5-b] Pyridine (Compound No. 1-001b of the present invention) 2- [3- (Ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl- To a mixed solution of 640 mg of 6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine and 4 ml of 1,4-dioxane, 256 mg of 2- (trifluoromethyl) benzenethiol, 4,5 ′ at room temperature. -Bis (diphenylphosphino) -9,9'-dimethylxanthene 68 mg, tris (dibenzylideneacetone) dipalladium (0) 54 mg and diisopropylethylamine 46 The mg was added. After replacing the inside of the reaction vessel with nitrogen gas, the mixture was stirred at 80 ° C. for 1 hour. After completion of the reaction, 10 ml of water was added to the reaction mixture and extracted with chloroform (10 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 [gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100 (volume ratio, the same applies hereinafter)] to obtain 579 mg of the desired product. Obtained as a white solid.
Melting point: 198-199 ° C
¹ H-NMR (CDCl ₃ ): δ9.05 (d, J = 4.5Hz, 1H), 8.72 (brs, 1H), 8.31 (brs, 1H), 7.95-7.85 (m, 1H), 7.80-7.60 ( m, 3H), 7.25-7.15 (m, 1H), 6.91 (dd, J = 7.5, 1.5Hz, 1H), 4.09 (s, 3H), 3.98 (q, J = 7.2Hz, 2H), 1.42 (t , J = 7.5Hz, 3H).
Step 2: 2- {3- (Ethylsulfonyl) -7-[(2- (trifluoromethyl) phenyl) sulfonyl] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6- ( Synthesis of Trifluoromethyl) -3H-imidazo [4,5-b] pyridine (Compound No. 1-001a of the Present Invention) 2- {3- (ethylsulfonyl) -7-[(2- (Trifluoromethyl) phenyl) thio] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine 250 mg and acetic acid To 1.5 ml of the mixed solution, 5 mg of sodium tungstate dihydrate and 142 mg of 30% by mass hydrogen peroxide were added under ice cooling, and the mixture was stirred at room temperature for 16 hours. After completion of the reaction, 5 ml of a saturated sodium thiosulfate aqueous solution was added to the reaction mixture, followed by extraction 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 (n-hexane: ethyl acetate = 100: 0 to 0: 100 gradient) to obtain 168 mg of the desired product as a white solid.
Melting point: 140-144 ° C
¹ H-NMR (CDCl ₃ ): δ 9.26 (dd, J = 7.5, 0.6Hz, 1H), 8.80-8.70 (m, 1H), 8.35-8.25 (m, 2H), 8.21 (d, J = 8.1 Hz, 1H), 7.85-7.75 (m, 2H), 7.75-7.60 (m, 1H), 7.21 (dd, J = 7.8, 1.8Hz, 1H), 4.17 (s, 3H), 4.12 (q, J = 7.2Hz, 2H), 1.41 (t, J = 7.8Hz, 3H).
Synthesis Example 2: 2- {3- (ethylsulfonyl) -7-[(2- (trifluoromethyl) phenyl) sulfinyl] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6 Synthesis of (trifluoromethyl) -3H-imidazo [4,5-b] pyridine (present compound No. 1-001c) 2- {3- (ethylsulfonyl) -7 obtained in Step 1 of Synthesis Example 1 -[(2- (trifluoromethyl) phenyl) thio] imidazo [1,2-a] pyridin-2-yl} -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b ] To a mixed solution of 250 mg of pyridine and 1.5 ml of acetic acid, 71 mg of 30% by mass hydrogen peroxide was added under ice cooling, and the mixture was stirred at room temperature for 16 hours. After completion of the reaction, 5 ml of a saturated sodium thiosulfate aqueous solution was added to the reaction mixture, followed by extraction 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 (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 180 mg of the desired product as a white solid.
Melting point: 157-159 ° C
¹ H-NMR (CDCl ₃ ): δ9.36 (d, J = 7.8Hz, 1H), 8.75 (s, 1H), 8.58 (d, J = 6.9Hz, 1H), 8.45-8.30 (m, 2H) , 8.00-7.80 (m, 4H), 7.45-7.40 (m, 1H), 4.17 (s, 3H), 4.10 (q, J = 7.2Hz, 2H), 1.43 (t, J = 7.2Hz, 3H).
Synthesis Example 3: 2- [3- (Ethylthio) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5 -B] pyridine (present compound No. 1-018b) and 2- [3- (ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- ( Trifluoromethyl) -3H-imidazo [4,5-b] pyridine (the present compound No. 1-018a) synthesis step 1: 2- [3- (ethylthio) -7-iodoimidazo [1,2-a Synthesis of Pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine (Compound No. 1-018b of the present invention) International Publication No. 2016/129684 Step 1 to Synthesis Example 27 2-Bromo-2- (ethylthio) -1- [3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridin-2-yl] ethanone 3 synthesized by the method of Step 2 To a mixed solution of 0.0 g and 26 ml of acetonitrile, 1.7 g of 4-iodo-2-aminopyridine was added at room temperature, and the mixture was stirred for 7 hours with heating under reflux. After completion of the reaction, 100 ml of water was added to the reaction mixture at room temperature. The precipitated solid was filtered to obtain 1.56 g of the target product as a white solid.
¹ H-NMR (CDCl ₃ ): δ8.87 (d, J = 1.2Hz, 1H), 8.82 (s, 1H), 8.48 (s, 1H), 8.41 (d, J = 7.2Hz, 1H), 7.51 (d, J = 7.2Hz, 1H), 4.38 (s, 3H), 3.14 (q, J = 7.5Hz, 2H), 1.25 (t, J = 7.5Hz, 3H).
Step 2: 2- [3- (Ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5 -B] Synthesis of Pyridine (Compound No. 1-018a of the Present Invention) 2- [3- (Ethylthio) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3 obtained in Step 1 -Methyl-6- (trifluoromethyl) -3H-imidazo [4,5-b] pyridine (1.56 g) and chloroform (10 ml) were mixed with 65 mass% metachloroperbenzoic acid (Tokyo Chemical Industry Co., Ltd.) under ice cooling. Manufactured; containing about 30% by mass of water, the same applies hereinafter.) 1.73 g was added and stirred at room temperature for 3 hours. After completion of the reaction, 10 ml of a saturated sodium thiosulfate aqueous solution was added to the reaction mixture, followed by extraction with chloroform (10 ml × 2). The obtained organic layer was washed with 10 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 precipitated solid was filtered, and the obtained solid was washed with 10 ml of diisopropyl ether to obtain 1.24 g of the desired product as a white solid.
¹ H-NMR (CDCl ₃ ): δ8.99 (dd, J = 7.5, 0.6Hz, 1H), 8.75 (d, J = 1.2Hz, 1H), 8.33 (d, J = 1.2Hz, 1H), 8.30 -8.26 (m, 1H), 7.38 (dd, J = 7.2, 1.2Hz, 1H), 4.13 (s, 3H), 4.02 (q, J = 7.5Hz, 2H), 1.43 (t, J = 7.5Hz, 3H).
Synthesis Example 4: 2- [3- (Ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4 5-b] Synthesis of pyridine (the present compound No. 1-018a) Step 1: Preparation of 2- (dichloromethyl) -7-iodoimidazo [1,2-a] pyridine (production intermediate No. i-004) Synthesis To a mixed solution of 3.0 g of 4-iodo-2-aminopyridine and 15 ml of chlorobenzene, 1.9 g of 1,1,3-trichloroacetone was added at room temperature, and the mixture was stirred for 1 hour with heating under reflux. To the reaction mixture, 1.37 g of 1,1,3-trichloroacetone was added at room temperature, and the mixture was stirred for 6.5 hours with heating under reflux. After completion of the reaction, 20 ml of a 1 mol / L sodium hydroxide aqueous solution was added to the reaction mixture, followed by extraction with chloroform (20 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 (gradient of n-hexane: ethyl acetate = 100: 0 to 0: 100) to obtain 2.12 g of the desired product as a light brown solid.
¹ H-NMR (CDCl ₃ ): δ8.04-8.01 (m, 1H), 7.84 (d, J = 7.2Hz, 1H), 7.78 (s, 1H), 7.10-7.05 (m, 1H), 6.89 ( s, 1H).
Step 2: Synthesis of 3-chloro-7-iodoimidazo [1,2-a] pyridine-2-carbaldehyde (Production Intermediate No. i-005) 2- (Dichloromethyl) -7 obtained in Step 1 -To a mixed solution of 1.78 g of iodoimidazo [1,2-a] pyridine and 10 ml of N, N-dimethylformamide was added 780 mg of N-chlorosuccinimide at room temperature, and the mixture was stirred at 50 ° C for 2.5 hours. To the reaction mixture, a solution of calcium carbonate (1.63 g) in water (15 ml) was added at room temperature, and the mixture was stirred at 50 ° C. for 4 hours. After completion of the reaction, a saturated aqueous sodium hydrogen carbonate solution was added to the reaction mixture under ice cooling. The reaction mixture was filtered using celite, and the celite was washed with chloroform. The obtained filtrate and washing solution were combined and extracted with chloroform (20 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 precipitated solid was filtered, and then the obtained solid was washed with diisopropyl ether to obtain 1.4 g of the desired product as a white solid.
Melting point: 170-171 ° C
¹ H-NMR (CDCl ₃ ): δ 10.20 (s, 1H), 8.12 (s, 1H), 7.91 (dd, J = 7.2, 1.2Hz, 1H), 7.28 (dd, J = 7.2, 1.5Hz, 1H).
Step 3: Synthesis of 3- (ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridine-2-carbaldehyde (Production Intermediate No. i-001a) 3-Chloro-7 obtained in Step 2 -To a mixed solution of 500 mg of iodoimidazo [1,2-a] pyridine-2-carbaldehyde and 5 ml of dimethyl sulfoxide, 568 mg of sodium ethanesulfinate was added at room temperature and stirred at 80 ° C for 4 hours. After completion of the reaction, 20 ml of water was added to the reaction mixture and extracted 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 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 0: 100 gradient) to obtain 279 mg of the desired product as a pale yellow solid.
Melting point: 199-202 ° C
¹ H-NMR (CDCl ₃ ): δ 10.45 (s, 1H), 8.81 (dd, J = 7.2, 0.9Hz, 1H), 8.29 (dd, J = 1.8, 0.9Hz, 1H), 7.40 (dd, J = 7.2, 1.8Hz, 1H), 3.49 (q, J = 7.5Hz, 2H), 1.36 (t, J = 7.5Hz, 3H).
Step 4: 2- [3- (Ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5 -B] Synthesis of pyridine (present compound No. 1-018a) 3- (ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridine-2-carbaldehyde obtained in Step 3 240 mg, N ² -To a mixed solution of 139 mg of methyl-5- (trifluoromethyl) pyridine-2,3-diamine and 2 ml of N, N-dimethylformamide, 140 mg of sodium bisulfite was added at room temperature and stirred at 120 ° C for 13.5 hours did. To the reaction mixture, 5 ml of water and 5 ml of 1 mol / L hydrochloric acid were added at room temperature, followed by extraction with chloroform (20 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 (n-hexane: ethyl acetate = 100: 0 to 0: 100 gradient) to obtain 275 mg of the desired product as a pale yellow solid.
¹ H-NMR (CDCl ₃ ): δ8.99 (dd, J = 7.5, 0.6Hz, 1H), 8.75 (d, J = 1.2Hz, 1H), 8.33 (d, J = 1.2Hz, 1H), 8.30 -8.26 (m, 1H), 7.38 (dd, J = 7.2, 1.2Hz, 1H), 4.13 (s, 3H), 4.02 (q, J = 7.5Hz, 2H), 1.43 (t, J = 7.5Hz, 3H).
Synthesis Example 5: 2- [3- (Ethylthio) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5 -B] Synthesis step of pyridine (the present compound No. 1-018b) 1: Synthesis of 7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid 7-Iodoimidazo [1,2-a] pyridine To a mixed solution of ethyl 2-carboxylate (3.0 g) and 1,4-dioxane (50 ml), 1 mol / L aqueous sodium hydroxide solution (50 ml) was added at room temperature, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, 1 mol / L hydrochloric acid was added to the reaction mixture to adjust the pH of the aqueous layer to 3-4. After the precipitated solid was filtered, the obtained solid was washed with 30 ml of water to obtain 3.52 g of the desired product as a white solid.
¹ H-NMR (DMSO-d6): δ 8.48 (d, J = 0.7Hz, 1H), 8.38 (d, J = 0.7Hz, 1H), 8.11 (d, J = 0.7Hz, 1H), 7.25 (dd , J = 7.2,1.7Hz, 1H) (CO ₂ H proton signal could not be observed).
Step 2: Synthesis of 7-iodoimidazo [1,2-a] pyridine-2-carboxamide 3.52 g of 7-iodoimidazo [1,2-a] pyridine-2-carboxylic acid obtained in Step 1 and triethylamine 1 To a mixed solution of 0.44 g and 100 ml of tetrahydrofuran was added 1.94 g of isobutyl chloroformate at room temperature, and the mixture was stirred at room temperature for 1 hour. To the reaction mixture, 720 mg of triethylamine and 970 mg of isobutyl chloroformate were added at room temperature, and the mixture was stirred at room temperature for 1 hour. To the reaction mixture, 3.2 ml of 28% by mass aqueous ammonia was added at room temperature, and the mixture was stirred at room temperature for 1 hour. After completion of the reaction, the solvent was distilled off from the reaction mixture. To the obtained residue, 50 ml of water was added and extracted with chloroform (50 ml × 3). The obtained organic layer was dehydrated and dried over anhydrous sodium sulfate, and then the solvent was distilled off under reduced pressure to obtain 3.79 g of the desired product as a white solid.
¹ H-NMR (DMSO-d6): δ 8.40 (dd, J = 7.0, 0.7Hz, 1H), 8.34 (d, J = 0.7Hz, 1H), 8.05 (dd, J = 1.8, 0.7Hz, 1H) , 7.71 (brs, 1H), 7.45 (brs, 1H), 7.23 (dd, J = 7.2, 1.7 Hz, 1H).
Step 3: Synthesis of 7-iodoimidazo [1,2-a] pyridine-2-carbonitrile 3.79 g of 7-iodoimidazo [1,2-a] pyridine-2-carboxamide obtained in Step 2 and triethylamine 4 To a mixed solution of 0.0 g and 100 ml of tetrahydrofuran was added 4.17 g of trifluoroacetic anhydride under ice cooling, and the mixture was stirred at room temperature for 30 minutes. After completion of the reaction, 50 ml of water was added to the reaction mixture and extracted with ethyl acetate (50 ml × 3). The obtained organic layer was dehydrated and dried in the order of saturated brine and then anhydrous sodium sulfate, and the solvent was distilled off under reduced pressure. The precipitated solid was filtered, and the obtained solid was washed with 30 ml of diisopropyl ether to obtain 1.89 g of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ 8.10 (t, J = 0.7 Hz, 1 H), 8.02 (d, J = 0.7 Hz, 1 H), 7.89 (dd, J = 7.2, 1.7 Hz, 1 H), 7.19 ( dd, J = 7.2,1.7Hz, 1H).
Step 4: Synthesis of 3-chloro-7-iodoimidazo [1,2-a] pyridine-2-carbonitrile 200 mg of 7-iodoimidazo [1,2-a] pyridine-2-carbonitrile obtained in Step 3 198 mg of N-chlorosuccinimide was added to a mixed solution of 2 ml of N, N-dimethylformamide at room temperature and stirred at 50 ° C. for 1 hour. To the reaction mixture, 198 mg of N-chlorosuccinimide was added at room temperature, and the mixture was stirred at 80 ° C. for 1 hour. After completion of the reaction, 30 ml of water was added to the reaction mixture and extracted with ethyl acetate (10 ml × 3). The obtained organic layer was dehydrated and dried in the order of saturated brine and then 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 0: 100 gradient) to obtain 217 mg of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ 8.09 (d, J = 0.7Hz, 1H), 7.83 (dd, J = 7.2, 0.9Hz, 1H), 7.32 (dd, J = 7.4, 1.5Hz, 1H).
Step 5: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carbonitrile (Production Intermediate No. i-002b) 3-Chloro-7- obtained in Step 4 To a mixed solution of 210 mg of iodoimidazo [1,2-a] pyridine-2-carbonitrile, 89 mg of ethanethiol and 2 ml of N, N-dimethylformamide, 116 mg of sodium bicarbonate was added at room temperature, and the mixture was stirred at room temperature for 1 hour. And stirred at 50 ° C. for 1 hour. To the reaction mixture, 89 mg of ethanethiol and 116 mg of sodium bicarbonate were added at room temperature, and the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, 30 ml of water was added to the reaction mixture and extracted with ethyl acetate (10 ml × 3). The obtained organic layer was dehydrated and dried in the order of saturated brine and then 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 0: 100 gradient) to obtain 144 mg of the objective product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ 8.15 (dd, J = 7.2,0.9Hz, 1H), 8.10 (dd, J = 1.5,0.7Hz, 1H), 7.30 (dd, J = 7.2,1.7Hz, 1H ), 2.84 (q, J = 7.4Hz, 2H), 1.27 (t, J = 7.4Hz, 3H).
Step 6: Synthesis of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carbaldehyde (Production Intermediate No. i-001b) 3− obtained in Step 5 under nitrogen atmosphere To a mixed solution of (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carbonitrile (144 mg) and dichloromethane (5 ml) at −78 ° C., a toluene solution of about 1.0 mol / L diisobutylaluminum hydride (Tokyo) Made by Kasei Kogyo Co., Ltd. The same applies hereinafter.) 0.65 ml was added and stirred at −78 ° C. for 30 minutes. To the reaction mixture, 0.5 ml of a toluene solution of about 1.0 mol / L diisobutylaluminum hydride at −78 ° C. was added and stirred at −78 ° C. for 2 hours. To the reaction mixture, 5 ml of 1 mol / L hydrochloric acid was added at −78 ° C., followed by stirring at room temperature for 1 hour. After completion of the reaction, 10 ml of water was added to the reaction mixture and extracted with dichloromethane (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 0: 100) to obtain 10 mg of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ 10.35 (s, 1H), 8.25 (d, J = 7.4Hz, 1H), 8.14 (dd, J = 1.6,0.8 Hz, 1H), 7.25 (dd, J = 7.2 , 1.7Hz, 1H), 2.86 (q, J = 7.4Hz, 2H), 1.20 (t, J = 7.4Hz, 3H).
Step 7: 2- [3- (Ethylthio) -7-iodoimidazo [1,2-a] pyridin-2-yl] -3-methyl-6- (trifluoromethyl) -3H-imidazo [4,5- b] Synthesis of pyridine (present compound No. 1-018b) 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carbaldehyde obtained in Step 6 10 mg, N ² -methyl To a mixed solution of 5.7 mg of -5- (trifluoromethyl) pyridine-2,3-diamine and 1 ml of N, N-dimethylformamide was added 3.7 mg of sodium bisulfite at room temperature, and 4. Stir for 5 hours. To the reaction mixture, 5 ml of water and 10 ml of 1 mol / L hydrochloric acid were added at room temperature, followed by extraction with ethyl acetate (10 ml). The obtained organic layer was dehydrated and dried in the order of saturated brine and then 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 13 mg of the desired product as a yellow solid.
¹ H-NMR (CDCl ₃ ): δ8.87 (d, J = 1.2Hz, 1H), 8.82 (s, 1H), 8.48 (s, 1H), 8.41 (d, J = 7.2Hz, 1H), 7.51 (d, J = 7.2Hz, 1H), 4.38 (s, 3H), 3.14 (q, J = 7.5Hz, 2H), 1.25 (t, J = 7.5Hz, 3H).
Intermediate Synthesis Example 1: Synthesis of 3- (ethylsulfonyl) -7-iodoimidazo [1,2-a] pyridine-2-carbonitrile (Production Intermediate No. i-002a) Step 1 to Step of Synthesis Example 5 65% by mass of metachloroperbenzoic acid under cooling with ice in a mixed solution of 620 mg of 3- (ethylthio) -7-iodoimidazo [1,2-a] pyridine-2-carbonitrile synthesized by the method 5 and 10 ml of chloroform 1.05 g was added and stirred at room temperature for 16 hours. After completion of the reaction, 20 ml of a 5% by mass aqueous sodium hydrogen sulfite solution was added to the reaction mixture, followed by extraction with chloroform (20 ml × 2). The obtained organic layer was washed with 40 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 precipitated solid was filtered, and the obtained solid was washed with 10 ml of ethyl acetate to obtain 340 mg of the desired product as a light brown solid.
¹ H-NMR (CDCl ₃ ): δ8.63 (dd, J = 7.4, 0.8Hz, 1H), 8.30-8.20 (m, 1H), 7.44 (dd, J = 7.4, 1.8Hz, 1H), 3.37 ( q, J = 7.4Hz, 2H), 1.40 (t, J = 7.4Hz, 3H).
The compound of the present invention can be synthesized according to the above production method and synthesis examples. Examples of fused heterocyclic compounds produced in the same manner as in Synthetic Examples 1 to 5 are shown in Tables 22 and 23, but the fused heterocyclic compounds included in the present invention are not limited to these. Absent.

  In the table, “Me” represents methyl, and “Et” represents ethyl. In the table, “* 1” represents that the compound is solid, and “mp” represents the melting point (unit: ° C.). In the description of the melting point in the table, “>” indicates that the melting point of the compound is higher than the indicated temperature. For example, the indication “> 350” means that the compound did not melt at 350 ° C.

  [Table 22]

―――――――――――――――――――――――――――――
No. R ³ Y1 Y2 Y3 m mp
―――――――――――――――――――――――――――――
1-001a CF ₃ CF ₃ HH 2 140-144
1-001b CF ₃ CF ₃ HH 0 198-199
1-001c CF ₃ CF ₃ HH 1 157-159
1-002a CF ₃ H CF ₃ H 2 * 1
1-002b CF ₃ H CF ₃ H 0 157-159
1-003a CF ₃ H H CF ₃ 2 310-311
1-003b CF ₃ H H CF ₃ 0 166-167
1-003c CF ₃ H H CF ₃ 1 253-256
1-004a CF ₃ H H SO ₂ Me 2> 350
1-005b CF ₃ H H SMe 0 185-187
―――――――――――――――――――――――――――――
[Table 23]

―――――――――――――――――――――――
No. Y7 Y8 n mp
―――――――――――――――――――――――
1-010a FH 2 187-189
1-011a Cl H 2 217-218
1-012a Br H 2 205-207
1-013a IH 2 215-218
1-014a CF ₃ H 2 212-213
1-015a HF 2 170-171
1-016a H Cl 2 214-215
1-017a H Br 2 205-206
1-018a HI 2 208-211
1-018b HI 0 202-205
1-019a H CF ₃ 2 203-205
―――――――――――――――――――――――
Although the example of a manufacturing intermediate for manufacturing the example of this invention compound shown to Table 22 and Table 23 is shown in Table 24 and Table 25, a manufacturing intermediate is not limited only to these. .

  In the table, “Et” represents ethyl. In the table, “* 1” represents that the compound is solid, and “mp” represents the melting point (unit: ° C.).

  [Table 24]

――――――――――――――――――――――――
No. Q1 Y7 Y8 n mp
――――――――――――――――――――――――
i-001a CHO HI 2 199-202
i-001b CHO HI 0 * 1
i-002a CN HI twenty one
i-002b CN HI 0 * 1
i-003a CHO CF ₃ H twenty one
――――――――――――――――――――――――
[Table 25]

―――――――――――――――――――――――――
No. Q2 Z Y7 Y8 mp
―――――――――――――――――――――――――
i-004 CHCl ₂ HHI * 1
i-005 CHO Cl HI 170-171
i-006 CHCl ₂ H CF ₃ H * 1
i-007 CHO Cl CF ₃ H * 1
―――――――――――――――――――――――――
Of the compounds of the present invention shown in Table 22, Table 26 shows the ¹ H-NMR data of compounds without melting point and intermediates i-003a, i-006 and i-007.

[Table 26]
―――――――――――――――――――――――――――――――――――――
No. ¹ H NMR (CDCl ₃ , Me ₄ Si, 300 MHz).
―――――――――――――――――――――――――――――――――――――
1-002a δ9.41 (d, J = 7.8Hz, 1H), 8.76 (brs, 1H), 8.52 (brs, 1H),
8.40-8.20 (m, 3H), 8.00-7.90 (m, 1H), 7.80-7.70 (m, 1H),
7.55-7.45 (m, 1H), 4.18 (s, 3H), 4.12 (q, J = 7.5Hz, 2H),
1.43 (t, J = 7.5Hz, 3H).
i-003a δ10.46 (s, 1H), 9.47 (s, 1H), 7.99 (d, J = 9.6Hz, 1H),
7.70 (dd, J = 9.6,1.5 Hz, 1H), 3.55 (q, J = 7.5Hz, 2H),
1.40 (t, J = 7.5Hz, 3H).
i-006 δ8.49 (s, 1H), 7.93 (s, 1H), 7.71 (d, J = 9.6Hz, 1H),
7.39 (dd, J = 9.6, 1.5 Hz, 1H), 6.93 (s, 1H).
i-007 δ10.23 (s, 1H), 8.56-8.51 (m, 1H), 7.81 (d, J = 9.6Hz, 1H),
7.50 (dd, J = 9.6, 1.5 Hz, 1H).
―――――――――――――――――――――――――――――――――――――
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 (Nilaparvata 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.

  Compounds of the present invention: 1-001a, 1-002b, 1-003b, 1-005b, 1-012a, 1-013a, 1-014a, 1-018a, 1-019a.

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 Plutella 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, 1-001b, 1-002b, 1-003b, 1-003c, 1-005b, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1- 015a, 1-016a, 1-017a, 1-018a, 1-018b, 1-019a.

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 kept 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, 1-001b, 1-001c, 1-002b, 1-003b, 1-003c, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1- 015a, 1-016a, 1-017a, 1-018a, 1-018b, 1-019a.

Test Example 4: Insecticidal test against peach aphid A moist absorbent cotton is laid on a glass petri dish with an inner diameter of 3 cm, and kanran leaves cut out to the same diameter are placed on the glass petri dish. 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 solution was sprayed (2.5 mg / cm ² ) in a rotary spray tower, covered, and stored in a thermostatic chamber at 25 ° C. 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: 1-001a, 1-002b, 1-003b, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1-015a, 1-016a, 1-018a, 1-018a, 1- 018b, 1-019a.

Test Example 5: 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 form a thin film of the compound on the inner wall of the glass container. The inner wall of the used glass container is 35 cm ² , and the treatment drug amount is 10 μg / cm ² . Five first nymphs (mixed male and female) of Rhipicephalus sanguineus were released in the treated glass container, covered, 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.

  Compounds of the present invention: 1-001a, 1-003a, 1-004a, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1-015a, 1-016a, 1-017a, 1- 019a.

Test Example 6: Effect test on cat fleas 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 glass container inner wall. The inner wall of the glass container used is 35 cm ² , and the treatment drug amount is 10 μg / cm ² . Five adult cat fleas (mixed male and female) (mixed male and female) were released into the treated glass container, 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.
Compounds of the present invention: 1-002b, 1-005b, 1-010a, 1-011a, 1-012a, 1-013a, 1-014a, 1-015a, 1-016a, 1-017a, 1-018a, 1-018a, 1- 018b, 1-019a.

  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 (12)

Formula (1):

[ ^Wherein , A ^1a represents a hydrogen atom or C ₁ -C ₆ alkyl,
A ⁴ represents a nitrogen atom or C (R ⁴ ),
A ⁵ represents a nitrogen atom or C (R ⁵ ),
R ¹ represents C ₁ -C ₆ alkyl or halo (C ₁ -C ₆ ) alkyl;
R ² and R ⁵ each independently represent a hydrogen atom or C ₁ -C ₆ alkyl,
R ³ and R ⁴ are each independently a hydrogen atom, a halogen atom, halo (C ₁ -C ₆ ) alkyl, halo (C ₁ -C ₆ ) alkylthio, halo (C ₁ -C ₆ ) alkylsulfinyl or halo. _(C 1 ~C ₆₎ alkyl sulfonyl,
Y6, Y7, Y8 and Y9 are each independently hydrogen atom, halogen _atom, C 1 -C ₆ alkyl, halo _(C 1 _{~C 6) alkyl,} C 1 -C ₆ alkoxy, halo _(C 1 -C _{6) alkoxy,} C 1 -C ₆ alkylthio, halo _(C 1 -C _{6) alkylthio,} C 1 -C ₆ alkylsulfinyl, halo _(C 1 -C _{6) alkylsulfinyl,} C 1 -C ₆ alkylsulfonyl, halo ( C ₁ -C ₆₎ alkylsulfonyl, represents cyano, nitro or G1, G1 represents a structure represented by G1-1,

Y1, Y2, Y3, Y4 and Y5 are independently a hydrogen atom, a halogen _atom, C 3 -C _{6 cycloalkyl,} C 1 -C ₆ alkyl, halo _(C 1 ~C _{6) alkyl, C} 1 ~ C ₆ alkoxy, halo (C ₁ -C ₆ ) alkoxy, C ₁ -C ₆ alkylthio, halo (C ₁ -C ₆ ) alkylthio, C ₁ -C ₆ alkylsulfinyl, halo (C ₁ -C ₆ ) alkylsulfinyl, Represents C ₁ -C ₆ alkylsulfonyl, halo (C ₁ -C ₆ ) alkylsulfonyl, —NH ₂ , —NHR ^{90 g} , cyano or nitro,
R ^90g is 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, C ₁ -C ₆ alkylsulfonyl or halo (C ₁ -C ₆ ) alkylsulfonyl,
n represents an integer of 0, 1 or 2;
m represents an integer of 0, 1 or 2. ] The condensed heterocyclic compound or its salt represented by these, or those N-oxides. A ^1a represents C ₁ -C ₆ alkyl,
A ⁴ represents C (R ⁴ ),
A ⁵ represents a nitrogen atom,
R ¹ represents C ₁ -C ₆ alkyl;
R ² and R ⁴ represent a hydrogen atom,
The condensed heterocyclic compound or a salt thereof, or an N-oxide thereof according to claim ₁ , wherein R ³ represents halo (C ₁ -C ₆ ) alkyl. Y6, Y7 and Y9 represent a hydrogen atom,
Y8 represents G1, Y1 and Y2 are each independently hydrogen atom or a halo _(C 1 _{~C 6)} alkyl,
Y3 represents a hydrogen atom, halo _(C 1 ~C _{6) alkyl,} a C 1 -C ₆ alkylthio or _C 1 -C ₆ alkylsulfonyl,
Y4 and Y5 represent a hydrogen atom,
n represents the integer of 2, The condensed heterocyclic compound of Claim 2 or its salt, or those N-oxides.   The pest control agent which contains as an active ingredient 1 or more types chosen from the condensed heterocyclic compound of any one of Claims 1-3, and its salt.   An agrochemical containing, as an active ingredient, one or more selected from the condensed heterocyclic compound according to any one of claims 1 to 3 and a salt thereof.   The control agent of the inside or ectoparasite of mammals or birds which contains as an active ingredient 1 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-3.   The control agent according to claim 6, wherein the ectoparasite is a flea or a tick.   An insecticide or acaricide containing as an active ingredient at least one selected from the condensed heterocyclic compounds according to any one of claims 1 to 3 and salts thereof.   The soil treatment agent which contains 1 or more types chosen from the condensed heterocyclic compound of any one of Claims 1-3, and its salt as an active ingredient.   The soil treatment agent according to claim 9, wherein the soil treatment is performed by a soil irrigation treatment.   The seed treatment agent which contains as an active ingredient 1 or more types chosen from the condensed heterocyclic compound and its salt of any one of Claims 1-3.   The seed treatment agent according to claim 11, wherein the seed treatment is performed by dipping treatment.